WO2015181879A1 - Gas analyzer - Google Patents
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- WO2015181879A1 WO2015181879A1 PCT/JP2014/063926 JP2014063926W WO2015181879A1 WO 2015181879 A1 WO2015181879 A1 WO 2015181879A1 JP 2014063926 W JP2014063926 W JP 2014063926W WO 2015181879 A1 WO2015181879 A1 WO 2015181879A1
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- gas
- light
- unit
- absorbing
- absorption
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- 239000007789 gas Substances 0.000 claims abstract description 1188
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000005259 measurement Methods 0.000 claims abstract description 66
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 56
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 39
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010521 absorption reaction Methods 0.000 claims description 160
- 238000001514 detection method Methods 0.000 claims description 51
- 230000005540 biological transmission Effects 0.000 claims description 47
- 230000003647 oxidation Effects 0.000 claims description 47
- 238000007254 oxidation reaction Methods 0.000 claims description 47
- 238000012545 processing Methods 0.000 claims description 30
- 238000012937 correction Methods 0.000 claims description 18
- 230000003750 conditioning effect Effects 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 230000000644 propagated effect Effects 0.000 claims description 4
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 abstract 4
- 238000002156 mixing Methods 0.000 description 37
- 238000004458 analytical method Methods 0.000 description 32
- 239000002994 raw material Substances 0.000 description 25
- 238000010586 diagram Methods 0.000 description 15
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- 238000004364 calculation method Methods 0.000 description 6
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- 229910052717 sulfur Inorganic materials 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- -1 aluminum nitride compound Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
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- 238000006477 desulfuration reaction Methods 0.000 description 1
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- 239000003546 flue gas Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Definitions
- the present invention relates to a gas analyzer that measures gas concentrations of a plurality of gases contained in a sample gas.
- Patent Literature 1 discloses a conventional gas analyzer. This prior art will be described with reference to the drawings.
- FIG. 12 is a conventional absorption spectrometer described in Patent Document 1.
- the absorption spectrometer 300 measures the concentration of NO 2 gas (nitrogen dioxide gas) contained in the sample gas by the ultraviolet absorption method.
- the absorption spectrometer 300 includes an ultraviolet light source 301, a visible light source 302, a reference cell 303, a sample cell 304, a light guide mechanism 305, a light detection unit 306, a control unit 307, and a calculation unit 308. ing.
- the ultraviolet light source 301 is a light emitting diode that emits ultraviolet light.
- the central emission wavelength of the ultraviolet light is 360 to 400 nm, and is included in the absorption wavelength band of NO 2 gas as shown in the wavelength-absorption coefficient characteristic diagram of FIG. Upon irradiation of such ultraviolet light to NO 2 gas, absorption by NO 2 gas.
- the visible light source 302 is a light emitting diode that emits visible light.
- the central emission wavelength of visible light is larger than the wavelength of ultraviolet light and is included in the absorption wavelength band of NO 2 gas as shown in the wavelength-absorption coefficient characteristic diagram of FIG. Is different. As such it absorbance of visible light by the NO 2 gas is irradiated to NO 2 gas is carried out, when compared with the absorption of ultraviolet light by the above-mentioned NO 2 gas, the absorbance of visible light is reduced by the NO 2 gas, The wavelength of the visible light source 302 is set.
- the reference cell 303 is filled with a reference gas.
- This reference gas is, for example, nitrogen gas.
- Ultraviolet light or visible light is incident through the windows 303a and 303b.
- the sample cell 304 is supplied with a sample gas that is a measurement target. Ultraviolet light or visible light is incident through the windows 304a and 304b. The sample gas flows into the sample cell 304 through the gas inlet 304c and flows out through the gas outlet 304d.
- the light guide mechanism 305 includes a mirror 305a and a half mirror 305b.
- the ultraviolet light from the ultraviolet light source 301 and the visible light from the visible light source 302 are reflected by the half mirror 305b and the mirror 305a and introduced into the reference cell 303 from one end side through the window 303a of the reference cell 303.
- ultraviolet light from the ultraviolet light source 301 and visible light from the visible light source 302 are transmitted through the half mirror 305 b and introduced into the sample cell 304 from one end side through the window 304 a of the sample cell 304.
- absorption by NO 2 gas is performed.
- the light detection unit 306 includes light detectors 306a and 306b.
- the photodetector 306a is provided on the other end side of the reference cell 303, and detects ultraviolet light or visible light transmitted through the window 303b of the reference cell 303.
- the photodetector 306b is provided on the other end side of the sample cell 304, and detects ultraviolet light and visible light transmitted through the window 304b of the sample cell 304.
- the control unit 307 causes the ultraviolet light source 301 and the visible light source 302 to emit light in a time-sharing manner.
- the light detection unit 306 obtains two-wavelength transmitted light that passes through the reference cell 303 and the sample cell 304. As a result, there are two optical paths and two wavelengths, and four signals are obtained: a sample signal for ultraviolet transmitted light, a sample signal for visible transmitted light, a reference signal for ultraviolet transmitted light, and a reference signal for visible transmitted light.
- the calculation unit 308 receives the four signals from the light detection unit 306 via the control unit 307, and calculates the NO 2 gas concentration based on the four signals. Thereby, compensation of drift of the ultraviolet light source 301 and the visible light source 302, correction of interference of other components other than the measurement component, correction of light amount decrease due to dirt and clouding of the transmission windows 304a and 304b of the sample cell 304, correction of sensitivity drift, Make it possible.
- the NO 2 gas concentration can be calculated after performing these corrections, and the measurement accuracy is improved.
- the measurable gas component is limited to one type. Therefore, in order to measure the concentration of two or more kinds of gases by the absorption method, a plurality of light emitting means for emitting a wavelength for absorbing a certain gas and a plurality of light receiving means for receiving the light are required for each gas. Become. Thus, in the prior art, there is a problem that the configuration increases in order to measure the concentration of two or more kinds of gases.
- the absorption of NO gas in the ultraviolet wavelength region includes the absorption of SO 2 gas and NO 2 gas, and is affected by other gases. Further, in the absorption of SO 2 gas in the ultraviolet wavelength region, there is also absorption of NO 2 gas, which is influenced by other gases.
- NO gas and SO 2 gas do not absorb, and visible transmitted light does not contain information about NO gas and SO 2 gas. Therefore, it is impossible to correct interference caused by NO gas or SO 2 gas, or to use it for concentration measurement of NO gas or SO 2 gas.
- the sample gas contains the gas components of NO gas and SO 2 gas as described above, it has been difficult to analyze the gas components of these NO gas and SO 2 gas in the prior art.
- a light source that emits light at a wavelength of 226 nm or less is required as shown in FIG.
- a light source that emits light in this wavelength region is limited to a lamp light source such as a deuterium lamp or a xenon lamp, or a light emitting diode using an aluminum nitride compound semiconductor (such as AlGaN).
- the former lamp light sources such as deuterium lamps and xenon lamps have problems with the heat generation, life and stability of the light source, and it is necessary to add an optical system such as a wavelength filter, and the apparatus is large and complicated.
- the latter light-emitting diode can reduce the size and simplification of the device as compared with the lamp light source, but has a short optical power and a short life. Further, in the wavelength region of wavelength 226 nm or less, various gases absorb light other than SO 2 gas and NO 2 gas, and it is difficult to remove the interference.
- an object of the present invention is to provide at least nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in the sample gas with a simple configuration. It is to provide a gas analyzer that can measure the gas concentration of two components. It is preferable to provide a gas analyzer capable of measuring the three component gas concentrations of sulfur dioxide gas (SO 2 gas), nitric oxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas).
- SO 2 gas sulfur dioxide gas
- NO gas nitric oxide gas
- NO 2 gas nitrogen dioxide gas
- the present invention A gas analyzer that measures the gas concentrations of two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in a sample gas, All nitric oxide gas contained in the sample gas (NO gas) by oxidation of ozone reacted in a nitrogen dioxide gas (NO 2 gas), further pentoxide a portion of the nitrogen dioxide gas (NO 2 gas) by oxidation of ozone
- a gas adjustment unit that performs an oxidation output that is output as a measurement target gas reacted with dinitrogen gas (N 2 O 5 gas), and a normal output that is output as a measurement target gas without any reaction;
- a light emitting part for absorbing O 3 gas that irradiates irradiation light for absorbing O 3 gas having a wavelength
- c m is calculated,
- the gas conditioning unit by using a signal from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the oxidation output state, gas concentration c 3 of ozone (O 3 gas) To calculate The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the irradiation light for NO 2 gas absorption is emitted.
- NO 2 gas nitrogen dioxide gas
- c 2 is calculated, From the gas concentration c 0 of the ozone gas (O 3 gas) supplied, the gas concentration c 3 of the measured ozone (O 3 gas), the gas concentration in the reaction consumption calculated by subtracting the, in the gas as the object of measurement based on the equal to the gas concentration (c 1 + c 2 -c m ) / 2 gas concentration by adding gas concentration c 1 to nitric oxide gas (N 2 O 5 gas) of nitric oxide gas (NO gas)
- the gas analyzer was configured to calculate the gas concentration c 1 of nitric oxide gas (NO gas) from the calculated c 0 , c m , c 3 , c 2 .
- the present invention also provides: A gas analyzer that measures the concentration of three components of nitrogen monoxide gas (NO gas), nitrogen dioxide gas (NO 2 ), and sulfur dioxide gas (SO 2 gas) contained in a sample gas, All nitric oxide gas contained in the sample gas (NO gas) by oxidation of ozone reacted in a nitrogen dioxide gas (NO 2 gas), further pentoxide a portion of the nitrogen dioxide gas (NO 2 gas) by oxidation of ozone
- a gas adjustment unit that performs an oxidation output that is output as a measurement target gas reacted with dinitrogen gas (N 2 O 5 gas), and a normal output that is output as a measurement target gas without any reaction;
- a light emitting part for absorbing O 3 gas that irradiates light for absorbing O 3 gas
- the gas conditioning unit by using a signal from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the oxidation output state, gas concentration c 3 of ozone (O 3 gas) And the gas concentration c s of sulfur dioxide gas (SO 2 gas),
- the gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the irradiation light for NO 2 gas absorption is emitted.
