WO2020230775A1 - 試料分析装置 - Google Patents

試料分析装置 Download PDF

Info

Publication number
WO2020230775A1
WO2020230775A1 PCT/JP2020/018928 JP2020018928W WO2020230775A1 WO 2020230775 A1 WO2020230775 A1 WO 2020230775A1 JP 2020018928 W JP2020018928 W JP 2020018928W WO 2020230775 A1 WO2020230775 A1 WO 2020230775A1
Authority
WO
WIPO (PCT)
Prior art keywords
sample
gas
signal
component
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/018928
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
井上　貴仁
内原　博
享司 渋谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Horiba Ltd
Original Assignee
Horiba Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Horiba Ltd filed Critical Horiba Ltd
Priority to US17/611,471 priority Critical patent/US12111254B2/en
Priority to CN202080034715.2A priority patent/CN113811758A/zh
Priority to JP2021519434A priority patent/JP7461937B2/ja
Priority to EP20805409.8A priority patent/EP3957979B1/en
Publication of WO2020230775A1 publication Critical patent/WO2020230775A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G01J3/10—Arrangements of light sources specially adapted for spectrometry or colorimetry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/42—Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
    • G01J3/433—Modulation spectrometry; Derivative spectrometry
    • G01J3/4338—Frequency modulated spectrometry
    • 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
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • 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
    • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • G01N21/274—Calibration, base line adjustment, drift correction
    • 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
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • 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
    • G01N2021/3129—Determining multicomponents by multiwavelength 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
    • G01N21/3504—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
    • G01N21/3518—Devices using gas filter correlation techniques; Devices using gas pressure modulation techniques

