WO2001050110A1 - Procede et appareil de mesure d'une substance chimique - Google Patents

Procede et appareil de mesure d'une substance chimique Download PDF

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Publication number
WO2001050110A1
WO2001050110A1 PCT/JP2000/007499 JP0007499W WO0150110A1 WO 2001050110 A1 WO2001050110 A1 WO 2001050110A1 JP 0007499 W JP0007499 W JP 0007499W WO 0150110 A1 WO0150110 A1 WO 0150110A1
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Prior art keywords
chemical substance
substance
detecting
infrared
detection
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PCT/JP2000/007499
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English (en)
Japanese (ja)
Inventor
Kazuyuki Maruo
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Advantest Corporation
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Publication date
Application filed by Advantest Corporation filed Critical Advantest Corporation
Priority to DE2000184330 priority Critical patent/DE10084330T1/de
Priority to KR1020017011285A priority patent/KR20010103041A/ko
Publication of WO2001050110A1 publication Critical patent/WO2001050110A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods

Definitions

  • the present invention relates to a method and apparatus for detecting a chemical substance such as environmental pollutants existing in the atmosphere or measuring the concentration thereof.
  • a measurement gas is adsorbed on a porous substance such as TENAX, and heated to release the adsorbed chemical substance.
  • identification and quantification method for performing thermal desorption GC- MS: Gas Chromatography- Mass Spectroscopy), etc. are Rere for power s Rereru.
  • FT-IR Fourier Transform Infrared Spectroscopy
  • smoke particles may absorb infrared rays or diffusely reflect, so that a spectrum of a target chemical substance may not be obtained correctly or with high sensitivity.
  • An object of the present invention is to provide a method and an apparatus for detecting a chemical substance that can measure various chemical substances with high sensitivity and in real time, including a chemical substance generated in a form attached to impurity particles such as dioxin. .
  • the object is to decompose a substance to be detected attached to an impurity and decompose a chemical substance specific to the substance to be inspected from the impurity, a chemical substance detecting means to detect the chemical substance, A filter for selectively introducing the chemical substance into the chemical substance detection means, wherein the target substance is indirectly detected based on a result of detection of the chemical substance. Achieved by the device.
  • the object is to provide a chemical substance decomposing means for decomposing a substance to be detected attached to an impurity and desorbing a chemical substance peculiar to the substance to be inspected from the impurity, and a chemical substance detecting means for detecting the chemical substance
  • a chemical substance detection device comprising: detecting a substance to be inspected indirectly based on a detection result of the chemical substance.
  • the chemical substance decomposing means may be an ultraviolet ray generator for irradiating the detection target substance with ultraviolet rays.
  • the chemical substance decomposition means may be a plasma generator for exposing the detection target substance to plasma.
  • the plasma generation device may generate plasma by a high-voltage pulse.
  • the plasma generation device may generate plasma using microwaves.
  • the chemical substance detection unit may include an infrared light source that irradiates an atmosphere containing the chemical substance with infrared light, and an infrared light source that emits infrared light from the atmosphere.
  • An infrared detector for detecting the infrared ray, and the chemical substance may be detected based on the detected absorption amount of the infrared ray.
  • the chemical substance detecting means includes: an infrared transmitting substrate to which the chemical substance is adhered; an infrared light source for emitting infrared light to the infrared transmitting substrate; An infrared detector that detects the infrared light emitted from the infrared transmitting substrate after multiple reflection inside, and the chemical substance may be detected based on the detected absorption amount of the infrared light.
  • the above-mentioned chemical substance detection device may further include an ultraviolet irradiation device for irradiating the infrared transmitting substrate with ultraviolet light to clean the surface of the infrared transmitting substrate.
  • the chemical substance detection means further includes a spectroscopic analyzer for spectrally analyzing the infrared ray detected by the infrared ray detector, and identifies the type of the chemical substance. And / or the amount of the chemical substance may be quantified.
  • the above object is to decompose a detection target substance attached to an impurity, desorb a chemical substance specific to the test target substance from the impurity, detect the desorbed chemical substance, and detect the chemical substance.
  • the present invention is also achieved by a chemical substance detection method characterized by indirectly detecting the test substance based on a result.
  • the desorbed chemical substance may be detected after being separated from the impurities.
  • a target substance for example, dioxin
  • a specific chemical substance generated by the decomposition is selectively introduced into a detection system and detected.
  • the target substance is indirectly detected, so that the target substance can be detected with high sensitivity without being affected by smoke particles.
  • FIG. 1 is a schematic diagram showing the principle of a chemical substance detection method and device according to the present invention.
  • FIG. 2 is a diagram showing an example of a plasma generator applicable to the present invention.
  • FIG. 3 is a diagram showing an example of a Fourier transform infrared spectroscopy apparatus applicable to the present invention.
  • C FIG. 4 is a graph showing an infrared absorption spectrum by a black phenol.
  • FIG. 5 is a schematic diagram showing a chemical substance measuring method and device according to the first embodiment of the present invention.
  • FIG. 6 is a schematic diagram showing a chemical substance measuring method and device according to a second embodiment of the present invention.