- c 2 is calculated, The gas concentration of sulfur dioxide gas (SO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the O 3 gas absorption irradiation light is emitted.
- c s is calculated, From the gas concentration c 0 of the ozone gas (O 3 gas) supplied, the gas concentration c 3 of the measured ozone (O 3 gas), the gas concentration in the reaction consumption calculated by subtracting the, in the gas as the object of measurement Based on the gas concentration c 1 of nitrogen monoxide gas (NO gas) plus the gas concentration (c 1 + c 2 ⁇ c m ) / 2 of nitrous oxide (N 2 O 5 gas) / 2.
- the gas analyzer was configured to calculate the gas concentration c 1 of nitric oxide gas (NO gas) from the calculated c 0 , c m , c 3 , c 2 .
- a correction unit connected to the reference light receiving unit, the NO 2 gas absorbing light emitting unit, and the O 3 gas absorbing light emitting unit;
- the reference light receiving unit receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas partially reflected by the partial reflection unit, and outputs a detection signal to the correction unit,
- the correction unit may be a gas analyzer that outputs a drive current that suppresses fluctuations based on the detection signal to the NO 2 gas absorption light emission unit and the O 3 gas absorption light emission unit.
- Collecting the O 3 irradiation light gas absorption from the NO 2 lens and the O 3 gas absorption for the light emitting portion condenses the NO 2 gas absorption for the irradiation light from the gas absorption for the light emitting portion is incident on the gas flow cell
- a gas analyzer that includes a lens that emits light and enters the gas flow cell may be used.
- a light emitting unit that integrally accommodates the NO 2 gas absorbing light emitting unit and the O 3 gas absorbing light emitting unit adjacent to each other;
- a lens for incident condenses O 3 irradiation light gas absorption from the NO 2 NO 2 gas absorption irradiation light and the O 3 gas absorption for the light emitting portion of the gas absorption for the light emitting portion to the gas flow cell, It is good to make it a gas analyzer equipped with.
- the gas analyzer has a lens for collecting the irradiation light for absorbing NO 2 gas after passing through the gas circulation cell and the irradiation light for absorbing O 3 gas after passing through the gas circulation cell.
- the gas flow cell has a light transmission window on one side and a reflection part on the other side, and transmits the light transmission window and reflects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas at the reflection part.
- the transmitted light receiving unit detects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas reflected by the partial reflection unit so as to reciprocate in the detection space so as to pass through the light transmission window later.
- a good gas analyzer is recommended.
- a light emitting / receiving unit that integrally accommodates the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, and the transmitted light receiving unit adjacent to each other;
- the gas flow cell has a light transmission window on one side and a reflection part on the other side, The NO 2 gas absorption irradiation light and the O 3 gas absorption irradiation light emitted from the light emitting / receiving section through the light transmission window are reflected by the reflection section and then pass through the light transmission window to pass through the light transmission window.
- the gas analyzer may be configured such that the transmitted light receiving unit of the light emitting / receiving unit detects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas transmitted through the partial reflection unit.
- the signal processing / drive control unit is a pulse that alternately performs output and stop of the NO 2 gas absorption light-emitting unit and the O 3 gas absorption light-emitting unit, and has a duty ratio that makes the output shorter than the stop. It is better to use a gas analyzer that uses the drive current.
- a gas analyzer capable of measuring the gas concentrations of at least two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in a sample gas with a simple configuration. be able to.
- a gas analyzer that can measure the three component gas concentrations of sulfur dioxide gas (SO 2 gas), nitrogen monoxide gas (NO gas), and nitrogen dioxide gas (NO 2 gas).
- FIG. 3 is a wavelength-absorption coefficient characteristic diagram showing absorption coefficients of NO gas, NO 2 gas, SO 2 gas, and O 3 gas in the visible region and ultraviolet region. It is a whole block diagram of the gas analyzer which concerns on the other form for implementing this invention. It is a partial block diagram of the gas analyzer which concerns on the other form for implementing this invention. It is a partial block diagram of the gas analyzer which concerns on the other form for implementing this invention. It is a partial block diagram of the gas analyzer which concerns on the other form for implementing this invention. It is a partial block diagram of the gas analyzer which concerns on the other form for implementing this invention. It is a partial block diagram of the gas analyzer which concerns on the other form for implementing this invention. It is a partial block diagram of the gas analyzer which concerns on the other form for implementing this invention.
- FIG. 6 is a characteristic diagram showing a duty ratio-allowable current characteristic of a light emitting diode. It is explanatory drawing of the time change of the drive signal of the light emitting diode produced
- FIG. 4 is a wavelength-absorption coefficient characteristic diagram showing absorption coefficients of NO gas, NO 2 gas, and SO 2 gas in the visible region and the ultraviolet region.
- FIG. 1 is an overall configuration diagram of a gas analyzer according to this embodiment.
- the sample gas contains two components of nitrogen monoxide gas (hereinafter simply referred to as NO gas) and nitrogen dioxide gas (hereinafter simply referred to as NO 2 gas), but sulfur dioxide gas (hereinafter simply referred to as SO 2 gas). Shall not be included.
- the gas analyzer analyzes these NO gas and NO 2 gas.
- a thick solid arrow indicates a gas flow path
- a dotted arrow indicates a light path
- a thin solid arrow indicates an electrical signal path.
- the gas analyzer 100 includes an NO 2 gas absorbing light emitting unit 11, an O 3 gas absorbing light emitting unit 12, a partial reflecting unit 13, a gas flow cell 21, a transmitted light receiving unit 31, and a reference light receiving unit.
- Unit 32 gas adjustment unit 41, gas suction unit 51, and signal processing / drive control unit 61.
- the NO 2 gas absorption light emitting unit 11 is a light emitting unit that emits NO 2 gas absorption irradiation light having a wavelength at which NO 2 gas absorbs and a wavelength at which O 3 gas does not absorb.
- a light emitting diode (LED) of irradiation light having a central emission wavelength in a wavelength range of 350 nm to 500 nm in a region extending from ultraviolet light to visible light. As shown in FIG. 2, only NO 2 gas absorbs light in this wavelength region.
- O 3 light-emitting unit 12 for gas absorption is a light-emitting unit that O 3 gas emits O 3 gas absorption for the irradiation light of a wavelength absorption.
- O 3 gas emits O 3 gas absorption for the irradiation light of a wavelength absorption.
- a light emitting diode (LED) for irradiation light having a central emission wavelength in the wavelength range of 240 nm to 330 nm in the ultraviolet region can be selected.
- LED light emitting diode
- NO 2 gas absorbs in this wavelength region. It is not taken into account because no SO 2 gas is present.
- the partial reflection unit 13 is a half mirror, and has a predetermined transmittance for irradiation light for absorbing NO 2 gas and irradiation light for absorbing O 3 gas (hereinafter simply referred to as irradiation light for absorbing light for absorbing NO 2 gas and for absorbing O 3 gas). Both the irradiation light and the irradiation light for NO 2 gas absorption and the irradiation light for O 3 gas absorption are not output at the same time, for example, each is output separately by time). Further, the irradiation light is reflected at a predetermined reflectance.
- Irradiation light emitted from the NO 2 gas absorption light-emitting unit 11 and the O 3 gas absorption light-emitting unit 12 is incident on the partial reflection unit 13.
- the partial reflection unit 13 a part of the irradiation light is reflected and the rest of the irradiation light is transmitted.
- the irradiation light reflected by the partial reflection unit 13 enters the reference light receiving unit 32. Further, the irradiation light transmitted through the partial reflection portion 13 is incident on the gas flow cell 21.
- the gas distribution cell 21 further includes a tube 22, light transmission windows 23 and 24, a detection space 25, a gas inlet 26, and a gas outlet 27.
- the tube 22 is a cylinder.
- the inner surface of the tube 22 can be, for example, a polished stainless steel inner surface. Thereby, the reflectance of irradiation light can be kept favorable, preventing adsorption of measurement object gas. In the tube 22, the irradiation light propagates while being reflected by the inner surface of the tube 22.
- the light transmission window 23 and the light transmission window 24 are made of a material exhibiting light transmittance in the emission wavelength region of the irradiation light emitted from the NO 2 gas absorption light emitting portion 11 and the O 3 gas absorption light emission portion 12.
- synthetic quartz or calcium fluoride can be used as the material.
- the detection space 25 is a closed space defined by the tube 22, the light transmission window 23, and the light transmission window 24.
- the gas inlet 26 and the gas outlet 27 communicate with the detection space 25.
- the measurement target gas flows into the detection space 25 from the gas inlet 26 and flows out of the gas outlet 27.
- irradiation light is irradiated to the flowing measurement target gas, and light absorption occurs.
- the transmitted light receiving unit 31 receives the irradiation light transmitted through the gas flow cell 21 and outputs a detection signal corresponding to the light intensity.
- the transmitted light receiving unit 31 includes a photodiode or a photomultiplier tube having sensitivity to the emission wavelength of irradiation light emitted from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12. You can choose. For example, a silicon photodiode can be selected.
- Such a transmitted light receiving unit 31 has a function of detecting light absorption by the measurement target gas. That is, compared with the case where there is no light absorption due to the measurement target gas, the light intensity of the irradiation light received by the transmitted light receiving unit 31 decreases when there is light absorption.
- the gas concentration is measured using the correlation.