Definitions

  • the present invention relates to a sample analyzer that analyzes a component to be measured contained in a sample.
  • Patent Document 1 As for analyzing carbon (C) and sulfur (S) in a solid sample such as steel, non-ferrous metal, ceramics or coke, as shown in Patent Document 1, a solid sample housed in a pot is used as a combustion furnace. Analyze carbon dioxide (CO 2 ), carbon monoxide (CO), and sulfur dioxide (SO 2 ) contained in the combustion gas generated from the solid sample by burning inside with a non-dispersion infrared absorption (NDIR) analyzer. There is something.
  • CO 2 carbon dioxide
  • CO carbon monoxide
  • SO 2 sulfur dioxide
  • an infrared lamp In the analysis of a solid sample using this NDIR analyzer, an infrared lamp is used, and since the infrared lamp emits broad infrared light including the absorption wavelength range of the component to be measured, the component to be measured In order to measure the density, it is necessary to provide a wavelength selection filter in front of the photodetector. By providing this wavelength selection filter, the amount of light detected by the photodetector decreases, and the SN ratio deteriorates. As a result, the analysis accuracy of the component to be measured deteriorates, especially in the low concentration region.
  • Patent Document 2 there is a method of measuring the SO 2 concentration contained in the combustion gas by using the ultraviolet fluorescence method.
  • the ultraviolet fluorescence method which is more sensitive than infrared absorption, SO 2 can be analyzed accurately even in a low concentration region.
  • the ultraviolet light source using the ultraviolet fluorescence method has a problem that the amount of light tends to decrease due to aged deterioration, the ultraviolet light source needs to be replaced frequently, and maintenance is frequently performed.
  • the present invention has been made to solve the above-mentioned problems, and its main object is to be able to reliably analyze the component to be measured while reducing the frequency of maintenance in the sample analyzer.
  • the sample analyzer is a heating furnace that heats the sample held by the sample holder that holds the sample, and gas analysis that analyzes the components to be measured contained in the gas generated by heating the sample.
  • the gas analysis unit includes a laser light source for irradiating the gas with a laser beam, and a light detector for detecting the intensity of the sample light transmitted by the laser beam through the gas. ..
  • the gas analyzer is equipped with a laser light source that irradiates the gas with laser light and an optical detector that detects the intensity of the sample light that the laser light has passed through the gas.
  • a laser light source that irradiates the gas with laser light
  • an optical detector that detects the intensity of the sample light that the laser light has passed through the gas.
  • the laser light source emits modulated light whose wavelength is modulated at a predetermined modulation frequency.
  • the component to be measured can be analyzed by a wavelength modulation method (WMS: Wavelength Modulation Spectroscopy) using an intensity-related signal obtained by emitting modulated light whose wavelength is modulated at a predetermined modulation frequency. ..
  • WMS Wavelength Modulation Spectroscopy
  • the gas analysis unit uses an intensity-related signal related to the intensity of the sample light and a feature signal obtained by obtaining a predetermined correlation with the intensity-related signal, and uses a representative value depending on the concentration of the component to be measured. It is desirable to further include a first calculation unit for calculating the above, and a second calculation unit for calculating the concentration of the component to be measured using the representative value obtained by the first calculation unit.
  • a representative value depending on the concentration of the component to be measured is calculated from the intensity-related signal related to the intensity of the sample light, and the concentration of the component to be measured is calculated using the representative value.
  • the first calculation unit calculates a sample correlation value which is a correlation value between the intensity-related signal and the feature signal as the representative value
  • the second calculation unit calculates the sample correlation value. It is desirable to use it to calculate the concentration of the component to be measured.
  • calculating the correlation value includes taking the inner product of the intensity-related signal and the feature signal in addition to obtaining the correlation between the intensity-related signal and the feature signal. With such a configuration, the sample correlation value between the intensity-related signal related to the intensity of the sample light and the feature signal is calculated, and the concentration of the component to be measured is calculated using the calculated sample correlation value.
  • the characteristics of the absorbed signal can be captured with dramatically fewer variables without converting the signal into an absorption spectrum, and the concentration of the component to be measured can be measured by a simple calculation without complicated spectrum calculation processing.
  • the concentration of the component to be measured can be measured by a simple calculation without complicated spectrum calculation processing.
  • the number of data points used in general spectrum fitting is required to be several hundred, but in the present invention, the concentration can be calculated with the same accuracy by using a few to several tens of correlation values at most.
  • the load of arithmetic processing can be dramatically reduced, an advanced arithmetic processing apparatus becomes unnecessary, the cost of the analyzer can be reduced, and the size can be reduced.
  • the sample analyzer of the present invention analyzes a plurality of measurement target components contained in the gas, and a plurality of the laser light sources are provided, and the plurality of laser light sources are provided with different measurement target components. It is desirable that the laser beam of the corresponding oscillation wavelength is emitted.
  • the plurality of measurement target components are at least one of CO 2 , CO, SO 2 , H 2 O, and NO X.
  • a dehydrating agent for removing the water contained in the gas is provided on the upstream side of the NDIR analyzer. Since it is not necessary to use an NDIR analyzer in the sample analyzer of the present invention, it is not necessary to provide a dehydrating agent on the upstream side of the gas analyzer. Therefore, in the sample analyzer of the present invention, the heating furnace and the gas analysis unit are connected to further provide a gas flow path for introducing the gas from the heating furnace into the gas analysis unit without dehydrating it with a dehydrating agent. It is desirable to prepare. With this configuration, the dehydrating agent can be eliminated, and the maintenance of periodically replacing the dehydrating agent can be eliminated. Further, since the dehydrating agent can be eliminated, the apparatus configuration can be simplified.
  • the sample analyzer of the present invention further includes an analyzer (NDIR analyzer) using a non-dispersive infrared absorption method in addition to the gas analyzer.
  • an analyzer NDIR analyzer
  • the measurement range can be expanded.
  • the sample analyzer 100 of the present embodiment analyzes carbon and sulfur in a sample of steel, non-ferrous metal, ceramics or coke, organic matter, minerals, heavy oil and the like.
  • a metal analyzer that analyzes carbon and sulfur in the solid sample W will be described.
  • the sample analyzer 100 burns the solid sample W in an oxygen stream and analyzes the component to be measured contained in the gas generated by the combustion by using the infrared absorption method, which is shown in FIG.
  • the heating furnace 2 that heats the container R that houses and holds the solid sample W to burn the solid sample W
  • the gas analysis unit that analyzes the components to be measured contained in the gas generated by the combustion of the solid sample W. It has 3 and.
  • the container R of the present embodiment which is a sample holder, is called a crucible made of a magnetic material such as ceramics.
  • the heating furnace 2 has a heating space 2S in which a container R containing a solid sample W is arranged, and oxygen gas (O 2 ) is supplied to the heating space 2S as a carrier gas. Therefore, the carrier gas supply path 4 is connected to the heating furnace 2. Further, the carrier gas supply path 4 is provided with a carrier gas purifier 42 for purifying the carrier gas (oxygen gas) from the gas cylinder 41. If the carrier gas of the gas cylinder 41 is a clean gas, the carrier gas purifier 42 may be omitted. Further, the carrier gas supply path 4 may be provided with a flow rate regulator 45 such as an on-off valve 43 and a pressure regulating valve 44, for example, a capillary, if necessary.
  • a flow rate regulator 45 such as an on-off valve 43 and a pressure regulating valve 44, for example, a capillary, if necessary.
  • the heating furnace 2 is of a high frequency induction heating furnace type, and is provided with a heating mechanism 5 for high frequency induction heating of the solid sample W in the container R arranged in the heating space 2S.
  • the heating mechanism 5 has a coil 51 and a power supply (not shown) that applies a high-frequency AC voltage to the coil 51.
  • the coil 51 is provided by winding along the side peripheral wall of the heating furnace 2. Further, the coil 51 is provided at a height position surrounding the container R arranged in the heating space 2S.