  • FIG. 7 is a schematic diagram showing a chemical substance measuring method and device according to a third embodiment of the present invention.
  • FIG. 8 is a schematic diagram showing a chemical substance measuring method and device according to a fourth embodiment of the present invention.
  • FIG. 9 is a schematic diagram showing a chemical substance measuring method and device according to a fifth embodiment of the present invention.
  • FIG. 10 is a schematic diagram showing a chemical substance measuring method and apparatus according to a sixth embodiment of the present invention.
  • FIG. 1 is a schematic diagram showing the principle of the chemical substance detection method and device according to the present invention
  • FIG. 2 is a diagram showing an example of a plasma generator
  • FIG. 3 is a diagram showing an example of a Fourier transform infrared spectrometer
  • FIG. 4 is a graph showing an infrared absorption spectrum by chlorophenol.
  • the chemical substance detection device according to the present invention comprises chemical substance decomposing means 10 for decomposing a substance to be detected attached to impurities and desorbing a specific chemical substance from the substance to be detected.
  • the filter 50 that selects the desorbed specific chemical substance, and the specific chemical substance that has passed through the filter 50 is detected, and the detected specific chemical substance is detected.
  • It has a main feature of having chemical substance detection means 30 for calculating the amount of a substance to be detected attached to an impurity based on the amount of the substance.
  • the present invention will be described with an example in which dioxin generated in a garbage incineration plant or the like is detected.
  • the chemical substance that can be measured by the method and apparatus for detecting a chemical substance according to the present invention is not limited to dioxin, and other environmental pollutants such as structural formulas
  • PCDF Polychlorodibenzofuran
  • Dioxin is formally called polychlorodibenzo-p-dioxin
  • the reaction shown in (Dani 4) is generated by irradiating dioxin with ultraviolet light, and chlorine is eliminated from dioxin by irradiation of ultraviolet light. Therefore, by detecting the eliminated chlorine, dioxin can be indirectly detected.
  • an ultraviolet irradiation light source that irradiates smoke particles with ultraviolet light can be applied.
  • UV irradiation a light source having an energy larger than the binding energy of chlorine of dioxin is applied.
  • an ultraviolet light source such as Xe (xenon) excimer light, a low-pressure mercury lamp having an emission wavelength of 185 nm and 254 nm, and a dielectric barrier discharge excimer lamp having an emission wavelength of 172 nm.
  • Irradiation with light having such energy can dissociate the C—C 1 bond and separate chlorine gas from dioxin adhering to the smoke particles.
  • reaction represented by the reaction formula (Formula 5) is caused by applying plasma energy to dioxin.
  • Dioxin is decomposed by exposing smoke particles to plasma, and a substance called chlorophenol is generated.
  • Chlorophenol is a liquid at normal temperature, but has a boiling point of 1 ⁇ 5 ° C. In a plasma environment, it evaporates and desorbs from smoke particles. Therefore, it is possible to indirectly detect dioxin by detecting the desorbed clonal phenol.
  • a plasma generator as shown in FIG. 2 can be applied as the chemical substance decomposition means 10 for giving plasma energy to dioxin to generate a reaction represented by the reaction formula (Formula 5).
  • plasma is a gas in which there are enough electrons and ions that can move freely, and macroscopically, the total charge is zero.
  • Plasma has a high temperature (electron temperature, ion temperature, gas temperature) because it is generated by electrons bound by atoms gaining energy and ionizing. Therefore, it has been applied to various energy sources such as nuclear fusion, laser, and chemical activation.
  • nitrogen or oxygen in the air is turned into plasma, and this energy is used to decompose and desorb chemical substances in impurities.
  • this energy is used to decompose and desorb chemical substances in impurities.
  • FIG. 2 by providing opposed flat electrodes 20 and 22 and applying a high-voltage AC electric field by a high-voltage AC power supply 24 connected between the electrodes 20 and 22.
  • a plasma 26 can be generated between these electrodes.
  • the energy of the generated plasma is determined by parameters such as power supply voltage and distance between electrodes.
  • the chemical substance detection means 30 detects a specific chemical substance separated from dioxin, for example, chlorine-chlorophenol, and calculates the concentration of dioxin from this concentration.
  • FT-IR Fourier Transform Infrared Spectroscoop
  • FT-II as shown in Fig. 3, in principle, an infrared light source 32 that irradiates the gas to be detected with infrared light, and a spectrometer that detects infrared light passing through the gas to be detected and performs spectral analysis.
  • a spectrometer that detects infrared light passing through the gas to be detected and performs spectral analysis.
  • dicloxin decomposes to produce a clofenphenol, which has the structural formula
  • a detection method may be used in which an infrared ray is incident on the exposed infrared-transmitting crystal substrate, multiple internal reflection is performed inside the substrate, and light emitted from the substrate is detected and spectrally analyzed.
  • Such a detection method is described in detail in, for example, Japanese Patent Application No. 11-231495.
  • FT-IR the amount of a specific chemical substance can be detected as described above, and the type of the chemical substance can be identified or the amount can be calculated.