- the irradiation light transmitted through the partial reflection portion 13 passes through the light-transmitting light transmission window 23 constituting one end of the gas flow cell 21, propagates through the detection space 25 inside the tube 22, and constitutes the other end.
- the light is transmitted through the light transmissive window 24 and enters the transmitted light receiving unit 31.
- the reference light receiving unit 32 is provided to receive the irradiation light reflected by the partial reflection unit 13.
- the reference light receiving unit 32 includes a photodiode, a photomultiplier tube, or the like that is sensitive to the emission wavelength of the irradiation light emitted from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12. You can choose. For example, a silicon photodiode can be selected.
- the reference light receiving unit 32 has a function of detecting fluctuations in irradiation light emitted from the NO 2 gas absorbing light emitting unit 11 and the O 3 gas absorbing light emitting unit 12.
- the irradiation light varies, the light intensity of the irradiation light received by the reference light receiving unit 32 varies.
- the gas concentration is corrected using the fluctuation amount of the light intensity.
- the gas adjustment unit 41 further includes an ozone generation unit 42 and a gas mixing unit 43.
- the ozone generator 42 has a function of generating ozone gas. Atmosphere containing oxygen to the ozone generator 42, instrument air, or the raw material gas G O such as oxygen gas (O 2 gas) flows. The operation of the ozone generator 42 is controlled by a signal processing / drive controller 61. In operation of the ozone generator 42, ozone generator 42, by electrical means, such as silent discharge, using an O 2 gas of the raw material gas G O generates O 3 gas, sufficiently containing the O 3 gas The source gas GO is caused to flow out. In an off-state, the ozone generator 42 is directly passing the raw material gas G O without generating the O 3 gas. In this way, the signal processing / drive control unit 61 controls the operation / non-operation of the ozone generation unit 42.
- the signal processing / drive control unit 61 controls the operation / non-operation of the ozone generation unit 42.
- Gas mixing unit 43 at the time the raw material gas G O (operation from the sample gas G S and ozone generator 42 is a raw material gas G O containing O 3 gas in large quantities, also in an off-state free of O 3 gas is provided to mix the free feed gas is G O).
- the gas mixing unit 43 causes the gas mixing unit 43 to directly flow out as a measurement target gas.
- the measurement target gas flowing out from the gas mixing unit 43 flows through the detection space 25 in the gas flow cell 21 from the gas inlet 26 and flows out from the gas outlet 27.
- the gas suction unit 51 has a function of sucking gas.
- the measurement target gas from the gas mixing unit 43 is drawn into the detection space 25 by exhausting the detection space 25 of the gas flow cell 21.
- the gas suction part 51 can also be provided between the gas mixing part 43 and the gas inlet 26.
- the signal processing / drive control unit 61 has a function of supplying a driving current necessary for causing the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 to emit light. Further, the signal processing / drive control unit 61 has a received light signal processing function for calculating the gas concentration based on the received light signals from the transmitted light receiving unit 31 and the reference light receiving unit 32. Further, the signal processing / drive control unit 61 has a control function for switching operation / non-operation of the ozone generation unit 42.
- the configuration of the gas analyzer 100 is as described above.
- the principle of measurement is an absorption method based on the following Lambert-Beer law.
- P 1 is the output intensity of the transmitted light that has passed through the measurement target gas flowing in the detection space 25
- P 0 is the output intensity of the reference light before passing through the measurement target gas
- ⁇ is the molar extinction coefficient
- c is The gas concentration, L, represents the optical path length.
- the molar extinction coefficient ⁇ is uniquely determined by determining the type of gas and the wavelength of the light source, and since the optical path length L is constant, the ratio between the output intensities P 1 and P 0 is an exponential function of the gas concentration c.
- the output intensities P 1 and P 0 are measured, and the gas concentration is detected by the above equation ( 1).
- the gas analyzer 100 emits irradiation light that is either NO 2 gas absorption irradiation light or O 3 gas absorption irradiation light.
- a part of the irradiation light at this time is reflected by the partial reflection unit 13 with a known constant reflectance and is incident on the reference light receiving unit 32.
- the output intensity P 0 by the reference light can be obtained from the signal of the reference light receiving unit 32.
- a part of the irradiation light is transmitted through the partial reflection unit 13 with a known constant transmittance, propagates through the detection space 25 through the light transmission window 23, and is transmitted through the light transmission window 24 after being absorbed. The light enters the light receiving unit 31.
- the output intensity P 1 by the transmitted light can be obtained from the signal of the transmitted light receiving unit 31. Therefore, the gas concentration c can be obtained from the ratio between the output intensities P 1 and P 0 .
- This principle can be applied to both the analysis using the irradiation light for absorbing NO 2 gas and the analysis using the irradiation light for absorbing O 3 gas. The detection principle is like this.
- the transmitted light receiving unit 31 and the reference light receiving unit 32 are commonly used when measuring the NO 2 gas concentration and the O 3 gas concentration. Therefore, if the NO 2 gas absorption light-emitting unit 11 and the O 3 gas absorption light-emitting unit 12 emit light at the same time, the light reception signal becomes the sum of the two and cannot be separated.
- the signal processing / drive control unit 61 controls the NO 2 gas absorption light-emitting unit 11 and the O 3 gas absorption light-emitting unit 12 to alternately emit light without simultaneously emitting light. Further, the measurement and processing of the received light signal are also performed in synchronization with the light emission period, thereby separating the signals. Measurement by absorption is like this.
- Such measurement is performed when the ozone generation unit 42 is in an operating state and the gas adjustment unit 41 is in an oxidized output, and when the ozone generation unit 42 is in a non-operational state and the gas adjustment unit 41 is in a normal output.
- a gas analyzer 100 is (A) Analysis with irradiation light for absorbing NO 2 gas at the time of oxidation output, (B) Analysis by irradiation light for absorbing O 3 gas at the time of oxidation output, (C) Analysis with irradiation light for absorbing NO 2 gas at normal output, (D) Normal analysis by the O 3 gas absorption for the irradiation light at the time of output, Four types of analysis are possible.
- the ozone generator 42 is in an operating state. At this time, the ozone generating unit 42 generates ozone gas (hereinafter simply referred to as O 3 gas) from O 2 gas contained in the source gas G 0 such as the atmosphere, instrument air, or oxygen gas. Although the generation amount of O 3 gas can be determined as appropriate, it is supplied in excess of at least the maximum amount in the measured concentration range of NO gas. From the ozone generator 42 to the gas mixing unit 43 supplies the raw material gas G O containing O 3 gas sufficiently.
- O 3 gas ozone gas
- O 3 gas amount supplied from the ozone generator 42 is, because it is excessive relative to NO gas amount in the sample gas G S, NO gas in the sample gas G S is according to the chemical reaction formula (1), All are converted to NO 2 gas.
- the gas mixing unit 43 and converted all NO gas in the sample gas G S is the NO 2 gas.
- some of the NO 2 gas in the sample gas G S, and, in some NO 2 gas produced by a chemical reaction formula (1) is converted to N 2 O 5 gas. Therefore, the amount of gas NO 2 gas, and NO 2 gas in the gas amount produced from NO in the sample gas G S, the sum of the amount of gas NO 2 gas in the sample gas G S, further N 2 O 5 The amount of gas is reduced by twice the amount of gas. This is because the amount of N 2 O 5 gas after the reaction is half of the amount of NO 2 gas according to the chemical reaction formula (2). Furthermore, a part of the surplus O 3 gas remains.
- the gas conditioning unit 41 as performs oxidation output for outputting a NO gas contained in the sample gas G S as a measurement object gas reacted to all oxidized NO 2 gas by the O 3 gas.
- a NO gas contained in the sample gas G S as a measurement object gas reacted to all oxidized NO 2 gas by the O 3 gas.
- NO 2 gas, N 2 O 5 gas, excess O 3 gas, the measurement object gas containing the raw material gas G O and excess sample gas G S excess is introduced into the gas flow cell 21.
- NO 2 irradiation light gas absorption incident on the detection space 25 of the passes through the partial reflection unit 13 light transmissive window 23 via a gas flow cell 21, while propagating the detection space 25, absorption by NO 2 gas Is done.
- Such absorbed light for absorbing NO 2 gas passes through the light transmission window 24 and enters the transmitted light receiving unit 31. Therefore, the output intensity P 1 can be obtained from the signal of the transmitted light receiving unit 31.
- the transmitted light receiving unit 31 and the reference light receiving unit 32 as the light receiving elements in this way, not only can the concentration be measured, but also the output of the NO 2 gas absorbing light emitting unit 11 varies due to various factors. Also, there is an effect that an error in density measurement can be reduced by calculating the ratio of the two received light signals.
- Output signals from the transmitted light receiving unit 31 and the reference light receiving unit 32 are transmitted to the signal processing / drive control unit 61.
- the signal processing / drive control unit 61 calculates the NO 2 gas concentration in the detection space 25 of the gas flow cell 21 based on the above mathematical formula 1. Since the raw material gas G O for producing O 3 gas is mixed in the gas mixing unit 43, NO 2 gas concentration is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S Yes. Therefore, by multiplying the flow mixing ratio of a gas mixing section 43, calculates the NO 2 gas concentration c m contained in the sample gas G S.
- the O 3 gas absorption light emitting unit 12 emits light. Irradiation light for absorbing O 3 gas from the light emitting unit 12 for absorbing O 3 gas is reflected by the partial reflection unit 13 with a known constant reflectance and enters the reference light receiving unit 32. Therefore, the output intensity P 0 can be obtained from the signal from the reference light receiving unit 32.
- the irradiation light for absorbing O 3 gas that has passed through the partial reflection portion 13 and entered the detection space 25 in the gas flow cell 21 through the light transmission window 23 propagates through the detection space 25, while O 3 gas and NO. Absorbed by two gases.