  • an induced current flows near the surface of the solid sample W housed in the container R made of a magnetic material, and the solid sample W generates Joule heat. Then, a combustion reaction by oxygen occurs with heat generation, and the solid sample W is burned to generate gas (hereinafter, also referred to as sample gas).
  • the solid sample W may be housed together with the solid sample W in the container R, an induced current may be passed through the combustion assisting material, and the solid sample W may be heated by the combustion assisting material.
  • the sample gas generated by the heating furnace 2 is introduced into the gas analysis unit 3 through the gas flow path 6.
  • One end of the gas flow path 6 is connected to the heating furnace 2, and a dust filter 61 and a gas analysis unit 3 are provided from the upstream side of the flow path.
  • the other end of the gas flow path 6 is open to the atmosphere.
  • a pressure regulating valve 62 and a flow rate regulator 63 such as a capillary are provided between the dust filter 61 and the gas analysis unit 3, but these are not essential configurations.
  • a flow rate regulator 64 such as a capillary and a flow meter 65 are provided on the downstream side of the gas analysis unit 3, but these are also not essential configurations.
  • the gas flow path 6 of the present embodiment is not provided with a dehumidifier, for example, 100 is provided by the heating mechanism 6H up to at least the gas analysis unit 3 in order to prevent dew condensation of water contained in the sample gas. It has been heated above ° C. At least the dust filter 61 is also heated to 100 ° C. or higher by this heating mechanism 6H.
  • the gas analysis unit 3 is a concentration measuring device for measuring the concentration of the component to be measured (here, for example, CO, CO 2 or SO 2 ) contained in the sample gas, and as shown in FIG. 2, the sample gas is introduced.
  • the cell 11 is made of a transparent material such as quartz, calcium fluoride, or barium fluoride, which absorbs almost no light in the absorption wavelength band of the component to be measured, and has an inlet and an outlet for light. Although not shown, the cell 11 is provided with an inlet port for introducing the sample gas into the inside and an outlet port for discharging the sample gas inside, and the sample gas is a cell from the inlet port. It is introduced into 11 and sealed.
  • the semiconductor laser 12 is a quantum cascade laser (QCL: Quantum Cascade Laser), which is a kind of semiconductor laser 12, and oscillates a mid-infrared (4 to 12 ⁇ m) laser beam.
  • the semiconductor laser 12 can modulate (change) the oscillation wavelength by a given current (or voltage). As long as the oscillation wavelength is variable, another type of laser may be used, and the temperature may be changed in order to change the oscillation wavelength.
  • the photodetector 13 uses a relatively inexpensive thermal type photodetector such as a thermopile, but other types such as quantum photoelectric devices such as HgCdTe, InGaAs, InAsSb, and PbSe with good responsiveness are used. An element may be used.
  • the signal processing device 14 includes an analog electric circuit composed of a buffer, an amplifier, etc., a digital electric circuit composed of a CPU, a memory, etc., and an AD converter, a DA converter, etc. that mediate between the analog / digital electric circuits.
  • a light source control unit 15 and an optical detector that control the output of the semiconductor laser 12 by cooperating with a CPU and its peripheral devices according to a predetermined program stored in a predetermined area of the memory. It exhibits a function as a signal processing unit 16 that receives an output signal from 13 and calculates the value thereof to calculate the concentration of the component to be measured.
  • the light source control unit 15 controls the current source (or voltage source) of the semiconductor laser 12 by outputting a current (or voltage) control signal. Specifically, the light source control unit 15 changes the drive current (or drive voltage) of the semiconductor laser 12 at a predetermined frequency, and modulates the oscillation wavelength of the laser light output from the semiconductor laser 12 at a predetermined frequency with respect to the center wavelength. .. As a result, the semiconductor laser 12 emits modulated light modulated at a predetermined modulation frequency.
  • the light source control unit 15 changes the drive current in a triangular wave shape and modulates the oscillation frequency in a triangular wave shape (see “oscillation wavelength” in FIG. 5).
  • the drive current is modulated by another function so that the oscillation frequency has a triangular wave shape.
  • the oscillation wavelength of the laser light is modulated with the peak of the light absorption spectrum of the component to be measured as the center wavelength.
  • the light source control unit 15 may change the drive current into a sinusoidal shape, a sawtooth shape, or an arbitrary function shape, and modulate the oscillation frequency into a sinusoidal shape, a sawtooth shape, or an arbitrary function shape.
  • the signal processing unit 16 includes a logarithmic calculation unit 161, a correlation value calculation unit (first calculation unit) 162, a storage unit 163, a concentration calculation unit (second calculation unit) 164, and the like.
  • the logarithmic calculation unit 161 performs logarithmic calculation on the light intensity signal which is the output signal of the photodetector 13.
  • the function I (t) indicating the change over time of the light intensity signal obtained by the photodetector 13 becomes as shown in the “light intensity I (t)” of FIG. 5, and by performing a logarithmic calculation, the function I (t) of FIG. Logarithmic strength L (t) ”.
  • the correlation value calculation unit 162 calculates the correlation value of each of the intensity-related signal related to the intensity of the sample light and the plurality of predetermined feature signals.
  • the feature signal is a signal for extracting the waveform feature of the intensity-related signal by correlating with the intensity-related signal.
  • the feature signal for example, a sine wave signal or various signals according to the waveform feature to be extracted from other intensity-related signals can be used.
  • the correlation value calculation unit 162 is a correlation value between an intensity-related signal related to the intensity of the sample light and a plurality of feature signals having a correlation different from that of the sinusoidal signal (sine function) with respect to the intensity-related signal. Is calculated.
  • the correlation value calculation unit 162 uses the logarithmically calculated light intensity signal (logarithmic intensity L (t)) as the intensity-related signal.
  • the correlation value calculation unit 162 uses the correlation value S i of the intensity-related signal L (t) of the sample light and the plurality of feature signals Fi (t) as the reference light as shown in Equation 1. it is desirable to calculate the intensity related signal L 0 (t) and a plurality of feature signals F i (t) sample correlation values to a correction of subtracting the reference correlation value R i is a correlation value between S i '. As a result, the offset included in the sample correlation value can be removed, and the correlation value becomes proportional to the concentration of the measurement target component and the interference component, and the measurement error can be reduced.
  • the configuration may be such that the reference correlation value is not subtracted.
  • the acquisition timing of the reference light is at the same time as the sample light, before or after the measurement, or at an arbitrary timing.
  • the intensity-related signal of the reference light or the reference correlation value may be acquired in advance and stored in the storage unit 163.
  • the modulated light from the semiconductor laser 12 is split by a beam splitter or the like, one is used for sample light measurement, and the other is used as a reference. It can be used for optical measurement.
  • the correlation value calculation unit 162 uses, as a plurality of feature signals Fi (t), a function that makes it easier to capture a waveform feature having a logarithmic intensity L (t) than a sine function.
  • Fi feature signals
  • a component to be measured for example, SO 2
  • one interference component for example, H 2 O
  • the two feature signals F 1 (t) and F 2 (t) for example, a function based on the Lorentz function close to the shape of the absorption spectrum and a differential function of the function based on the Lorentz function are used. Can be considered.
  • a function based on the Voigt function, a function based on the Gaussian function, or the like can be used instead of the function based on the Lorentz function.
  • a function based on the Voigt function a function based on the Gaussian function, or the like can be used instead of the function based on the Lorentz function.
  • the offset of the feature signal so that the DC component is removed, that is, it becomes zero when integrated in the modulation period.
  • the DC component of the intensity-related signal may be removed, or the DC component of both the feature signal and the intensity-related signal may be removed.
  • the measured value of the absorption signal of the component to be measured and / or the interference component, or a signal imitating them may be used.
  • the features of the logarithmic intensity L (t) can be more efficiently characterized. It can be extracted, and the concentration obtained by the simultaneous equations described later can be made accurate.