  • FT_IR For details on the identification and quantification of substances using FT_IR, see, for example, Japanese Patent Application Nos. 11-95583 and 11-2311495. Has been described. Also, FT-IR is described in detail in, for example, “Basic and Actual FT-IR Second Edition”, edited by Mio Takuma (Tokyo Kagaku Dojin).
  • the smoke particles against the molecular weight is about 1 0 6 -1 0 8
  • molecular weight of Daioki Shin class is 3 0 0 about. Therefore, when the smoke particles are directly irradiated with infrared rays, most of the infrared rays are absorbed by the smoke particles, and there is a possibility that the absorption spectrum of dioxin cannot be observed. Therefore, in order to measure dioxin with good sensitivity, it is desirable to measure specific chemical substances separated from dioxin (eg, chlorophenol) after separating them from smoke molecules.
  • a filter 50 is provided between the chemical substance decomposition means 10 and the chemical substance detection means 30 as shown in Fig. 1. It is effective.
  • the decomposition chamber 12 in which the chemical substance decomposition means 10 is installed and the detection chamber 14 in which the chemical substance detection means 30 is installed are separated by a filter 50.
  • the pressure in the decomposition chamber 12 or the negative pressure in the detection chamber 14 with respect to the decomposition chamber 12 allows the gas in the decomposition chamber 12 to flow to the detection chamber 14 through the filter 50. Therefore, as the filter 50, a substance that does not pass through particles having a very high molecular weight such as smoke particles but passes particles having a small molecular weight such as chlorophenol is applied.
  • smoke particles have a diameter of 1 m or more, so apply filters such as those used for oil-repellent dust masks with a mesh roughness of 1 m.
  • an inspection object introducing means 16 for introducing incineration gas into the detection chamber 12 may be provided.
  • an exhaust means 18 for discharging the gas in the detection chamber 14 may be provided.
  • a filter 50 In order to increase the detection sensitivity of dioxin, it is desirable to provide a filter 50.However, the infrared absorption spectrum of a specific chemical substance separated from dioxin, such as low absorption of infrared rays by smoke particles, is sufficient. If the filter 50 can be obtained, it is not always necessary to provide the filter 50.
  • FIG. 5 is a schematic diagram showing the chemical substance measuring method and device according to the present embodiment.
  • the chemical measuring device according to c present embodiment will be described with reference to FIG. 5 chemical measuring device according to the present embodiment, degradation of the analyte (e.g. dioxins) that are contained in the impurities such as waste incineration ash or incineration gas And a detection chamber 14 that detects specific chemical substances obtained by decomposing substances to be measured contained in incinerated gas.
  • the separation chamber 12 and the detection chamber 14 are separated by a filter 50 that blocks substances having a large molecular weight such as smoke particles.
  • the decomposition chamber 12 is provided with an inspection object introduction means 16 for introducing impurities such as incineration ash and incineration gas to be inspected.
  • An ultraviolet light source 28 for decomposing a substance to be measured and desorbing a specific chemical substance is provided in the decomposition chamber 12.
  • the detection chamber 14 has an infrared light source 32 and a spectroscopic analyzer 34 for detecting a specific chemical substance obtained by decomposing a measurement target substance contained in incineration gas.
  • a Fourier transform infrared spectrometer is provided.
  • the detection chamber 14 is also provided with an exhaust means 18 for discharging gas in the detection chamber.
  • the chemical substance detection device uses ultraviolet rays as a chemical substance decomposition means for decomposing a test target substance such as dioxin and desorbing a specific chemical substance.
  • a Fourier transform infrared spectrometer is applied as a chemical substance detection means for detecting a specific chemical substance desorbed from a substance to be inspected by applying a light source 28.
  • impurities such as refuse incineration ash and incineration gas to be inspected are introduced into the decomposition chamber 12 by the inspection object introduction means 16.
  • ultraviolet light is generated from the ultraviolet light source 28 and irradiated to the refuse incineration ash or the incineration gas introduced into the decomposition chamber 12.
  • dioxin adhering to refuse incineration ash or incineration gas is decomposed according to the decomposition reaction of (Chem. 4), and chlorine is generated.
  • the pressure in the decomposition chamber 12 is set to a positive pressure with respect to the detection chamber 14, or the pressure in the detection chamber 14 is set to a negative pressure with respect to the decomposition chamber 12, so that the gas in the decomposition chamber 12 is filled.
  • Filo 50 does not pass through particles having a very high molecular weight, such as smoke particles, but passes only particles having a low molecular weight, such as chlorine, chlorine separated from dioxin is selectively used for smoke particles. Can be introduced into the detection chamber 14.
  • impurities in the detection chamber 14 are analyzed by a Fourier transform infrared spectrometer.
  • Infrared light emitted from the infrared light source 32 of the spectrometer is absorbed in a specific wavelength range by chlorine generated from dioxin. Therefore, the amount of chlorine can be detected by analyzing the infrared absorption spectrum of the infrared light that has passed through the detection chamber 14, and as a result, the presence or absence of dioxin, which is the source of chlorine, or the presence of dioxin Can be calculated.