- Such absorbed light for absorbing O 3 gas is transmitted through the light transmission window 24 and enters the transmitted light receiving unit 31. Therefore, it is possible to determine the output intensity P 1 from the signal of the transmitted light receiving unit 31.
- the output intensity P 1 includes light absorption by NO 2 gas.
- the transmitted light receiving unit 31 and the reference light receiving unit 32 as the light receiving elements in this way, not only can the concentration be measured, but the output of the light emitting unit 12 for absorbing O 3 gas varies due to various factors. Also, there is an effect that an error in density measurement can be reduced by calculating the ratio of the two received light signals.
- Output signals from the transmitted light receiving unit 31 and the reference light receiving unit 32 are transmitted to the signal processing / drive control unit 61.
- the signal processing / drive control unit 61 calculates the output intensities P 0 and P 1 , calculates the O 3 gas concentration + NO 2 gas concentration based on Equation 1, and multiplies the flow rate mixing ratio in the gas mixing unit 43. by, O 3 calculates the gas concentration c 3 + NO 2 gas concentration c m contained in the sample gas G S.
- the measurement is performed after the ozone generating unit 42 is in an inoperative state and the gas adjusting unit 41 is normally output.
- the ozone generator 42 is in an inoperative state. At this time, the raw material gas G O is passes through the ozone generator 42 as described above, is mixed with the sample gas G S in the gas mixing portion 43. O 3 never since the gas is not present chemical reaction occurs, and the raw material gas G O and the sample gas G S-free reaction as it flows out from the gas mixing unit 43. Gas conditioning unit 41 performs a normal output that outputs the sample gas G S and the raw material gas G O unresponsive as a measurement target gas.
- the detection of the gas concentration itself is obtained in the same manner as the operation of the ozone generator 42 described above (during oxidation output). In this way, the NO 2 gas concentration c 2 is calculated.
- the NO 2 gas concentration c m oxidation output state, of the measurement target gas, from the sum of the sample gas G of the original that was included in the S NO gas concentration c 1 and the original NO 2 gas concentration c 2 The concentration obtained by subtracting twice the N 2 O 5 gas concentration. This is because the production of N 2 O 5 requires two NO 2 .
- the N 2 O 5 gas concentration is 1 ⁇ 2 of the concentration obtained by subtracting the NO 2 gas concentration cm from the sum of the original NO gas concentration c 1 and the original NO 2 gas concentration c 2 .
- the O 3 gas concentration supplied by the ozone generator 42 can be known in advance by an ozone meter or the like built in the ozone generator 42, and the value is c 0 .
- the O 3 gas consumed by the reaction is used for a reaction from NO gas to NO 2 gas, and further used for a reaction from NO 2 gas to N 2 O 5 gas. Therefore, the following equation is obtained.
- the NO gas concentration c 1 is expressed by the following equation.
- the NO gas concentration c 1 and the NO 2 gas concentration c 2 can be measured.
- the gas concentrations of NO gas and NO 2 can be measured.
- zero gas G ZERO or span gas G SPAN can be used for gas concentration calibration.
- the zero gas G ZERO is a gas in which the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 do not absorb light, for example, nitrogen gas (N 2 gas).
- Span gas G SPAN is a gas that has been calibrated at a maximum concentration value of the desired measurement range, such as NO gas, NO 2 gas is used.
- Stopping the supply of the sample gas G S, followed by performing the supply of the zero gas G ZERO calibrated by measuring the light signal at the zero gas G ZERO distribution, or at the time span G SPAN flow by performing the supply of the span gas G SPAN Calibration can be performed by measuring the absorbed light-receiving signal. Although this calibration can be performed at any time, it is performed when it is assumed that the gas concentration indicating value fluctuates due to aging of the component parts, and an accurate value is indicated.
- the gas analyzer 100 is like this.
- the configuration as a gas analyzer is the same as that of the first embodiment described with reference to FIG. 1, but the analysis object is different.
- the NO gas concentration c 1 and the NO 2 gas concentration c 2 are calculated, but the SO 2 gas concentration c S is measured simultaneously with the above measurement.
- the sample gas contains NO gas, NO 2 gas, and SO 2 gas, and these NO gas concentration c 1 , NO 2 gas concentration c 2 , and SO 2 gas concentration c S are measured.
- UV absorption spectrum of the SO 2 gas is near 270 nm ⁇ 310 nm, as shown in FIG. 2, overlaps the ultraviolet absorption spectrum of the O 3 gas.
- the central wavelength of the O 3 gas light-absorbing light emitting portion 12 is around 280 nm, an SO 2 gas absorption signal can be obtained.
- Such measurement is performed when the ozone generation unit 42 is in an operating state and the gas adjustment unit 41 is in an oxidized output, and when the ozone generation unit 42 is in a non-operational state and the gas adjustment unit 41 is in a normal output. Is called.
- such a gas analyzer 100 is (A) Analysis with irradiation light for absorbing NO 2 gas at the time of oxidation output, (B) analysis by the O 3 gas absorption for the irradiation light at the time of oxidation output, (C) Analysis with irradiation light for absorbing NO 2 gas at normal output, (D) Analysis with irradiation light for absorbing O 3 gas at normal output,
- A Analysis with irradiation light for absorbing NO 2 gas at the time of oxidation output
- B analysis by the O 3 gas absorption for the irradiation light at the time of oxidation output
- C Analysis with irradiation light for absorbing NO 2 gas at normal output
- D Analysis with irradiation light for absorbing O 3 gas at normal output
- the following four types of analysis are possible: (a), (b), (c), and (d) are all analyzed, and the gas concentration is calculated using the measured values obtained by these.
- the ozone generator 42 is in an operating state.
- Gas conditioning unit 41 as described above this time, an oxidation output for outputting a NO gas contained in the sample gas G S as a measurement object gas reacted to all oxidized NO 2 gas by the O 3 gas.
- the SO 2 gas and the O 3 gas do not cause a chemical reaction.
- Such as these SO 2 gas, NO 2 gas is introduced into the N 2 O 5 gas, excess O 3 gas, the excess of the raw material gas G O and excess sample gas G S measurement target gas is gas flow cell 21 comprising The
- NO 2 gas concentration cm of the gas analyzer 100 is calculated.
- NO 2 gas concentration measurement emits light only NO 2 gas absorption for the light emitting unit 11.
- NO 2 irradiation light gas absorption from NO 2 gas absorption for the light emitting unit 11 is reflected by the known constant reflectivity by the partial reflection unit 13 and enters the reference light receiving unit 32. Therefore, the output intensity P 0 can be obtained from the signal from the reference light receiving unit 32.
- NO 2 irradiation light gas absorption incident on the detection space 25 of the passes through the partial reflection unit 13 light transmissive window 23 via a gas flow cell 21, while propagating the detection space 25, absorption by NO 2 gas Is done.
- Such absorbed light for absorbing NO 2 gas passes through the light transmission window 24 and enters the transmitted light receiving unit 31. Therefore, the output intensity P 1 can be obtained from the signal of the transmitted light receiving unit 31.
- Output signals from the transmitted light receiving unit 31 and the reference light receiving unit 32 are transmitted to the signal processing / drive control unit 61.
- the signal processing / drive control unit 61 calculates the NO 2 gas concentration in the detection space 25 of the gas flow cell 21 based on the above mathematical formula 1. Since the raw material gas G O for producing O 3 gas is mixed in the gas mixing unit 43, NO 2 gas concentration is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S Yes. Therefore, by multiplying the flow mixing ratio of a gas mixing section 43, calculates the NO 2 gas concentration c m contained in the sample gas G S.
- the O 3 gas absorption light emitting unit 12 emits light. Irradiation light for absorbing O 3 gas from the light emitting unit 12 for absorbing O 3 gas is reflected by the partial reflection unit 13 with a known constant reflectance and enters the reference light receiving unit 32. Therefore, the output intensity P 0 can be obtained from the signal from the reference light receiving unit 32.
- O 3 irradiation light gas absorption incident on the detection space 25 in the gas flow cell 21 passes through the partial reflection unit 13 through the light transmission window 23, while propagating the detection space 25, SO 2 gas, O Absorbed by 3 gas and NO 2 gas.
- Such absorbed light for absorbing O 3 gas is transmitted through the light transmission window 24 and enters the transmitted light receiving unit 31. Therefore, the output intensity P 1 can be obtained from the signal of the transmitted light receiving unit 31.
- the output intensity P 1 includes light absorption by SO 2 gas, O 3 gas and NO 2 gas.
- Output signals from the transmitted light receiving unit 31 and the reference light receiving unit 32 are transmitted to the signal processing / drive control unit 61.
- the signal processing / drive control unit 61 calculates the output intensities P 0 and P 1 , calculates the O 3 gas concentration + SO 2 gas concentration + NO 2 gas concentration based on Equation 1, and further mixes the flow rate in the gas mixing unit 43. by multiplying the ratio to calculate the sample gas G O 3 gas concentration is being included in the S c 3 + SO 2 gas concentration c S + NO 2 gas concentration c m.
- the measurement is performed after the ozone generating unit 42 is in an inoperative state and the gas adjusting unit 41 is normally output.
- the ozone generator 42 is in an inoperative state.
- This state gas contained in the sample gas G S that circulates in the gas flow cell 21, NO gas contained in the sample gas G S, NO 2 gas, SO 2 gas has become all intact state.
- the raw material gas G O are mixed in the gas mixing portion 43, the concentration of NO gas, NO 2 gas, SO 2 gas is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S ing. And such feed gas G O and the sample gas G S is introduced into the gas flow cell 21.