  • the unit concentration of the measurement target component and each interference component obtained from the respective intensity-related signals and the plurality of feature signals Fi (t) when the measurement target component and each interference component are present alone It stores the single correlation value, which is the per-correlation value.
  • a plurality of feature signals F i used to determine the single correlation value (t) is the same as the plurality of feature signals F i to be used in the correlation value calculation section 162 (t).
  • the storage unit 163 when the storage unit 163 stores the single correlation value, the storage unit 163 makes a correction for converting per unit concentration after subtracting the reference correlation value from the correlation value when the measurement target component and each interference component exist independently. It is desirable to store the single correlation value. As a result, the offset included in the single correlation value can be removed, and the correlation value becomes proportional to the concentration of the measurement target component and the interference component, and the measurement error can be reduced.
  • the configuration may be such that the reference correlation value is not subtracted.
  • the concentration calculation unit 164 calculates the concentration of the component to be measured by using a plurality of sample correlation values obtained by the correlation value calculation unit 162.
  • the concentration calculation unit 164 calculates the concentration of the component to be measured based on the plurality of sample correlation values obtained by the correlation value calculation unit 162 and the plurality of single correlation values stored in the storage unit 163. It is a thing. More specifically, the concentration calculation unit 164 includes a plurality of sample correlation values obtained by the correlation value calculation unit 162, a plurality of single correlation values stored in the storage unit 163, a measurement target component, and each interference component. The concentration of the component to be measured is calculated by solving a simultaneous equation consisting of the concentration.
  • the sample gas contains one measurement target component (for example, SO 2 ) and one interference component (for example, H 2 O).
  • one measurement target component for example, SO 2
  • one interference component for example, H 2 O
  • the light source control unit 15 controls the semiconductor laser 12 to modulate the wavelength of the laser light at the modulation frequency and centering on the peak of the absorption spectrum of the component to be measured.
  • the reference measurement using span gas the reference measurement using zero gas may be performed and the reference correlation value may be measured.
  • the span gas gas having a known component concentration
  • the reference measurement is performed in each of the span gas in which the measurement target component is present alone and the span gas in which the interference component is present alone.
  • the logarithmic calculation unit 161 receives the output signal of the photodetector 13 and calculates the logarithmic intensity L (t). Then, the correlation value calculation unit 162 calculates the correlation value between the logarithmic intensity L (t) and the two feature signals F 1 (t) and F 2 (t), and subtracts the reference correlation value from the correlation value.
  • the correlation value calculation unit 162 calculates the correlation value between the logarithmic intensity L (t) and the two feature signals F 1 (t) and F 2 (t), and subtracts the reference correlation value from the correlation value.
  • a single correlation value which is the correlation value of each span gas per unit concentration, is calculated. Instead of calculating the single correlation value, the relationship between the span gas concentration and the correlation value of the span gas may be stored.
  • the correlation value calculation unit 162 calculates the correlation values S 1t and S 2t of the measurement target component (see FIG. 6).
  • S 1t is a correlation value with the first feature signal
  • S 2t is a correlation value with the second feature signal.
  • the correlation value calculation section 162 those correlation values S 1t, by dividing the span gas concentration c t of the measurement target component minus the S reference correlation value from 2t R i, alone correlation value s 1t, the s 2t calculate.
  • span gas concentration c t of the measurement target component is preliminarily input by the user or the like to the signal processing unit 16.
  • the correlation value calculation unit 162 calculates the correlation values S 1i and S 2i of the interference component (see FIG. 6).
  • S 1i is a correlation value with the first feature signal
  • S 2i is a correlation value with the second feature signal.
  • the correlation value calculation section 162 those correlation values S 1i, divided by the span gas concentration c i of the interference components minus the reference correlation values from S 2i, alone correlation value s 1i, calculates the s 2i.
  • span gas concentration c i of the interference component is input in advance by the user or the like to the signal processing unit 16.
  • the single correlation values s 1t , s 2t , s 1i , and s 2i calculated as described above are stored in the storage unit 163.
  • this reference measurement may be performed before the product is shipped, or may be performed regularly.
  • the light source control unit 15 controls the semiconductor laser 12 and modulates the wavelength of the laser light at the modulation frequency and centering on the peak of the absorption spectrum of the component to be measured.
  • the sample gas generated in the heating furnace 2 is introduced into the cell 11 through the gas flow path 6 by the operator or automatically, and the sample measurement is performed.
  • the logarithmic calculation unit 161 receives the output signal of the photodetector 13 and calculates the logarithmic intensity L (t). Then, the correlation value calculation unit 162 calculates sample correlation values S 1 and S 2 between the logarithmic intensity L (t) and the plurality of feature signals F 1 (t) and F 2 (t), and calculates the sample correlation values S 1 and S 2 from the correlation values. sample correlation values S 1 by subtracting the reference correlation values R i ', S 2' is calculated (see FIG. 6).
  • the concentration calculating unit 164, a sample correlation value S 1 is the correlation value calculating section 162 calculated ', S 2' and, alone correlation value s 1t storing part 163, s 2t, s 1i, and s 2i, measured component and the interference components each concentration C tar, solving the following binary simultaneous equations consisting of a C int.
  • the concentration Tar of the component to be measured from which the interference effect has been removed can be determined by a simple and reliable calculation of solving the simultaneous equations of the above equation (Equation 2).
  • the interference effect can be similarly affected by adding a single correlation value for the number of interference components and solving a simultaneous equation with the same number of elements as the number of component species.
  • the concentration of the removed component to be measured can be determined.
  • Equation 3 the concentration of each gas of the measurement target component and the interference component can be determined.
  • the sample analyzer 100 using the gas analysis unit 3 of the present embodiment (hereinafter, also referred to as “the present embodiment”) and the metal analyzer using the conventional NDIR analyzer (hereinafter, also referred to as “NDIR”).
  • the difference in the analysis accuracy of the SO 2 concentration from that of) will be described.
  • a dehumidifier is provided on the upstream side of the NDIR analyzer.
  • FIG. 7 shows the peak waveforms detected in the NDIR and this example in the high concentration region (2.4 to 20.10 ppm) and the low concentration region (0.48 to 2.4 ppm). As can be seen from FIG. 7, in the low concentration region, the peak waveform detected in this example is smoother than the peak waveform detected by NDIR.
  • FIG. 8 shows the peak waveforms detected in NDIR and this example when the SO 2 concentration is 0.48 ppm.
  • the SN ratio is 1.3, whereas in this embodiment, the SN ratio is 35.9. As described above, by using this embodiment, the SN ratio is about 27 times that of NDIR.
  • Fig. 9 shows the results of examining the linearity between NDIR and this example.
  • the vertical axis is the measured concentration
  • the horizontal axis is the theoretical concentration.
  • NDIR detection is difficult at a concentration of 1 ppm or less, and the detection concentration of NDIR varies widely.
  • the concentration is 1 ppm or less, it is detected without variation as in the case of the concentration higher than that.
  • FIG. 10 the results of measurement of SO 2 concentration in the case of not providing the case of providing the dehumidifier in the present embodiment and NDIR.
  • NDIR the ratio of the measurement results of the case of not providing the case of providing the dehumidifier ( "SO 2 concentration in the case without the dehumidifier” / "SO 2 concentration obtained when a dehumidifier") is 121.4 In this example, their ratio was 100.9%, whereas it was%. From this, it was found that in this example, the influence of water interference was removed without providing a dehumidifier.