  • the detection sensitivity does not deteriorate due to the smoke particles.
  • dioxin adsorbed on smoke particles is decomposed, and a specific chemical substance generated thereby is selectively introduced into the detection system and detected.
  • dioxin is detected indirectly, dioxin can be detected with high sensitivity without being affected by smoke particles.
  • the detection system using FT-IR has real-time measurement, the detection time can be significantly reduced as compared with the conventional measurement method using GC-MS.
  • dioxin can be detected in a measurement time of about 10 minutes according to the present invention, while a conventional measurement method requires a measurement time of about one month.
  • the ultraviolet light source 28 is used as the chemical substance decomposing device.
  • a plasma generating device as shown in FIG. 2 may be used.
  • both the infrared light source 32 and the spectroscopic analyzer 34 are placed in the detection chamber 14, but the infrared light source 32 and / or the spectroscopic analyzer 34 are 4 Outside, the infrared light emitted from the infrared light source 3 2 is introduced into the detection chamber 14 through the infrared transmission window, or the infrared light is emitted from the detection chamber 14 through the infrared transmission window, and the spectroscopic analyzer It may be introduced in 34.
  • the infrared ray was analyzed using the spectroscopic analyzer, but it is not always necessary to provide the spectroscopic analyzer.
  • the infrared absorption band of the chemical substance to be detected is clear, if the infrared light in the absorption band is selectively detected, the amount of the chemical substance can be quantified based on the intensity of the detected infrared light. .
  • FIG. 6 is a schematic view showing a chemical substance measuring method and apparatus according to the present embodiment.
  • the chemical substance measuring method according to the present embodiment includes a filter between the decomposition chamber 12 and the detection chamber 14 of the chemical substance measuring apparatus according to the first embodiment shown in FIG.
  • the feature is that 0 is not provided.
  • the filter 50 is used to suppress the introduction of smoke particles having a high molecular weight into the detection chamber 14 and to prevent the detection sensitivity from lowering due to absorption of infrared light, which is the measurement light, by the smoke particles.
  • infrared light which is the measurement light
  • FIG. 7 is a schematic diagram showing the chemical substance measuring method and device according to the present embodiment.
  • the chemical measuring device according to c present embodiment will be described with reference to FIG chemical measuring device according to the present embodiment, degradation of the analyte (e.g. dioxins) that are contained in the impurities such as waste incineration ash or incineration gas And a detection chamber that detects specific chemical substances obtained by decomposing substances to be measured contained in incineration gas.
  • the separation chamber 12 and the detection chamber 14 are separated by a filter 50 that blocks substances having a high molecular weight such as smoke particles.
  • the decomposition chamber 12 is provided with an inspection object introduction means 16 for introducing impurities such as incineration ash and incineration gas to be inspected.
  • a plasma generator for decomposing a substance to be measured contained in refuse incineration ash or incineration gas to generate a plasma for desorbing a specific chemical substance.
  • the plasma generator includes a pair of electrodes 20 and 22 arranged opposite to each other, and a high-voltage AC power supply 24 is connected between the electrodes 20 and 22.
  • the detection chamber 14 has an infrared light source 32 and a spectrometer 34, and is a Fourier transform for detecting a specific chemical substance obtained by decomposing a substance to be measured contained in the incineration gas.
  • An infrared spectrometer is provided.
  • the detection chamber 14 also has gas in the detection chamber 14.
  • An exhaust means 18 for exhausting the gas is provided.
  • the chemical substance detection device applies a plasma generator as a chemical substance decomposition means for decomposing a test substance such as dioxin and desorbing a specific chemical substance, and removes the substance from the test substance.
  • the Fourier transform infrared spectrometer is applied as a chemical substance detecting means for detecting a specific chemical substance separated.
  • dioxin adsorbed on the smoke particles is exposed to the plasma generated by the plasma generation device, and generates chlorophenol by a decomposition reaction of (dani 5). . Therefore, by detecting the amount of chlorophenol thus generated by a Fourier transform infrared spectrometer, the presence or absence of dioxin, which is the source of chlorophenol, or the amount of dioxin can be measured.
  • impurities such as garbage incineration ash and incineration gas to be inspected are introduced into the decomposition chamber 12 from 16 through the means for introducing inspection targets.
  • a plasma generator is used to generate plasma 26 in the decomposition chamber 12 c.
  • an AC voltage having an effective voltage of 10 kV and a frequency of 1 kHz is applied between the electrodes 20 and 22.
  • discharge occurs even at atmospheric pressure, and plasma 26 is generated.
  • dioxin adhering to refuse incineration ash or incineration gas is decomposed according to the decomposition reaction of (dani 5), and chlorophenol is generated.
  • the pressure in the decomposition chamber 12 is set to a positive pressure with respect to the detection chamber 14, or the pressure in the detection chamber 14 is set to a negative pressure with respect to the decomposition chamber 12, so that the gas in the decomposition chamber 12 is filled. It flows to the detection chamber side through 0.