- the gas concentration detection itself is obtained in the same manner as the operation of the ozone generator 42 described above (at the time of oxidation output), and the NO 2 gas concentration is calculated. Further, by multiplying the flow mixing ratio of a gas mixing section 43, it calculates the NO 2 gas concentration c 2 contained in the sample gas G S.
- the measurement is performed after the ozone generating unit 42 is in an inoperative state and the gas adjusting unit 41 is normally output. At this time, obtaining the SO 2 gas concentration c S + NO 2 gas concentration c 2 in the sample gas G S. This is the analysis by the above (d) irradiation light for absorbing O 3 gas at normal output.
- the ozone generator 42 is in an inoperative state.
- This state gas contained in the sample gas G S that circulates in the gas flow cell 21, NO gas contained in the sample gas G S, NO 2 gas, SO 2 gas has become all intact state.
- the raw material gas G O are mixed in the gas mixing portion 43, the concentration of NO gas, NO 2 gas, SO 2 gas is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S ing. And such feed gas G O and the sample gas G S is introduced into the gas flow cell 21.
- the gas concentration detection itself is obtained in the same manner as described above, and the SO 2 gas concentration + NO 2 gas concentration is calculated. Further, by multiplying the flow mixing ratio of a gas mixing section 43, and calculates the SO 2 gas concentration c S + NO 2 gas concentration c 2 contained in the sample gas G S.
- the SO 2 gas concentration c S is determined.
- the O 3 gas concentration c 3 is determined.
- the NO gas concentration c 1 is also expressed by the above [Equation 5].
- the NO gas concentration c 1 , the NO 2 gas concentration c 2 , and the SO 2 gas concentration c S can be measured.
- the gas concentrations of NO gas, NO 2 gas, and SO 2 gas can be measured.
- zero gas G ZERO or span gas G SPAN can be used for gas concentration calibration.
- Zero gas G ZERO is a gas, for example, nitrogen gas, in which the NO 2 gas absorption light-emitting unit 11 and the O 3 gas absorption light-emitting unit 12 do not absorb light.
- the span gas G SPAN is a gas calibrated with the maximum concentration value of a desired measurement range, and for example, NO, NO 2 , SO 2 gas is used.
- Stopping the supply of the sample gas G S, followed by performing the supply of the zero gas G ZERO calibrated by measuring the light signal at the zero gas G ZERO distribution, or at the time span G SPAN flow by performing the supply of the span gas G SPAN Calibration can be performed by measuring the absorbed light-receiving signal. Although this calibration can be performed at any time, it is performed when it is assumed that the gas concentration indicating value fluctuates due to aging of the component parts, and an accurate value is indicated.
- the gas analyzer 100 is like this.
- the gas analyzer 100 performs the analysis in this way. According to the present invention, the gas concentrations of NO gas, NO 2 gas, and SO 2 gas can be accurately measured with a simple configuration.
- the gas analyzer 200 includes a light emitting unit 11 for absorbing NO 2 gas, a light emitting unit 12 for absorbing O 3 gas, a partial reflecting unit 13, a gas flow cell 21, a transmitted light receiving unit 31, and a reference light receiving unit.
- Unit 32 gas adjustment unit 41, gas suction unit 51, signal processing / drive control unit 61, and correction unit 71.
- correction unit 71 is added.
- the correction unit 71 and its operation will be described with emphasis, and the other components will be assigned the same numbers and redundant description will be omitted.
- the correction unit 71 is connected to the reference light receiving unit 32, the signal processing / drive control unit 61, the NO 2 gas absorption light emitting unit 11, and the O 3 gas absorption light emitting unit 12. Based on this, it has a function of correcting the current for driving the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12.
- Reference-light receiving part 32 by receiving the reference light by NO 2 gas absorption for the irradiation light from the NO 2 gas absorption for the light emitting unit 11 and outputs the intensity signal. Based on the intensity signal, the correction unit 71 corrects and outputs the drive signal, which is a light emitting diode drive current, so that the output intensity is constant.
- the reference light receiving unit 32 by receiving the reference light by the O 3 gas absorption for the irradiation light from the O 3 gas absorption for the light emitting unit 12 and outputs the intensity signal. Based on the intensity signal, the correction unit 71 corrects and outputs the drive signal, which is a light emitting diode drive current, so that the output intensity is constant.
- a lens 14 is further provided on the optical axis of the NO 2 gas absorption light emitting unit 11, and O 3
- a lens 15 is provided on the optical axis of the gas absorption light emitting unit 12.
- NO 2 gas light-absorbing light-emitting unit 11 and the lens 14 may be integrally configured by modularization
- O 3 gas light-absorbing light-emitting unit 12 and the lens 15 may be integrally configured by modularization
- the light emitting portion 16 is arranged in place of NO 2 gas absorption for the light emitting portion 11 and the O 3 light-emitting unit 12 for gas absorption.
- the light emitting unit 16 is a light emitting diode array in which the NO 2 gas absorbing light emitting unit 11 and the O 3 gas absorbing light emitting unit 12 are integrated in close proximity.
- a lens 17 is disposed on the optical axis of the light emitting unit 11 for absorbing NO 2 gas and the light emitting unit 12 for absorbing O 3 gas.
- the optical axes of the NO 2 gas absorbing light emitting portion 11 and the O 3 gas absorbing light emitting portion 12 are close to each other, so that only one lens 17 for enhancing directivity is required. Further, since the optical axes are close to each other, the incident efficiency to the reference light receiving unit 32 is also improved. As a result, there is an effect that the signal intensity is increased, and consequently the accuracy and stability of the gas concentration measurement are improved.
- the lens 18 is further disposed between the light transmitting window 24 and the transmitted light receiving unit 31. It is arranged.
- the lens 18 collects the NO 2 gas absorption irradiation light and the O 3 gas absorption irradiation light transmitted through the light transmission window 24, and efficiently enters the transmitted light receiving unit 31. As a result, there is an effect that the signal intensity is increased, and consequently the accuracy and stability of the gas concentration measurement are improved.
- the light transmission window 24 and the lens 18 may be integrally configured by modularization.
- the light transmission window 24 itself may be a convex lens 18 that is light transmissive and has a light collecting effect, and the gas flow cell 21 may be configured by fixing the lens 18 to the tube 22.
- the light transmission window 24 of the gas flow cell 21 is replaced with a reflection part 28, and the transmitted light receiving part 31 is arranged at a position where the return light is reflected by the partial reflection part 13.
- forward light that is irradiation light emitted from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 passes through the light transmission window 23 and propagates in the detection space 25 of the tube 22. Then, the light is reflected by the reflecting portion 28 and becomes return path light. The reflected return light propagates in the detection space 25 of the tube 22 in the opposite direction, exits from the light transmission window 23, is reflected by the partial reflection unit 13, and enters the transmitted light receiving unit 31.
- the optical path length with light absorption by gas is doubled, so that the light absorption signal is improved and the gas concentration measurement accuracy is improved. And can improve the stability.
- FIG. 1 This is provided with a light emitting / receiving part 19 integrated by modularization while bringing the NO 2 gas absorbing light emitting part 11, the O 3 gas absorbing light emitting part 12 and the transmitted light receiving part 31 close to each other. Further, the light transmission window 24 of the gas flow cell 21 is replaced with the reflection portion 28, and the transmitted light receiving portion 31 is disposed at a position where the return light is transmitted by the partial reflection portion 13.
- the lens 17 condenses the irradiation light incident on the transmitted light receiving unit 31 and the function of increasing the directivity of the irradiation light from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12. It will have the function to do. Further, since the optical path length with light absorption by gas is doubled, it is possible to expect the effect of improving the light absorption signal and improving the accuracy and stability of gas concentration measurement.
- FIG. 9 is a duty ratio-allowable current characteristic diagram of the light emitting diode. This embodiment further improves the measurement accuracy of the gas analyzers of the first, second, third, fourth, fifth, sixth, and seventh embodiments described above.
- the allowable current of the light emitting diode is characterized in that, generally, the smaller the duty ratio and the shorter the output period, the larger the current value can be secured. Therefore, the drive current of the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 is changed from a large duty ratio as shown in FIG. 10 to a small duty ratio as shown in FIG. Shorter). At this time, the output time is shortened as shown in FIG. 11, but the drive current value can be increased. Therefore, the output intensity of the irradiation light can be increased to ensure a high signal level, the signal level against noise is relatively high, and a stable gas concentration value can be calculated.
- the light emission time of the light emitting diode 11 for absorbing NO 2 gas and the light emitting portion 12 for absorbing O 3 gas can be shortened, deterioration due to heat or the like is suppressed, and the lifetime is longer than that of continuous light emission. It becomes possible to keep for a long time.
- Such a gas analyzer of the present invention comprises two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 ), or nitrogen monoxide gas (NO gas), nitrogen dioxide gas (NO 2 ) and It is good for analysis for measuring three components of sulfur dioxide gas (SO 2 ), and is optimal for measurement of combustion exhaust gas such as boiler and garbage incineration.
- NO gas nitrogen monoxide gas
- NO 2 nitrogen dioxide gas
- SO 2 sulfur dioxide gas
- gas analysis for steel blast furnace, converter, heat treatment furnace, sintering (pellet equipment), coke oven], fruit and vegetable storage and ripening, biochemistry (microorganism) [fermentation], air pollution [incinerator, flue gas desulfurization / Denitration], exhaust gas (removal tester) of internal combustion engines such as automobiles and ships, disaster prevention [explosive gas detection, toxic gas detection, new building material combustion gas analysis], plant growth, chemical analysis [oil refinery plant, petrochemical Plants, gas generation plants], environmental [landing concentration, concentration in tunnels, parking lots, building management], and analytical instruments for various physics and chemistry experiments.