  • the gas analyzer 3 detects the intensity of the laser light source 12 that irradiates the gas with the laser beam and the sample light that the laser beam has passed through the gas. Since the detector 13 is provided, it is not necessary to provide a wavelength selection filter in front of the light detector 13 by irradiating a laser beam having an oscillation wavelength that matches the component to be measured, and the light amount is reduced by the wavelength selection filter. It can be prevented and the SN ratio can be increased. As a result, the component to be measured can be reliably analyzed. Further, since the laser light source 12 is used, the maintenance frequency can be reduced.
  • the sample analyzer 100 can reliably analyze the component to be measured while reducing the frequency of maintenance. Further, according to the present embodiment, in WMS using the intensity-related signal obtained by emitting the modulated light modulated at a predetermined modulation frequency, the concentration of the component to be measured from the intensity-related signal related to the intensity of the sample light. Since the representative value depending on the above is calculated and the concentration of the component to be measured is calculated using the representative value, the solid sample W is not required for the spectrum calculation processing for concentration quantification required in the conventional WMS. It is possible to reliably analyze the components to be measured contained in.
  • the logarithmic intensity L (t) which is an intensity-related signal related to the intensity of the sample light
  • the plurality of feature signals Fi (t) with respect to the logarithmic intensity L (t)
  • calculating a correlation value S i of so to calculate the concentration of the measurement target component by using a plurality of correlation values S i calculated, without converting the absorption signals to the absorption spectrum, dramatically the characteristics of the absorption signal It can be captured with a small number of variables, and the concentration of the component to be measured can be measured by a simple calculation without complicated spectral calculation processing.
  • the number of data points used in general spectrum fitting is required to be several hundred, but in the present invention, the concentration can be calculated with the same accuracy by using a few to several tens of correlation values at most.
  • the load of arithmetic processing can be dramatically reduced, an advanced arithmetic processing apparatus becomes unnecessary, the cost of the sample analyzer 100 can be reduced, and the size can be reduced.
  • the ultraviolet fluorescence method since the ultraviolet fluorescence method is not used, it is not necessary to use an ultraviolet light source, and maintenance such as frequent replacement of the ultraviolet light source can be eliminated.
  • the dehydrating agent can be eliminated, and the dehydrating agent is replaced regularly. It is possible to eliminate the need for maintenance. Further, since the dehydrating agent can be eliminated, the apparatus configuration can be simplified. That is, the gas flow path 6 of the present embodiment can be configured not to be provided with a dehydrating agent.
  • the sample analyzer 100 of the second embodiment has a different configuration of the signal processing device 14 from the first embodiment.
  • the other configurations are the same as those of the first embodiment, and the description thereof will be omitted below.
  • the signal processing device 14 includes an analog electric circuit composed of a buffer, an amplifier, etc., a digital electric circuit composed of a CPU, a memory, etc., and an AD converter, a DA converter, etc. that mediate between the analog / digital electric circuits.
  • a light source control unit 15 that controls the output of the semiconductor laser 12 and an optical detector are provided by the cooperation of a CPU and its peripheral devices according to a predetermined program stored in a predetermined area of the memory. It exhibits a function as a signal processing unit 16 that receives an output signal from 13 and calculates the value thereof to calculate the concentration of the component to be measured.
  • the light source control unit 15 controls the current source (or voltage source) of the semiconductor laser 12 by outputting a current (or voltage) control signal, and thereby determines the drive current (or drive voltage) thereof.
  • the frequency is changed, and the oscillation wavelength of the laser light output from the semiconductor laser 12 is modulated by the predetermined frequency.
  • the light source control unit 15 changes the drive current in a sinusoidal shape and modulates the oscillation frequency in a sinusoidal shape (see the modulated signal in FIG. 12). Further, as shown in FIG. 4, the oscillation wavelength of the laser beam is modulated around the peak of the light absorption spectrum of the component to be measured.
  • the signal processing unit 16 includes an absorbance signal calculation unit 166, a synchronous detection signal generation unit (first calculation unit) 167, a concentration calculation unit (second calculation unit) 168, and the like.
  • the absorbance signal calculation unit 166 includes the light intensity of the laser light (hereinafter, also referred to as transmitted light) transmitted through the cell 11 in a state where the sample gas is sealed and the component to be measured in the sample gas absorbs the light, and the light absorption. Is to calculate the logarithm of the ratio of the laser beam (hereinafter, also referred to as reference light) transmitted through the cell 11 in a substantially zero state to the light intensity (hereinafter, also referred to as intensity ratio logarithm).
  • both the light intensity of the transmitted light and the light intensity of the reference light are measured by the light detector 13, and the measurement result data is stored in a predetermined area of the memory.
  • the absorbance signal calculation unit 166 The intensity ratio logarithmic value (hereinafter, also referred to as an absorbance signal) is calculated with reference to this measurement result data.
  • sample measurement is, of course, performed for each sample gas.
  • reference measurement may be performed either before or after the sample measurement, or at an appropriate timing, for example, only once, and the result is stored in the memory for each sample. It may be commonly used for measurement.
  • zero gas optical absorption is substantially zero, for example, N 2
  • the gas is sealed in the cell 11, other gas may be used, or the inside of the cell 11 may be evacuated.
  • the synchronous detection signal generation unit 167 locks in the absorbance signal calculated by the absorbance signal calculation unit 66 with a sine wave signal (reference signal) having a frequency n times the modulation frequency (n is an integer of 1 or more).
  • the frequency component of the reference signal is extracted from the absorbance signal to generate a synchronous detection signal.
  • the lock-in detection may be performed by digital calculation or calculation by an analog circuit. Further, the extraction of the frequency component may be performed not only by lock-in detection but also by a method such as Fourier series expansion.
  • the concentration calculation unit 168 calculates the concentration of the component to be measured based on the synchronous detection result by the synchronous detection signal generation unit 167.
  • the light source control unit 15 controls the semiconductor laser 12 as described above, and modulates the wavelength of the laser light at the modulation frequency and centering on the peak of the absorption spectrum of the component to be measured.
  • the absorbance signal calculation unit 166 that detects this performs a reference measurement.
  • the output signal from the photodetector 13 in the state where the zero gas is sealed in the cell 11 is received, and the value is stored in the measurement result data storage unit.
  • the value of the output signal of the photodetector 13 in this reference measurement that is, the reference light intensity is represented by a time series graph as shown in FIG. 12A. That is, only the change in the optical output due to the modulation of the laser drive current (voltage) appears in the output signal of the photodetector 13.
  • the absorbance signal calculation unit 166 performs the sample measurement. Specifically, it receives an output signal from the photodetector 13 in a state where the sample gas is sealed in the cell 11, and stores the value in a predetermined area of the memory.
  • the value of the output signal of the photodetector 13 in this sample measurement, that is, the transmitted light intensity is represented by a time series graph as shown in FIG. 12B. It can be seen that a peak due to absorption appears every half cycle of modulation.
  • the absorbance signal calculation unit 166 synchronizes each measurement data with the modulation cycle, and calculates the intensity ratio logarithm (absorbance signal) between the light intensity of the transmitted light and the light intensity of the reference light. Specifically, the calculation equivalent to the following equation (Equation 4) is performed.
  • D m (t) is the transmitted light intensity
  • D z (t) is the reference light intensity
  • a (t) is the intensity ratio logarithm (absorbance signal).
  • FIG. 12 (c) shows a graph showing this absorbance signal with time as the horizontal axis.
  • the logarithm may be obtained after calculating the ratio of the transmitted light intensity to the reference light intensity, or the logarithm of the transmitted light intensity and the logarithm of the reference light intensity may be obtained and subtracted from each other.