  • Filo 50 does not pass through particles having a very high molecular weight such as smoke particles, but only through particles having a small molecular weight such as phenol, so that chlorophenol separated from dioxin is converted into smoke particles. In contrast, it can be selectively introduced into the detection chamber 14.
  • impurities in the detection chamber 14 were analyzed by a Fourier transform infrared spectrometer.
  • U Infrared light emitted from the infrared light source 32 of the spectrometer is absorbed in a specific wavelength range by chlorophenol generated from dioxin. Therefore, the amount of black phenol can be detected by analyzing the infrared absorption spectrum, and as a result, the amount of dioxin, which is the source of black phenol, can be calculated.
  • the detection sensitivity does not deteriorate due to the smoke particle.
  • dioxin adsorbed on smoke particles is decomposed, and a specific chemical substance generated thereby is selectively introduced into the detection system and detected.
  • dioxin is detected indirectly, dioxin can be detected with high sensitivity without being affected by smoke particles.
  • the detection system using FT-IR has real-time measurement, the detection time can be significantly reduced as compared with the conventional measurement method using GC-MS.
  • dioxin can be detected in a measurement time of about 10 minutes according to the present invention, while a conventional measurement method requires a measurement time of about one month.
  • a plasma generation device as shown in FIG. 2 is used as the chemical substance decomposition device, but an ultraviolet light source 28 may be applied as in the first embodiment. Further, another plasma generator can be applied.
  • FIG. 8 is a schematic diagram showing a chemical substance measuring method and apparatus according to the present embodiment.
  • the chemical substance measuring method according to the present embodiment employs a filter 50 between the decomposition chamber 12 and the detection chamber 14 of the chemical substance measuring apparatus according to the third embodiment shown in FIG.
  • the feature is that it is not provided.
  • the filter 50 suppresses the introduction of smoke particles having a high molecular weight into the detection chamber 14 and prevents the detection sensitivity from lowering due to absorption of infrared light, which is the measurement light, by the smoke particles. It is necessary to provide a filter 50 when sufficient infrared absorption spectrum by chlorine separated from dioxin can be obtained, for example, due to little infrared absorption by smoke particles. Absent. By configuring the chemical substance measuring device in this way, the device configuration can be simplified.
  • FIG. 9 is a schematic diagram showing the chemical substance measuring method and device according to the present embodiment.
  • the chemical substance measuring apparatus decomposes a substance to be measured (for example, dioxin) contained in impurities such as refuse incineration ash and incineration gas to desorb a specific chemical substance (for example, chlorophenol). And a detection chamber 14 for detecting a specific chemical substance obtained by decomposing a substance to be measured contained in the incineration gas, and a space between the decomposition chamber 12 and the detection chamber 14 for smoke particles is provided. It is separated by a filter 50 that blocks such high molecular weight substances.
  • a substance to be measured for example, dioxin
  • impurities such as refuse incineration ash and incineration gas
  • a specific chemical substance for example, chlorophenol
  • the decomposition chamber 12 is provided with an inspection object introduction means 16 for introducing impurities such as incineration ash and incineration gas to be inspected.
  • the decomposition chamber 12 is provided with a plasma generator for decomposing a substance to be measured contained in refuse incineration ash or incineration gas to generate plasma for desorbing a specific chemical substance.
  • the plasma generator includes a pair of electrodes 20 and 22 arranged opposite to each other, and a high-voltage AC power supply 24 is connected between the electrodes 20 and 22.
  • an infrared transmitting substrate 40 for adsorbing a chemical substance introduced into the detecting chamber 14 for use in the measurement and a substance adhering to the surface of the infrared transmitting substrate 40 are removed.
  • An ultraviolet light source 42 for initializing the surface state, an infrared light source 32 for entering infrared light into the infrared transmitting substrate 40 and performing multiple internal reflection, and an inside of the infrared transmitting substrate 40 The transmitted infrared rays emitted after multiple reflections are spectrally analyzed and attached to the infrared transmitting substrate 40.
  • a spectrometer 34 for detecting chemical substances is provided.
  • the detection chamber 14 is provided with an exhaust means 18 for discharging gas in the detection chamber 14.
  • the chemical substance detection device applies a plasma generator as a chemical substance decomposition means for decomposing a test substance such as dioxin and desorbing a specific chemical substance, and removes the substance from the test substance.
  • a multiple internal reflection FT-IR device is applied as a chemical substance detection means for detecting a specific chemical substance separated.
  • the detection sensitivity of the chemical substance introduced into the detection chamber 14 can be greatly increased.
  • the infrared transmitting substrate 40 is for adsorbing the chemical substance to be measured and providing it for measurement, and is a material that transmits light in a wavelength range corresponding to the molecular vibration of the substance to be measured. It is necessary to be. Wavenumber range corresponding to the basic vibration of organic substances which are typical contaminants, 5 00 cm- 1 (wavelength 2 O ju) ⁇ 5 000 c ⁇ 1 ( wavelength 2 jm) about the infrared and near-infrared region It is. Therefore, the material constituting the infrared transmitting substrate 40 is selected from a group of infrared transmitting substances that can transmit light in the wavenumber range (wavelength range). For example, zinc selenide (ZnSe) has a transmission wavelength range of about 0.6 to 13 0m, which is an extremely wide infrared transmission wavelength range, and constitutes the infrared transmission substrate 40. It can be selected as one material.