Abstract
Provided is a gas analyzer capable of measuring, by a simple configuration, the gas concentration of two components including nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO2 gas), or three components also including sulfur dioxide gas (SO2 gas), included in a sample gas. A gas analyzer for calculating the gas concentration c1 of nitrogen monoxide gas (NO gas) from a calculated c0, cm, c3, and c2 on the basis of the gas concentration at the time of reaction consumption calculated by subtracting the measured gas concentration c3 of ozone gas (O3 gas) from the gas concentration c0 of supplied ozone gas (O3 gas) being equal to the gas concentration obtained by adding the gas concentration (c1 + c2 – cm)/2 of dinitrogen pentoxide gas (N2O5 gas) to the gas concentration c1 of nitrogen monoxide gas (NO gas) in a measurement subject gas.
Description
本発明は、サンプルガスに含まれる複数ガスのガス濃度を測定するガス分析計に関する。
The present invention relates to a gas analyzer that measures gas concentrations of a plurality of gases contained in a sample gas.
ガス分析計の従来技術が、例えば、特許文献１に開示されている。この従来技術について、図を参照しつつ説明する。図１２は、特許文献１に記載の従来技術の吸光分析計である。
吸光分析計３００は、サンプルガスに含まれるＮＯ２ガス（二酸化窒素ガス）濃度を紫外吸収法により測定する。吸光分析計３００は、紫外光源３０１と、可視光源３０２と、リファレンスセル３０３と、サンプルセル３０４と、光案内機構３０５と、光検出部３０６と、制御部３０７と、演算部３０８と、を備えている。 For example,Patent Literature 1 discloses a conventional gas analyzer. This prior art will be described with reference to the drawings. FIG. 12 is a conventional absorption spectrometer described in Patent Document 1. In FIG.
Theabsorption spectrometer 300 measures the concentration of NO 2 gas (nitrogen dioxide gas) contained in the sample gas by the ultraviolet absorption method. The absorption spectrometer 300 includes an ultraviolet light source 301, a visible light source 302, a reference cell 303, a sample cell 304, a light guide mechanism 305, a light detection unit 306, a control unit 307, and a calculation unit 308. ing.
吸光分析計３００は、サンプルガスに含まれるＮＯ２ガス（二酸化窒素ガス）濃度を紫外吸収法により測定する。吸光分析計３００は、紫外光源３０１と、可視光源３０２と、リファレンスセル３０３と、サンプルセル３０４と、光案内機構３０５と、光検出部３０６と、制御部３０７と、演算部３０８と、を備えている。 For example,
The
紫外光源３０１は、紫外光を発光する発光ダイオードである。この紫外光の中心発光波長は波長３６０～４００ｎｍであり、図１３の波長－吸光係数特性図で示すように、ＮＯ２ガスの吸光波長帯域内に含まれる。このような紫外光をＮＯ２ガスに照射すると、ＮＯ２ガスによる吸光が行われる。
The ultraviolet light source 301 is a light emitting diode that emits ultraviolet light. The central emission wavelength of the ultraviolet light is 360 to 400 nm, and is included in the absorption wavelength band of NO 2 gas as shown in the wavelength-absorption coefficient characteristic diagram of FIG. Upon irradiation of such ultraviolet light to NO 2 gas, absorption by NO 2 gas.
可視光源３０２は、可視光を発光する発光ダイオードである。この可視光の中心発光波長は、紫外光の波長よりも大きく、図１３の波長－吸光係数特性図で示すように、ＮＯ２ガスの吸光波長帯域内に含まれるが、紫外光の中心波長とは異なる。このような可視光をＮＯ２ガスに照射するとＮＯ２ガスによる吸光が行われるが、上記のＮＯ２ガスによる紫外光の吸光と比較すると、ＮＯ２ガスによる可視光の吸光が小さくなるように、可視光源３０２の波長が設定される。
The visible light source 302 is a light emitting diode that emits visible light. The central emission wavelength of visible light is larger than the wavelength of ultraviolet light and is included in the absorption wavelength band of NO 2 gas as shown in the wavelength-absorption coefficient characteristic diagram of FIG. Is different. As such it absorbance of visible light by the NO 2 gas is irradiated to NO 2 gas is carried out, when compared with the absorption of ultraviolet light by the above-mentioned NO 2 gas, the absorbance of visible light is reduced by the NO 2 gas, The wavelength of the visible light source 302 is set.
リファレンスセル３０３は、基準ガスが封入されている。この基準ガスは例えば窒素ガスである。窓３０３ａ、３０３ｂを通じて紫外光や可視光が入射される。
The reference cell 303 is filled with a reference gas. This reference gas is, for example, nitrogen gas. Ultraviolet light or visible light is incident through the windows 303a and 303b.
サンプルセル３０４は、測定対象であるサンプルガスが供給される。窓３０４ａ、３０４ｂを通じて紫外光や可視光が入射される。サンプルガスは、ガス入口３０４ｃを通じてサンプルセル３０４内に流入し、ガス出口３０４ｄを通じて流出する。
The sample cell 304 is supplied with a sample gas that is a measurement target. Ultraviolet light or visible light is incident through the windows 304a and 304b. The sample gas flows into the sample cell 304 through the gas inlet 304c and flows out through the gas outlet 304d.
光案内機構３０５は、ミラー３０５ａ、ハーフミラー３０５ｂを備える。紫外光源３０１からの紫外光や可視光源３０２からの可視光がハーフミラー３０５ｂおよびミラー３０５ａで反射し、リファレンスセル３０３の窓３０３ａを介してリファレンスセル３０３内に一端側から導入される。また、紫外光源３０１からの紫外光や可視光源３０２からの可視光が、ハーフミラー３０５ｂを透過し、サンプルセル３０４の窓３０４ａを介してサンプルセル３０４内に一端側から導入される。サンプルセル３０４内ではＮＯ２ガスによる吸光が行われる。
The light guide mechanism 305 includes a mirror 305a and a half mirror 305b. The ultraviolet light from the ultraviolet light source 301 and the visible light from the visible light source 302 are reflected by the half mirror 305b and the mirror 305a and introduced into the reference cell 303 from one end side through the window 303a of the reference cell 303. Also, ultraviolet light from the ultraviolet light source 301 and visible light from the visible light source 302 are transmitted through the half mirror 305 b and introduced into the sample cell 304 from one end side through the window 304 a of the sample cell 304. In the sample cell 304, absorption by NO 2 gas is performed.
光検出部３０６は、光検出器３０６ａ、３０６ｂを備える。光検出器３０６ａは、リファレンスセル３０３の他端側に設けられ、このリファレンスセル３０３の窓３０３ｂを透過した紫外光や可視光を検出する。光検出器３０６ｂは、サンプルセル３０４の他端側に設けられ、サンプルセル３０４の窓３０４ｂを透過した紫外光や可視光を検出する。
The light detection unit 306 includes light detectors 306a and 306b. The photodetector 306a is provided on the other end side of the reference cell 303, and detects ultraviolet light or visible light transmitted through the window 303b of the reference cell 303. The photodetector 306b is provided on the other end side of the sample cell 304, and detects ultraviolet light and visible light transmitted through the window 304b of the sample cell 304.
制御部３０７は、紫外光源３０１および可視光源３０２を時分割発光させる。光検出部３０６は、リファレンスセル３０３およびサンプルセル３０４を透過する２波長の透過光を得る。これにより二光路、二波長を有することとなり、紫外透過光のサンプル信号、可視透過光のサンプル信号、紫外透過光のリファレンス信号、および、可視透過光のリファレンス信号という４つの信号を得る。
The control unit 307 causes the ultraviolet light source 301 and the visible light source 302 to emit light in a time-sharing manner. The light detection unit 306 obtains two-wavelength transmitted light that passes through the reference cell 303 and the sample cell 304. As a result, there are two optical paths and two wavelengths, and four signals are obtained: a sample signal for ultraviolet transmitted light, a sample signal for visible transmitted light, a reference signal for ultraviolet transmitted light, and a reference signal for visible transmitted light.
演算部３０８は、光検出部３０６からの４つの信号を制御部３０７経由で受信し、この４つの信号に基づいてＮＯ２ガス濃度を演算する。これにより、紫外光源３０１および可視光源３０２のドリフトの補償、測定成分以外の他成分干渉の補正、サンプルセル３０４の透過窓３０４ａ、３０４ｂの汚れや曇りによる光量低下の補正、感度ドリフトの補正、を可能とする。これら補正を行った上でＮＯ２ガス濃度を算出することができ、測定精度を向上させている。
The calculation unit 308 receives the four signals from the light detection unit 306 via the control unit 307, and calculates the NO 2 gas concentration based on the four signals. Thereby, compensation of drift of the ultraviolet light source 301 and the visible light source 302, correction of interference of other components other than the measurement component, correction of light amount decrease due to dirt and clouding of the transmission windows 304a and 304b of the sample cell 304, correction of sensitivity drift, Make it possible. The NO 2 gas concentration can be calculated after performing these corrections, and the measurement accuracy is improved.
しかしながら、上記の従来技術は、測定可能なガス成分が１種類に限られていた。したがって、２種類以上のガスの濃度を吸光法によって測定するためには、あるガスを吸光する波長を発光する発光手段と、この光を受光する受光手段と、が、それぞれガス別に複数個必要となる。このように従来技術では２種類以上のガスの濃度を測定するには、構成が多くなるという課題があった。
However, in the above-described conventional technology, the measurable gas component is limited to one type. Therefore, in order to measure the concentration of two or more kinds of gases by the absorption method, a plurality of light emitting means for emitting a wavelength for absorbing a certain gas and a plurality of light receiving means for receiving the light are required for each gas. Become. Thus, in the prior art, there is a problem that the configuration increases in order to measure the concentration of two or more kinds of gases.