  • the synchronous detection signal generation unit 167 extracts a lock-in detection, that is, a frequency component twice the modulation frequency of the absorbance signal with a reference signal having a frequency twice the modulation frequency, and the synchronous detection signal (hereinafter referred to as the synchronous detection signal). , Also referred to as lock-in data) is stored in a predetermined area of the memory.
  • the value of this lock-in data becomes a value proportional to the concentration of the component to be measured, and the concentration calculation unit 168 calculates a concentration indicated value indicating the concentration of the component to be measured based on the value of this lock-in data.
  • f m is the modulation frequency
  • n represents a multiple with respect to the modulation frequency
  • a (t) is also expressed by the above formula (Equation 1).
  • A'(t) is a laser in which -ln ( ⁇ ), which is a constant value, is simply added to the absorbance signal A (t) when there is no fluctuation in the laser light intensity. Even if the light intensity is changed value a n of the respective frequency components it can be seen that unchanged.
  • the above is an operation example of the sample analyzer 100 when the sample gas does not contain an interference component other than the component to be measured.
  • one or more interfering compounds e.g., H 2 O
  • one or more interfering compounds will be described operation example of the sample analysis device 100 when contained in a sample gas having a light absorption peak light absorption wavelength of the measurement target component.
  • the principle will be described. Since the light absorption spectra of the component to be measured and the interference component have different shapes, the absorbance signal when each component exists alone has a different waveform, and the ratio of each frequency component is different (linearly independent). Taking advantage of this, interference is achieved by solving simultaneous equations using the relationship between the value of each frequency component of the measured absorbance signal and each frequency component of the absorbance signal of the measurement target component and the interference component obtained in advance. It is possible to obtain the concentration of the component to be measured whose influence has been corrected.
  • the absorbance signals per unit concentration when the measurement target component and the interference component are present independently are Am (t) and A i (t), respectively, and the frequency components of the respective absorbance signals are nm and an ni. Then, the following equations (Equation 7 and Equation 8) hold.
  • the analyzer 100 operates based on the above-mentioned principle. That is, in this case, the analyzer 100 has a frequency component of each absorbance signal when the measurement target component and the interference component are present alone, for example, by flowing span gas in advance in a predetermined area of the memory and measuring in advance. It stores a 1m , a 2m , a 1i , and a 2i . Specifically, as in the previous example, for each of the measurement target component and the interference component, the measurement target light intensity and the reference light intensity are measured, their intensity ratio logarithm (absorbance signal) is calculated, and the lock is obtained from this intensity ratio logarithm.
  • Frequency components a 1m , a 2m , a 1i , and a 2i are obtained by in-detection and stored. Instead of the said frequency component, the absorbance signal A m per unit concentration (t), and stores the A i (t), the equation (7, 8) from the frequency components a 1m, a 2m, a 1i , A 2i may be calculated.
  • the analyzer 100 identifies the measurement target component and the interference component by input from the operator or the like.
  • the absorbance signal calculation unit 166 calculates the intensity ratio logarithm A (t) according to the equation (Equation 4). Thereafter, the synchronous detection signal generation unit 167, and lock-in detection with the reference signal having a frequency 2f m of the intensity ratio logarithmic modulation frequency f m and twice, each frequency component a 1, a 2 (lock-in data) Is extracted and stored in a predetermined area of memory.
  • the concentration calculation unit 168 applies the lock-in data values a 1 , a 2, and the values of the frequency components a 1 m , a 2 m , a 1i , and a 2i stored in the memory to the above equation (Equation 10), or Performing an equal calculation to this, the concentration (or concentration indicated value) C m indicating the concentration of the measurement target gas from which the interference effect has been removed is calculated. At this time, the concentration of each interference component (or concentration indicated value) may be calculated C i.
  • the gas analysis unit 3 comprises a laser light source 12 that irradiates the gas with laser light and a light detector 13 that detects the intensity of the sample light transmitted by the laser light through the gas. Since it is provided, by irradiating laser light with an oscillation wavelength that matches the component to be measured, it is not necessary to provide a wavelength selection filter in front of the light detector 13, preventing a decrease in the amount of light due to the wavelength selection filter, and reducing the SN ratio. Can be made larger. As a result, the component to be measured can be reliably analyzed. Further, since the laser light source 12 is used, the maintenance frequency can be reduced.
  • the sample analyzer 100 can reliably analyze the component to be measured while reducing the frequency of maintenance. Further, according to the present embodiment, in WMS using the intensity-related signal obtained by emitting the modulated light modulated at a predetermined modulation frequency, the concentration of the component to be measured from the intensity-related signal related to the intensity of the sample light. Since the representative value depending on the above is calculated and the concentration of the component to be measured is calculated using the representative value, the solid sample W is not required for the spectrum calculation processing for concentration quantification required in the conventional WMS. It is possible to reliably analyze the components to be measured contained in.
  • a frequency component n times the modulation frequency is extracted from the absorbance signal A (t), and the concentration of the component to be measured is calculated using the extracted frequency component, so that complicated spectral calculation processing is performed.
  • the concentration of the component to be measured can be measured by a simple calculation without doing so. As a result, an advanced arithmetic processing unit becomes unnecessary, the cost of the sample analyzer 100 can be reduced, and the size can be reduced.
  • the ultraviolet fluorescence method since the ultraviolet fluorescence method is not used, it is not necessary to use an ultraviolet light source, and maintenance such as frequent replacement of the ultraviolet light source can be eliminated.
  • the dehydrating agent can be eliminated, and the dehydrating agent is replaced regularly. It is possible to eliminate the need for maintenance. Further, since the dehydrating agent can be eliminated, the apparatus configuration can be simplified. That is, the gas flow path 6 of the present embodiment can be configured not to be provided with a dehydrating agent.
  • the logarithmic calculation unit 161 of the first embodiment performs logarithmic calculation of the light intensity signal of the photodetector 13, but the light intensity signal of the photodetector 13 is used to calculate the intensity and reference of the sample light.
  • the logarithm of the ratio to the intensity of light (so-called absorbance) may be calculated.
  • the logarithm calculation unit 161 may calculate the logarithm of the intensity of the sample light, calculate the logarithm of the intensity of the reference light, and then subtract them to calculate the absorbance, or the intensity of the sample light and the reference light.
  • the absorbance may be calculated by taking the logarithm of the ratio after obtaining the ratio with the intensity of.
  • the correlation value calculation unit 162 of the first embodiment calculates the correlation value between the intensity-related signal and the feature signal, but calculates the inner product value of the intensity-related signal and the feature signal. You may.
  • the storage unit 163 stores the single correlation value corrected by using the reference correlation value, but the storage unit 163 stores the single correlation value before correction and the concentration.
  • the calculation unit 164 may be configured to subtract the reference correlation value from the single correlation value before correction and then obtain the corrected single correlation value converted per unit concentration.
  • the plurality of feature signals are not limited to the first embodiment, and may be functions different from each other.
  • the feature signal for example, a function showing a waveform (measured spectrum) of light intensity, logarithmic intensity or absorbance obtained by flowing a span gas having a known concentration may be used. Further, when measuring the concentration of one component to be measured, at least one feature signal is sufficient.
  • the light source control unit 15 of each of the above embodiments continuously oscillates (CW) the semiconductor laser, but as shown in FIG. 13, it may oscillate pseudo-continuously (pseudo-CW).
  • the light source control unit 15 controls the current source (or voltage source) of each semiconductor laser 12 by outputting a current (or voltage) control signal to drive the current (or voltage source) drive current (drive).
  • the voltage) is set to be equal to or higher than a predetermined threshold value for pulse oscillation.