  • ZnSe zinc selenide
  • the inclination of the end face is desirably set to 45 °.
  • the efficiency of incidence of infrared light into the infrared transmitting substrate 40 can be increased, and the infrared light can be reflected multiple times inside the infrared transmitting substrate 40.
  • a substrate having an edge shape such as 300 mm silicon wafer can be applied.
  • Other materials that can constitute the infrared transmitting substrate 40 include, for example, gallium arsenide (Ga As: transmission wavelength range 1.0 to 18 m), silicon (S i: transmission wavelength range 1.2 to 6 jm).
  • Potassium bromide (KBr: transmission wavelength range 0.4 to 22 ⁇ m), chlorinated lithium (KC1: transmission wavelength range 0.3 to 15 ⁇ m), barium fluoride (BaF) 2 : Transmission wavelength range 0.2 to 5 ⁇ m), cesium bromide (CsBr: Transmission wavelength range 0.5 to 30 ⁇ m), germanium (Ge: Transmission wavelength range 2 to 18 ⁇ m) ), full Uz lithium (L i:?
  • transmission wavelength range from 0.2 to 5 ⁇ 111), calcium fluoride (C aF 2: transmission wavelength range 0.5 2 ⁇ 8 ⁇ M), sapphire (A 1 2 0 3 : Transmission wavelength range 0.3 to 5 ⁇ m), Cesium iodide (CsI: Transmission wavelength range 0.5 to 28 rn), magnesium fluoride (MgF 2: Transmission wavelength range 0.2 to 6 ⁇ ) m), thallium bromide (KRS-5: transmission wavelength range 0.6 to 28 jum), zinc sulfide (ZnS: transmission wavelength range) 0.7 to 1 lm).
  • CsI Transmission wavelength range 0.5 to 28 rn
  • MgF 2 Transmission wavelength range 0.2 to 6 ⁇
  • KRS-5 transmission wavelength range 0.6 to 28 jum
  • ZnS transmission wavelength range
  • the infrared light source 32 a light source that emits infrared light in a band of 2 to 25 m corresponding to molecular vibration of organic molecules can be applied.
  • a silicon carbide (SiC) as a filament or a hot wire generated by applying a current to a nichrome wire can be used as a light source.
  • a reflecting plate having an appropriate shape may be provided to increase the efficiency of the light source and increase the intensity of infrared light.
  • various infrared light sources described in Japanese Patent Application No. 11-95853 by the same applicant can be applied.
  • the frequency component of the light (evanescent light) that exudes when the light is reflected on the substrate surface matches the molecular vibration frequency of the contaminant on the substrate surface. Is absorbed by resonance. Therefore, the information of the substrate surface state is reflected on the infrared rays by multiple reflection of the incident infrared rays inside the infrared transmitting substrate 40.
  • the type and amount of the organic pollutant can be specified.
  • FIG. 4 is a graph showing an absorption spectrum obtained by performing Fourier transform spectroscopy on infrared light detected after multiple internal reflections on the infrared transmitting substrate 40 to which chlorophenol is attached.
  • a beak is observed in the wavenumber range corresponding to the molecular vibration of a specific organic contaminant, so that it can be identified as a black phenol, and the amount of the attached phenol must be calculated from the peak intensity. Can be.
  • chlorophenol adheres to the surface of the infrared-transmitting substrate 40 with a size of about 5 ⁇ 10 11 molecules Z cm 2 or more, it should be detected as an absorption spectrum as shown in FIG. Was completed.
  • an infrared spectrometer using a diffraction grating may be used instead of the FT-IR device.
  • the chemical substance detection device measures contaminants in an environmental atmosphere such as incineration ash and incineration gas by identifying and quantifying chemical substances adsorbed on the surface of the infrared transmitting substrate 40.
  • an environmental atmosphere such as incineration ash and incineration gas
  • the amount of contaminants adsorbed on the infrared transmitting substrate 40 saturates over time. Therefore, when it is necessary to investigate changes in the concentration of contaminants in the air over a long period of time, a cleaning step is required to periodically remove the contaminants attached to the surface of the infrared transmitting substrate 40.
  • an ultraviolet light source 42 is provided as a means for cleaning the chemical substance adsorbed on the substrate.
  • the ultraviolet light source 42 is for dissociating and evaporating a chemical substance attached to the surface of the infrared transmitting substrate 40, and is a light source that generates light having energy larger than the binding energy of the attached chemical substance.
  • ultraviolet light sources such as Xe (xenon) excimer light, low-pressure mercury lamps having emission wavelengths of 185 nm and 254 nm, and dielectric barrier discharge excimer lamps having an emission wavelength of 172 nm are used. Can be applied. Irradiation with light having such energy can dissociate organic contaminants such as C—C, C—H, and C—O, and remove or evaporate them from the surface of the infrared transmitting substrate 10.