また、従来技術では、測定しようとするガスが１種類であっても、ＳＯ２ガス（二酸化硫黄ガス）やＮＯガス（一酸化窒素ガス）を測定できなかった。例えば図１３に示すように、紫外波長領域のＮＯガスの吸光では、ＳＯ２ガスおよびＮＯ２ガスの吸光もあり、他のガスの影響を受ける。また、紫外波長領域のＳＯ２ガスの吸光では、ＮＯ２ガスの吸光もあり、他のガスの影響を受ける。
Further, in the prior art, even if there is only one kind of gas to be measured, SO 2 gas (sulfur dioxide gas) and NO gas (nitrogen monoxide gas) cannot be measured. For example, as shown in FIG. 13, the absorption of NO gas in the ultraviolet wavelength region includes the absorption of SO 2 gas and NO 2 gas, and is affected by other gases. Further, in the absorption of SO 2 gas in the ultraviolet wavelength region, there is also absorption of NO 2 gas, which is influenced by other gases.
さらに、可視波長領域（波長４００ｎｍ以上）のＮＯ２ガスの吸光波長では、ＮＯガスおよびＳＯ２ガスの吸光はなく、可視透過光にＮＯガスおよびＳＯ２ガスについての情報が含まれていない。したがって、ＮＯガスやＳＯ２ガスによる干渉を補正すること、または、ＮＯガスやＳＯ２ガスの濃度測定に利用することが不可能である。
このようにサンプルガスにＮＯガスおよびＳＯ２ガスのガス成分が含まれている場合には、従来技術では、これらのＮＯガスおよびＳＯ２ガスのガス成分の分析が困難であった。 Further, at the absorption wavelength of NO 2 gas in the visible wavelength region (wavelength of 400 nm or more), NO gas and SO 2 gas do not absorb, and visible transmitted light does not contain information about NO gas and SO 2 gas. Therefore, it is impossible to correct interference caused by NO gas or SO 2 gas, or to use it for concentration measurement of NO gas or SO 2 gas.
When the sample gas contains the gas components of NO gas and SO 2 gas as described above, it has been difficult to analyze the gas components of these NO gas and SO 2 gas in the prior art.
このようにサンプルガスにＮＯガスおよびＳＯ２ガスのガス成分が含まれている場合には、従来技術では、これらのＮＯガスおよびＳＯ２ガスのガス成分の分析が困難であった。 Further, at the absorption wavelength of NO 2 gas in the visible wavelength region (wavelength of 400 nm or more), NO gas and SO 2 gas do not absorb, and visible transmitted light does not contain information about NO gas and SO 2 gas. Therefore, it is impossible to correct interference caused by NO gas or SO 2 gas, or to use it for concentration measurement of NO gas or SO 2 gas.
When the sample gas contains the gas components of NO gas and SO 2 gas as described above, it has been difficult to analyze the gas components of these NO gas and SO 2 gas in the prior art.
また、ＮＯガスを吸光により測定する場合、図１３に示すように波長２２６ｎｍ以下の波長で発光する光源が必要となる。この波長領域で発光する光源は、重水素ランプやキセノンランプなどのランプ光源、または、窒化アルミニウム系化合物半導体（ＡｌＧａＮなど）を用いた発光ダイオードに限られる。
Further, when NO gas is measured by absorption, a light source that emits light at a wavelength of 226 nm or less is required as shown in FIG. A light source that emits light in this wavelength region is limited to a lamp light source such as a deuterium lamp or a xenon lamp, or a light emitting diode using an aluminum nitride compound semiconductor (such as AlGaN).
前者の重水素ランプやキセノンランプなどのランプ光源は、光源の発熱や寿命、安定性に問題があるうえ、波長フィルタなどの光学系を追加する必要があり、装置が大型、複雑である。
The former lamp light sources such as deuterium lamps and xenon lamps have problems with the heat generation, life and stability of the light source, and it is necessary to add an optical system such as a wavelength filter, and the apparatus is large and complicated.
後者の発光ダイオードは、ランプ光源と比べて装置の小型化や簡略化が可能であるが、光パワーが不足し、寿命も短い。また、波長２２６ｎｍ以下の波長領域においては、ＳＯ２ガス、ＮＯ２ガス以外にもさまざまなガスの吸光があり、それらの干渉を除去することは困難である。
The latter light-emitting diode can reduce the size and simplification of the device as compared with the lamp light source, but has a short optical power and a short life. Further, in the wavelength region of wavelength 226 nm or less, various gases absorb light other than SO 2 gas and NO 2 gas, and it is difficult to remove the interference.
そこで本発明は、上記の課題を全て解決するためになされたものであり、その目的は、簡易な構成でサンプルガスに含まれる少なくとも一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の２成分のガス濃度を計測可能とするガス分析計を提供することにある。
好ましくは、二酸化硫黄ガス（ＳＯ２ガス）、一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の３成分のガス濃度を計測可能とするガス分析計を提供することにある。 Therefore, the present invention has been made to solve all of the above problems, and an object of the present invention is to provide at least nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in the sample gas with a simple configuration. It is to provide a gas analyzer that can measure the gas concentration of two components.
It is preferable to provide a gas analyzer capable of measuring the three component gas concentrations of sulfur dioxide gas (SO 2 gas), nitric oxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas).
好ましくは、二酸化硫黄ガス（ＳＯ２ガス）、一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の３成分のガス濃度を計測可能とするガス分析計を提供することにある。 Therefore, the present invention has been made to solve all of the above problems, and an object of the present invention is to provide at least nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in the sample gas with a simple configuration. It is to provide a gas analyzer that can measure the gas concentration of two components.
It is preferable to provide a gas analyzer capable of measuring the three component gas concentrations of sulfur dioxide gas (SO 2 gas), nitric oxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas).
本発明は、
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の２成分のガス濃度を測定するガス分析計であって、
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）をオゾンの酸化により全て二酸化窒素ガス（ＮＯ２ガス）に反応させ、さらに二酸化窒素ガス（ＮＯ２ガス）の一部をオゾンの酸化により五酸化二窒素ガス（Ｎ２Ｏ５ガス）に反応させた測定対象ガスとして出力する酸化出力と、サンプルガスを無反応のまま測定対象ガスとして出力する通常出力と、を行うガス調整部と、
二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域から可視領域までの波長のＮＯ２ガス吸光用照射光を照射するＮＯ２ガス吸光用発光部と、
オゾンガス（Ｏ３ガス）および二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域の波長のＯ３ガス吸光用照射光を照射するＯ３ガス吸光用発光部と、
ＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光の一部を反射し、残りを透過する部分反射部と、
ガス調整部からの測定対象ガスが流通する検出空間と、部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を検出空間へ入射させる光透過窓と、を有するガス流通セルと、
光透過窓を透過しガス流通セル内を伝播したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する透過光受光部と、
部分反射部で反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する基準光受光部と、
ガス調整部、ＮＯ２ガス吸光用発光部、Ｏ３ガス吸光用発光部、透過光受光部および基準光受光部と接続される信号処理・駆動制御部と、
を備え、
この信号処理・駆動制御部は、
ガス調整部を酸化出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃｍを算出し、
ガス調整部を酸化出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、オゾンガス（Ｏ３ガス）のガス濃度ｃ３を算出し、
ガス調整部を通常出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃ２を算出し、
供給されるオゾンガス（Ｏ３ガス）のガス濃度ｃ０から、測定されたオゾンガス（Ｏ３ガス）のガス濃度ｃ３を、減じて算出された反応消費時のガス濃度が、測定対象ガス中の一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１に五酸化二窒素ガス（Ｎ２Ｏ５ガス）のガス濃度（ｃ１＋ｃ２－ｃｍ）／２を加えたガス濃度に等しいことに基づいて、算出されたｃ０、ｃｍ、ｃ３、ｃ２、から一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１を算出するようなガス分析計とした。 The present invention
A gas analyzer that measures the gas concentrations of two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in a sample gas,
All nitric oxide gas contained in the sample gas (NO gas) by oxidation of ozone reacted in a nitrogen dioxide gas (NO 2 gas), further pentoxide a portion of the nitrogen dioxide gas (NO 2 gas) by oxidation of ozone A gas adjustment unit that performs an oxidation output that is output as a measurement target gas reacted with dinitrogen gas (N 2 O 5 gas), and a normal output that is output as a measurement target gas without any reaction;
A light emitting part for absorbing NO 2 gas that irradiates irradiation light for absorbing NO 2 gas having a wavelength from an ultraviolet region to a visible region in which nitrogen dioxide gas (NO 2 gas) absorbs;
A light emitting part for absorbing O 3 gas that irradiates irradiation light for absorbing O 3 gas having a wavelength in the ultraviolet region where ozone gas (O 3 gas) and nitrogen dioxide gas (NO 2 gas) absorb;
A partially reflecting portion that reflects part of the irradiation light for NO 2 gas absorption and part of the irradiation light for O 3 gas absorption and transmits the rest;
Gas having a detection space which the measurement target gas from the gas conditioning unit flows, and the light transmission window for entering the partial reflection region permeated NO 2 gas absorption irradiation light and the O 3 irradiation light gas absorption into the detection space, the A distribution cell;
A transmitted light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas transmitted through the light transmission window and propagated in the gas flow cell;
A reference light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas reflected by the partial reflection unit;
A signal processing / drive control unit connected to the gas adjusting unit, the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, the transmitted light receiving unit, and the reference light receiving unit;
With
This signal processing / drive control unit
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled by using the signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the oxidation output state and the irradiation light for NO 2 gas absorption is emitted. c m is calculated,
The gas conditioning unit by using a signal from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the oxidation output state, gas concentration c 3 of ozone (O 3 gas) To calculate
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the irradiation light for NO 2 gas absorption is emitted. c 2 is calculated,
From the gas concentration c 0 of the ozone gas (O 3 gas) supplied, the gas concentration c 3 of the measured ozone (O 3 gas), the gas concentration in the reaction consumption calculated by subtracting the, in the gas as the object of measurement based on the equal to the gas concentration (c 1 + c 2 -c m ) / 2 gas concentration by adding gas concentration c 1 tonitric oxide gas (N 2 O 5 gas) of nitric oxide gas (NO gas) Thus, the gas analyzer was configured to calculate the gas concentration c 1 of nitric oxide gas (NO gas) from the calculated c 0 , c m , c 3 , c 2 .