  • the light source control unit 15 oscillates pseudo-continuously by pulse oscillation having a predetermined pulse width (for example, 10 to 50 ns, duty ratio 5%) repeated in a predetermined period (for example, 1 to 5 MHz).
  • the light source control unit 15 changes the temperature by changing the drive current (drive voltage) of the current source (or voltage source) at a predetermined frequency with a wavelength sweeping value that is less than the threshold value for pulse oscillation. Is generated to sweep the oscillation wavelength of the laser beam.
  • the modulation signal that modulates the drive current varies in a triangular wave shape, a saw wave shape, or a sinusoidal shape, and its frequency is, for example, 1 to 100 Hz.
  • the light intensity signal obtained by the photodetector 13 by oscillating the semiconductor laser in a pseudo-continuous manner is as shown in FIG. In this way, the absorption spectrum can be acquired for the entire pulse train.
  • Pseudo-continuous oscillation requires less power consumption of the light source than continuous oscillation, facilitates exhaust heat treatment, and can extend the life of the light source.
  • the gas analysis unit 3 may include a plurality of semiconductor lasers 12 which are light sources for irradiating the cell 11 with laser light.
  • the signal processing device 14 separates the signal for each semiconductor laser 12 from the light intensity signal obtained by the light source control unit 15 and the photodetector 13 that control the output of the semiconductor laser 12. It functions as a signal processing unit 16 or the like that receives signals for each of the signal separation unit 17 and the semiconductor laser 12 separated by the signal separation unit 17 and calculates and processes the values to calculate the concentration of the component to be measured. To do.
  • the light source control unit 15 pulse-oscillates each of the plurality of semiconductor lasers 12 and modulates the oscillation wavelength of the laser light at a predetermined frequency. Further, the light source control unit 15 controls the plurality of semiconductor lasers 12 so as to have oscillation wavelengths corresponding to different measurement target components, and pulses so that they have the same oscillation period and their oscillation timings are different from each other. Oscillate.
  • the light source control unit 15 controls the current source (or voltage source) of each semiconductor laser 12 by outputting a current (or voltage) control signal.
  • the light source control unit 15 of the present embodiment repeats each semiconductor laser 12 in a predetermined period (for example, 0.5 to 5 MHz) with a predetermined pulse width (for example, 10 to 100 ns, duty ratio 5). %) Pulse oscillation is used for pseudo continuous oscillation (pseudo CW).
  • the light source control unit 15 causes a temperature change by changing the drive current (drive voltage) of the current source (or voltage source) at a predetermined frequency to sweep the oscillation wavelength of the laser light. Is to do.
  • the oscillation wavelength of the laser light in each semiconductor laser is modulated around the peak of the light absorption spectrum of the component to be measured.
  • the modulation signal that changes the drive current is a signal that changes in a triangular wave shape, a saw wave shape, or a sinusoidal shape, and whose frequency is, for example, 100 Hz to 10 kHz. Note that FIG. 13 shows an example in which the modulated signal changes in a triangular wave shape.
  • the light intensity signal obtained by the photodetector 13 by oscillating one semiconductor laser 12 in a pseudo-continuous manner is as shown in FIG. In this way, the absorption signal can be acquired for the entire pulse train.
  • the light source control unit 15 oscillates a plurality of semiconductor lasers 12 in pulses at different timings. Specifically, as shown in FIG. 17, a plurality of semiconductor lasers 12 sequentially pulse oscillate, and one pulse of each of the other semiconductor lasers 12 is included in one cycle of pulse oscillation in one semiconductor laser 12. That is, one pulse of each of the other semiconductor lasers 12 is included in the pulses of one semiconductor laser 12 adjacent to each other. At this time, the pulses of the plurality of semiconductor lasers 12 are oscillated so as not to overlap each other.
  • the signal separation unit 17 separates the signals of each of the plurality of semiconductor lasers 12 from the light intensity signal obtained by the photodetector 13.
  • the signal separation unit 17 of the present embodiment includes a plurality of sample hold circuits provided corresponding to each of the plurality of semiconductor lasers 12 and an AD converter that digitally converts the light intensity signal separated by the sample hold circuits. doing.
  • the sample hold circuit and the AD converter may be one common to the plurality of semiconductor lasers 12.
  • the sample hold circuit uses the sampling signal synchronized with the current (or voltage) control signal of the corresponding semiconductor laser 12 to obtain the light intensity signal of the photodetector 13 at the timing synchronized with the pulse oscillation timing of the semiconductor laser 12.
  • the signal of the corresponding semiconductor laser 12 is separated and held.
  • the sample hold circuit is configured to separate and hold the signal corresponding to the latter half of the pulse oscillation of the semiconductor laser 12.
  • the waveform can be reproduced by collecting the signal at the same timing as the pulse oscillation. Further, since the signal corresponding to a part of the pulse oscillation is separated by the sample hold circuit, the AD converter may have a slow processing speed. A plurality of light absorption signals obtained for each semiconductor laser 12 may be used on a time average.
  • the signal processing unit 16 calculates the concentration of the component to be measured corresponding to each semiconductor laser 12.
  • the signal processing unit 16 calculates the concentration of the component to be measured in the same manner as in the above embodiment.
  • an intensity-related signal related to the intensity of the sample light and a feature signal obtained with a predetermined correlation with the intensity-related signal are obtained.
  • a first calculation unit that calculates a representative value depending on the concentration of the measurement target component, and a second calculation unit that calculates the concentration of the measurement target component using the representative value obtained by the first calculation unit may be used.
  • the light source may be any other type of laser regardless of the semiconductor laser, and any light source is used as long as it is a single-wavelength light source having a half-value width sufficient to ensure measurement accuracy and can even perform wavelength modulation. You may. Further, the light source may be intensity-modulated.
  • one gas analyzer 3 is provided on the gas flow path 6, but as shown in FIG. 18, an NDIR analyzer 8 may be provided in addition to the gas analyzer 3. good.
  • a dehumidifier 7 is provided on the downstream side of the gas analyzer 3
  • an NDIR analyzer 8 is provided on the downstream side of the dehumidifier 7.
  • the dehumidifier 7 may be provided on the upstream side of the gas analysis unit 3.
  • the gas flow path 6 may be branched into a first flow path for supplying gas to the gas analysis unit 3 and a second flow path for supplying gas to the NDIR analyzer 8.
  • the measurement range of the gas analyzer 3 is set to 200 ppm or less
  • the measurement range of the NDIR analyzer 8 is set to 200 ppm to 5%
  • the measurement result of the gas analyzer 3 is adopted in the low concentration region
  • the NDIR analyzer 8 is adopted in the high concentration region. It is possible to adopt the measurement result of.
  • the cell 11 of the gas analyzer 3 acts like a buffer tank, and the signal may become dull and the sensitivity may decrease. Therefore, when determining the sensitivity of the NDIR analyzer 8, the NDIR analyzer 8 may be provided on the upstream side and the gas analysis unit 3 may be provided on the downstream side in the gas flow path 6. With this configuration, it is possible to perform analysis utilizing the sensitivity of the NDIR analyzer 8.
  • the heating furnace 2 of each of the above embodiments was a high frequency induction heating furnace type, but may be an electric resistance furnace type. Further, the heating furnace 2 may be an infrared gold image furnace that heats a sample using an infrared lamp. Further, the fixed sample may be heated by sandwiching the graphite crucible containing the fixed sample between the lower electrode and the upper electrode and passing an electric current through the graphite crucible. Further, the present invention can be applied to an apparatus having a gas generating unit that generates gas by burning a fixed sample housed in a crucible.
  • the sample holder of each of the above embodiments was a container R such as a crucible for accommodating the sample W, but it may be configured to hold the sample W without accommodating it.
  • the sample W is heated by arranging the sample holder holding the sample W in the heating furnace 2.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
PCT/JP2020/018928 2019-05-15 2020-05-12 試料分析装置 Ceased WO2020230775A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/611,471 US12111254B2 (en) 2019-05-15 2020-05-12 Sample analyzing apparatus
CN202080034715.2A CN113811758A (zh) 2019-05-15 2020-05-12 试样分析装置
JP2021519434A JP7461937B2 (ja) 2019-05-15 2020-05-12 試料分析装置
EP20805409.8A EP3957979B1 (en) 2019-05-15 2020-05-12 Sample analyzing apparatus