  • a reflecting mirror (not shown) for efficiently irradiating the ultraviolet light emitted from the ultraviolet light source 42 to the infrared transmitting substrate 40 may be provided.
  • a reflecting mirror having an elliptical cross-sectional shape as described in Japanese Patent Application No. 111-213495, the ultraviolet light emitted from the ultraviolet light source 42 can be applied. Irradiation can be efficiently performed on both surfaces of the infrared transmitting substrate 40.
  • the spectrum measurement data obtained by the spectrometer is sent to the calculation and display means, where the identification of the chemical substance and the calculation of the quantity are performed.
  • the types of chemical substances and the calibration curves are stored separately in the storage unit of the calculation and display means as a database, and the measurement data is quantified by referring to those data.
  • the calculation and display means stores, as a database, the relationship between the amount of the chemical substance adsorbed on the surface of the infrared transmitting substrate 40 and the amount of the contaminant in the environmental atmosphere.
  • the concentration of the contaminant in the environmental atmosphere can be calculated from the amount of the contaminant on the surface of the substrate 40.
  • the result analyzed in this way can be displayed on a display device (not shown) as necessary.
  • impurities such as garbage incineration ash and incineration gas to be inspected are introduced into the decomposition chamber 12 from 16 through the means for introducing inspection targets.
  • a plasma generator is used to generate plasma 26 in the decomposition chamber 12 c.
  • an AC voltage having an effective voltage of 10 kV and a frequency of 1 kHz is applied between the electrodes 20 and 22.
  • discharge occurs even at atmospheric pressure, and plasma 26 is generated.
  • dioxin adhering to refuse incineration ash or incineration gas is decomposed according to the decomposition reaction of (Dani 5), and phenol is generated.
  • the pressure in the decomposition chamber 12 is set to a positive pressure with respect to the detection chamber 14, or the pressure in the detection chamber 14 is set to a negative pressure with respect to the decomposition chamber 12, so that the gas in the decomposition chamber 12 is filled.
  • Filo 50 does not pass through particles with very high molecular weight, such as smoke particles, but only through particles with low molecular weight, such as black mouth phenol, so the black mouth phenol separated from dioxin can be converted into smoke particles. To Then, it can be selectively introduced into the detection chamber 14.
  • the black phenol introduced into the detection chamber 14 is adsorbed on the surface of the infrared transmitting substrate 40 placed in the detection chamber 14.
  • multiple internal reflections are performed, and at the same time, information on the phenolic phenol adsorbed on the surface of the infrared transmitting substrate 40 is accumulated and probed, and emitted outside the infrared transmitting substrate 40.
  • the chlorophenol is quantified by calculation and display means (not shown), and the amount of chlorophenol is determined from the amount of chlorophenol. Calculate the presence or absence of dioxin, the source of dioxin.
  • the detection sensitivity does not deteriorate due to the smoke particle.
  • the ultraviolet light emitted from the ultraviolet light source 42 is applied to the infrared transmitting substrate 40 to remove contaminants adsorbed on the surface of the infrared transmitting substrate 40, and the substrate surface is removed. Is initialized.
  • dioxin adsorbed on smoke particles is decomposed, and a specific chemical substance generated thereby is selectively introduced into the detection system and detected.
  • dioxin is detected indirectly, dioxin can be detected with high sensitivity without being affected by smoke particles.
  • the detection system using FT-IR since the detection system using FT-IR has real-time measurement, the detection time can be significantly reduced compared to the conventional measurement method using GC-MS. According to a typical measurement example, the conventional measurement method requires a measurement time of about one month, whereas the present invention can detect dioxin in a measurement time of about 10 minutes. It can be carried out. Also, since multiple internal reflection FT-IR is applied to the detection system, the detection sensitivity of dioxin can be greatly improved.
  • a plasma generation device as shown in FIG. 2 is used as the chemical substance decomposition device, but an ultraviolet light source 28 may be applied as in the first embodiment. Further, another plasma generator can be applied.
  • the infrared ray was analyzed using the spectroscopic analyzer, but it is not always necessary to provide the spectroscopic analyzer.
  • the infrared absorption band of the chemical substance to be detected is clear, if the infrared light in the absorption band is selectively detected, the amount of the chemical substance can be quantified based on the intensity of the detected infrared light. .
  • FIG. 10 is a schematic diagram showing a chemical substance measuring method and apparatus according to the present embodiment.
  • the chemical substance measuring method according to the present embodiment comprises a filter 50 between the decomposition chamber 12 and the detection chamber 14 of the chemical substance measuring apparatus according to the fifth embodiment shown in FIG.
  • the feature is that it is not provided.
  • the filter 50 is used to suppress the introduction of smoke particles having a high molecular weight into the detection chamber 14 and to prevent the detection sensitivity from lowering due to absorption of infrared light, which is the measurement light, by the smoke particles.
  • infrared light which is the measurement light
  • the method and apparatus for detecting a chemical substance according to the present invention decomposes a substance to be measured, selectively introduces a specific chemical substance generated thereby into a detection system, and detects the specific chemical substance.