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-092441 2019-05-15
JP2019092441 2019-05-15

Publications (1)

Publication Number Publication Date
WO2020230775A1 true WO2020230775A1 (ja) 2020-11-19

Family

ID=73289441

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/018928 Ceased WO2020230775A1 (ja) 2019-05-15 2020-05-12 試料分析装置

Country Status (5)

Country Link
US (1) US12111254B2 (https=)
EP (1) EP3957979B1 (https=)
JP (1) JP7461937B2 (https=)
CN (1) CN113811758A (https=)
WO (1) WO2020230775A1 (https=)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116148309B (zh) * 2023-04-20 2023-08-15 钢研纳克检测技术股份有限公司 一种基于热导-红外法多组合的氧氮氢联测装置及方法
CN117007545A (zh) * 2023-08-11 2023-11-07 内蒙古科技大学 锅炉烟道尾气co2浓度红外吸收检测模型及其构建方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06265475A (ja) 1993-03-13 1994-09-22 Horiba Ltd 酸素気流中燃焼ガス分析装置
JP2007040995A (ja) * 2005-08-04 2007-02-15 Ir Microsystems Sa ガス検出方法及びガス検出装置
JP2011043461A (ja) * 2009-08-24 2011-03-03 Shimadzu Corp ガス分析装置
JP2011169753A (ja) 2010-02-18 2011-09-01 Jfe Steel Corp 金属試料中の硫黄の分析方法および分析装置
JP2011220758A (ja) * 2010-04-07 2011-11-04 Shimadzu Corp ガス分析装置
JP2013050403A (ja) * 2011-08-31 2013-03-14 Shimadzu Corp ガス分析装置
JP2013134236A (ja) * 2011-12-27 2013-07-08 Horiba Ltd ガス計測装置およびガス計測装置における波長変調幅の設定方法。
CN108458984A (zh) * 2018-05-21 2018-08-28 郑州力创光电技术有限公司 基于光电传感原理的气体绝缘设备在线气体监测控制系统
JP2019027867A (ja) * 2017-07-28 2019-02-21 富士電機株式会社 ガス分析装置

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4216508A1 (de) 1992-05-19 1993-11-25 Ortwin Dr Brandt Feststoffanalysengerät (Vorrichtung und Verfahren)
US5984998A (en) * 1997-11-14 1999-11-16 American Iron And Steel Institute Method and apparatus for off-gas composition sensing
US6326620B1 (en) 1999-05-07 2001-12-04 Leco Corporation Switched mode NDIR system
CA2351792C (en) * 2000-06-26 2010-07-27 Murray J. Thomson Method and apparatus for improved process control in combustion applications
US20020152797A1 (en) * 2001-01-09 2002-10-24 Mcandrew James J.F. Gas delivery apparatus and method for monitoring a gas phase species therein
US6827903B2 (en) 2001-10-26 2004-12-07 Leco Corporation Inert gas fusion analyzer
JP3762729B2 (ja) * 2002-09-11 2006-04-05 株式会社堀場製作所 多成分分析装置
EP2118638B2 (en) 2007-02-26 2017-08-16 Yokogawa Corporation of America Combustion gas analysis
JP5667912B2 (ja) * 2010-05-18 2015-02-12 株式会社堀場製作所 吸着性ガス分析装置
EP2685230B1 (en) * 2011-03-09 2020-09-30 HORIBA, Ltd. Gas analysis device
CN111537669A (zh) 2013-09-25 2020-08-14 株式会社堀场制作所 分析装置和分析方法
CN104316480B (zh) * 2014-11-06 2016-08-24 中国科学院合肥物质科学研究院 一种含砷金精矿焙烧炉内氧气浓度的激光原位检测系统
WO2016208424A1 (ja) * 2015-06-22 2016-12-29 国立大学法人京都大学 Ｎｄｉｒ式のガスセンサ、ガス分析計、光合成速度測定装置、及び、光合成速度測定方法
JP6651126B2 (ja) * 2015-09-08 2020-02-19 富士電機株式会社 ガス分析計
GB2544507B (en) * 2015-11-18 2017-11-22 Servomex Group Ltd Method and system for reduction of influence of baseline distortion in absorption spectroscopy measurements
JP6513762B2 (ja) 2016-12-15 2019-05-15 株式会社堀場製作所 分析装置、分析装置用プログラム及び分析方法
NO345903B1 (en) 2017-06-16 2021-10-04 Neo Monitors As Chemical analysis method for measurement of tetrafluoromethane, cf4, with improved selectivity
CN109596538B (zh) * 2017-10-03 2023-08-25 株式会社堀场制作所 分析装置和分析方法
JP7075862B2 (ja) 2017-10-16 2022-05-26 株式会社堀場製作所 分析装置
CN109490250B (zh) 2018-11-22 2021-06-25 宁波海尔欣光电科技有限公司 校准激光器的波长的方法及装置、气体浓度分析仪
JP6886507B2 (ja) * 2018-12-26 2021-06-16 株式会社堀場製作所 分析装置、分析装置用プログラム及び分析方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06265475A (ja) 1993-03-13 1994-09-22 Horiba Ltd 酸素気流中燃焼ガス分析装置
JP2007040995A (ja) * 2005-08-04 2007-02-15 Ir Microsystems Sa ガス検出方法及びガス検出装置
JP2011043461A (ja) * 2009-08-24 2011-03-03 Shimadzu Corp ガス分析装置
JP2011169753A (ja) 2010-02-18 2011-09-01 Jfe Steel Corp 金属試料中の硫黄の分析方法および分析装置
JP2011220758A (ja) * 2010-04-07 2011-11-04 Shimadzu Corp ガス分析装置
JP2013050403A (ja) * 2011-08-31 2013-03-14 Shimadzu Corp ガス分析装置
JP2013134236A (ja) * 2011-12-27 2013-07-08 Horiba Ltd ガス計測装置およびガス計測装置における波長変調幅の設定方法。
JP2019027867A (ja) * 2017-07-28 2019-02-21 富士電機株式会社 ガス分析装置
CN108458984A (zh) * 2018-05-21 2018-08-28 郑州力创光电技术有限公司 基于光电传感原理的气体绝缘设备在线气体监测控制系统

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3957979A4

Also Published As

Publication number Publication date
JP7461937B2 (ja) 2024-04-04
CN113811758A (zh) 2021-12-17
EP3957979A4 (en) 2023-01-11
JPWO2020230775A1 (https=) 2020-11-19
US20220244176A1 (en) 2022-08-04
US12111254B2 (en) 2024-10-08
EP3957979A1 (en) 2022-02-23
EP3957979B1 (en) 2025-04-16

Similar Documents

Publication Publication Date Title
EP3218695B1 (en) Target analyte detection and quantification in sample gases with complex background compositions
CN108226064B (zh) 分析装置、计算机可读存储介质和分析方法
CN109596538B (zh) 分析装置和分析方法
JP6886507B2 (ja) 分析装置、分析装置用プログラム及び分析方法
CN115667884B (zh) 分析装置、记录介质及分析方法
JP7461937B2 (ja) 試料分析装置
JP2013040826A (ja) 分析方法及び分析装置
JP6791214B2 (ja) 分光分析装置
EP3992614B1 (en) Analysis device
EP4439049A1 (en) Analysis device and analysis method
CN118176413A (zh) 分析装置、分析装置用程序以及分析方法
CN118202228A (zh) 分析装置、分析装置用程序以及分析方法
JPWO2023095864A5 (https=)
EP4446728A1 (en) Analysis device and analysis method
JP6028889B2 (ja) レーザ式ガス分析計

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20805409

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021519434

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020805409

Country of ref document: EP

Effective date: 20211118

WWG Wipo information: grant in national office

Ref document number: 2020805409

Country of ref document: EP