  • Chemical substance detection method and apparatus for measuring various chemical substances including dioxins and other chemical substances generated in the form attached to impurity particles with high sensitivity and real time Useful for

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Abstract

L'invention porte sur un appareil de mesure d'une substance chimique qui comprend un organe (10) de décomposition, la substance à mesurer adhérant à une impureté étant décomposée et convertie en une substance chimique caractéristique de la substance à mesurer ; un organe (30) de mesure et un filtre (50) à travers lequel la substance chimique est introduite sélectivement dans l'organe de mesure (30) et qui mesure indirectement la substance en fonction du résultat de la mesure de la substance chimique. L'appareil peut être utilisé pour réaliser la mesure en temps réel, avec une haute sensibilité des diverses substances chimiques, y compris une substance chimique se présentant sous forme d'une partie adhérée à une impureté telle que la dioxine.
PCT/JP2000/007499 2000-01-06 2000-10-26 Procede et appareil de mesure d'une substance chimique WO2001050110A1 (fr)

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DE2000184330 DE10084330T1 (de) 2000-01-06 2000-10-26 Nachweisverfahren und -vorrichtung für chemischen Stoff
KR1020017011285A KR20010103041A (ko) 2000-01-06 2000-10-26 화학물질 검출 방법 및 장치

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JP2000000963A JP2001194306A (ja) 2000-01-06 2000-01-06 化学物質検出方法及び装置
JP2000/963 2000-01-06

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106248560A (zh) * 2016-10-09 2016-12-21 杨继新 二噁英在线检测装置
WO2020200980A1 (fr) 2019-04-04 2020-10-08 Richter Gedeon Nyrt. Amélioration de la chromatographie d'affinité d'immunoglobulines au moyen d'une floculation de pré-capture

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002168776A (ja) * 2000-12-01 2002-06-14 Advantest Corp 環境モニタ方法及び装置並びに半導体製造装置
DE102005035932A1 (de) * 2005-07-28 2007-02-08 Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG Optischer Sensor für in-situ Messungen

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57111435A (en) * 1980-12-27 1982-07-10 Horiba Ltd Measuring device for absorption intensity of infrared ray by atr method
US4630464A (en) * 1984-06-14 1986-12-23 Kernforschungszentrum Karlsruhe Gmbh Method for the continuous surveillance of the poison content of exhaust gases containing particulate matter
EP0447158A2 (fr) * 1990-03-13 1991-09-18 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Revenue Détecteur pour explosifs cachés et substances narcotiques
JPH07218494A (ja) * 1994-02-01 1995-08-18 Takuma Co Ltd ダイオキシンの測定分析方法及びその装置
JPH08313430A (ja) * 1995-05-18 1996-11-29 Nippon Telegr & Teleph Corp <Ntt> ガスセンサ
JPH09243601A (ja) * 1996-03-07 1997-09-19 Nkk Corp 排ガス中の微量有機化合物の測定装置
JPH10153591A (ja) * 1996-11-20 1998-06-09 Nkk Corp ダイオキシン類の分析方法
JPH10230120A (ja) * 1997-02-20 1998-09-02 Honda Motor Co Ltd 集じん装置の集じん効率測定装置
JPH112607A (ja) * 1997-06-13 1999-01-06 Nec Corp 大気中微量不純物の分析方法
JPH11281540A (ja) * 1998-01-28 1999-10-15 Miura Co Ltd ダイオキシン類の採取装置

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57111435A (en) * 1980-12-27 1982-07-10 Horiba Ltd Measuring device for absorption intensity of infrared ray by atr method
US4630464A (en) * 1984-06-14 1986-12-23 Kernforschungszentrum Karlsruhe Gmbh Method for the continuous surveillance of the poison content of exhaust gases containing particulate matter
EP0447158A2 (fr) * 1990-03-13 1991-09-18 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Revenue Détecteur pour explosifs cachés et substances narcotiques
JPH07218494A (ja) * 1994-02-01 1995-08-18 Takuma Co Ltd ダイオキシンの測定分析方法及びその装置
JPH08313430A (ja) * 1995-05-18 1996-11-29 Nippon Telegr & Teleph Corp <Ntt> ガスセンサ
JPH09243601A (ja) * 1996-03-07 1997-09-19 Nkk Corp 排ガス中の微量有機化合物の測定装置
JPH10153591A (ja) * 1996-11-20 1998-06-09 Nkk Corp ダイオキシン類の分析方法
JPH10230120A (ja) * 1997-02-20 1998-09-02 Honda Motor Co Ltd 集じん装置の集じん効率測定装置
JPH112607A (ja) * 1997-06-13 1999-01-06 Nec Corp 大気中微量不純物の分析方法
JPH11281540A (ja) * 1998-01-28 1999-10-15 Miura Co Ltd ダイオキシン類の採取装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106248560A (zh) * 2016-10-09 2016-12-21 杨继新 二噁英在线检测装置
WO2020200980A1 (fr) 2019-04-04 2020-10-08 Richter Gedeon Nyrt. Amélioration de la chromatographie d'affinité d'immunoglobulines au moyen d'une floculation de pré-capture

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