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の２成分のガス濃度を測定するガス分析計であって、
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）をオゾンの酸化により全て二酸化窒素ガス（ＮＯ２ガス）に反応させ、さらに二酸化窒素ガス（ＮＯ２ガス）の一部をオゾンの酸化により五酸化二窒素ガス（Ｎ２Ｏ５ガス）に反応させた測定対象ガスとして出力する酸化出力と、サンプルガスを無反応のまま測定対象ガスとして出力する通常出力と、を行うガス調整部と、
二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域から可視領域までの波長のＮＯ２ガス吸光用照射光を照射するＮＯ２ガス吸光用発光部と、
オゾンガス（Ｏ３ガス）および二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域の波長のＯ３ガス吸光用照射光を照射するＯ３ガス吸光用発光部と、
ＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光の一部を反射し、残りを透過する部分反射部と、
ガス調整部からの測定対象ガスが流通する検出空間と、部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を検出空間へ入射させる光透過窓と、を有するガス流通セルと、
光透過窓を透過しガス流通セル内を伝播したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する透過光受光部と、
部分反射部で反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する基準光受光部と、
ガス調整部、ＮＯ２ガス吸光用発光部、Ｏ３ガス吸光用発光部、透過光受光部および基準光受光部と接続される信号処理・駆動制御部と、
を備え、
この信号処理・駆動制御部は、
ガス調整部を酸化出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃｍを算出し、
ガス調整部を酸化出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、オゾンガス（Ｏ３ガス）のガス濃度ｃ３を算出し、
ガス調整部を通常出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃ２を算出し、
供給されるオゾンガス（Ｏ３ガス）のガス濃度ｃ０から、測定されたオゾンガス（Ｏ３ガス）のガス濃度ｃ３を、減じて算出された反応消費時のガス濃度が、測定対象ガス中の一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１に五酸化二窒素ガス（Ｎ２Ｏ５ガス）のガス濃度（ｃ１＋ｃ２－ｃｍ）／２を加えたガス濃度に等しいことに基づいて、算出されたｃ０、ｃｍ、ｃ３、ｃ２、から一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１を算出するようなガス分析計とした。 The present invention
A gas analyzer that measures the gas concentrations of two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in a sample gas,
All nitric oxide gas contained in the sample gas (NO gas) by oxidation of ozone reacted in a nitrogen dioxide gas (NO 2 gas), further pentoxide a portion of the nitrogen dioxide gas (NO 2 gas) by oxidation of ozone A gas adjustment unit that performs an oxidation output that is output as a measurement target gas reacted with dinitrogen gas (N 2 O 5 gas), and a normal output that is output as a measurement target gas without any reaction;
A light emitting part for absorbing NO 2 gas that irradiates irradiation light for absorbing NO 2 gas having a wavelength from an ultraviolet region to a visible region in which nitrogen dioxide gas (NO 2 gas) absorbs;
A light emitting part for absorbing O 3 gas that irradiates irradiation light for absorbing O 3 gas having a wavelength in the ultraviolet region where ozone gas (O 3 gas) and nitrogen dioxide gas (NO 2 gas) absorb;
A partially reflecting portion that reflects part of the irradiation light for NO 2 gas absorption and part of the irradiation light for O 3 gas absorption and transmits the rest;
Gas having a detection space which the measurement target gas from the gas conditioning unit flows, and the light transmission window for entering the partial reflection region permeated NO 2 gas absorption irradiation light and the O 3 irradiation light gas absorption into the detection space, the A distribution cell;
A transmitted light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas transmitted through the light transmission window and propagated in the gas flow cell;
A reference light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas reflected by the partial reflection unit;
A signal processing / drive control unit connected to the gas adjusting unit, the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, the transmitted light receiving unit, and the reference light receiving unit;
With
This signal processing / drive control unit
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled by using the signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the oxidation output state and the irradiation light for NO 2 gas absorption is emitted. c m is calculated,
The gas conditioning unit by using a signal from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the oxidation output state, gas concentration c 3 of ozone (O 3 gas) To calculate
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the irradiation light for NO 2 gas absorption is emitted. c 2 is calculated,
From the gas concentration c 0 of the ozone gas (O 3 gas) supplied, the gas concentration c 3 of the measured ozone (O 3 gas), the gas concentration in the reaction consumption calculated by subtracting the, in the gas as the object of measurement based on the equal to the gas concentration (c 1 + c 2 -c m ) / 2 gas concentration by adding gas concentration c 1 to
また、本発明は、
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）、二酸化窒素ガス（ＮＯ２）および二酸化硫黄ガス（ＳＯ２ガス）の３成分のガス濃度を測定するガス分析計であって、
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）をオゾンの酸化により全て二酸化窒素ガス（ＮＯ２ガス）に反応させ、さらに二酸化窒素ガス（ＮＯ２ガス）の一部をオゾンの酸化により五酸化二窒素ガス（Ｎ２Ｏ５ガス）に反応させた測定対象ガスとして出力する酸化出力と、サンプルガスを無反応のまま測定対象ガスとして出力する通常出力と、を行うガス調整部と、
二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域から可視領域までの波長のＮＯ２ガス吸光用照射光を照射するＮＯ２ガス吸光用発光部と、
オゾンガス（Ｏ３ガス）、二酸化硫黄ガス（ＳＯ２ガス）および二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域の波長のＯ３ガス吸光用照射光を照射するＯ３ガス吸光用発光部と、
ＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光の一部を反射し、残りを透過する部分反射部と、
ガス調整部からの測定対象ガスが流通する検出空間と、部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を検出空間へ入射させる光透過窓と、を有するガス流通セルと、
光透過窓を透過しガス流通セル内を伝播したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する透過光受光部と、
部分反射部で反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する基準光受光部と、
ガス調整部、ＮＯ２ガス吸光用発光部、Ｏ３ガス吸光用発光部、透過光受光部および基準光受光部と接続される信号処理・駆動制御部と、
を備え、
この信号処理・駆動制御部は、
ガス調整部を酸化出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃｍを算出し、
ガス調整部を酸化出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、オゾンガス（Ｏ３ガス）のガス濃度ｃ３および二酸化硫黄ガス（ＳＯ２ガス）のガス濃度ｃｓを算出し、
ガス調整部を通常出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃ２を算出し、
ガス調整部を通常出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化硫黄ガス（ＳＯ２ガス）のガス濃度ｃｓを算出し、
供給されるオゾンガス（Ｏ３ガス）のガス濃度ｃ０から、測定されたオゾンガス（Ｏ３ガス）のガス濃度ｃ３を、減じて算出された反応消費時のガス濃度が、測定対象ガス中の一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１に五酸化二窒素ガス（Ｎ２Ｏ５ガス）のガス濃度（ｃ１＋ｃ２－ｃｍ）／２を加えたガス濃度に等しいことに基づいて、算出されたｃ０、ｃｍ、ｃ３、ｃ２、から一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１を算出するようなガス分析計とした。 The present invention also provides:
A gas analyzer that measures the concentration of three components of nitrogen monoxide gas (NO gas), nitrogen dioxide gas (NO 2 ), and sulfur dioxide gas (SO 2 gas) contained in a sample gas,
All nitric oxide gas contained in the sample gas (NO gas) by oxidation of ozone reacted in a nitrogen dioxide gas (NO 2 gas), further pentoxide a portion of the nitrogen dioxide gas (NO 2 gas) by oxidation of ozone A gas adjustment unit that performs an oxidation output that is output as a measurement target gas reacted with dinitrogen gas (N 2 O 5 gas), and a normal output that is output as a measurement target gas without any reaction;
A light emitting part for absorbing NO 2 gas that irradiates irradiation light for absorbing NO 2 gas having a wavelength from an ultraviolet region to a visible region in which nitrogen dioxide gas (NO 2 gas) absorbs;
A light emitting part for absorbing O 3 gas that irradiates light for absorbing O 3 gas having a wavelength in the ultraviolet region where ozone gas (O 3 gas), sulfur dioxide gas (SO 2 gas) and nitrogen dioxide gas (NO 2 gas) absorb; ,
A partially reflecting portion that reflects part of the irradiation light for NO 2 gas absorption and part of the irradiation light for O 3 gas absorption and transmits the rest;
A gas having a detection space in which a measurement target gas from the gas adjustment unit flows, and a light transmission window through which the irradiation light for NO 2 gas absorption and the irradiation light for O 3 gas absorption transmitted through the partial reflection unit enter the detection space A distribution cell;
A transmitted light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas transmitted through the light transmission window and propagated in the gas flow cell;
A reference light receiving unit for receiving the reflected NO 2 irradiated light and gas absorption O 3 irradiation light gas absorption by the partially reflecting portion,
A signal processing / drive control unit connected to the gas adjusting unit, the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, the transmitted light receiving unit, and the reference light receiving unit;
With
This signal processing / drive control unit
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled by using the signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the oxidation output state and the irradiation light for NO 2 gas absorption is emitted. c m is calculated,
The gas conditioning unit by using a signal from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the oxidation output state, gas concentration c 3 of ozone (O 3 gas) And the gas concentration c s of sulfur dioxide gas (SO 2 gas),
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the irradiation light for NO 2 gas absorption is emitted. c 2 is calculated,
The gas concentration of sulfur dioxide gas (SO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the O 3 gas absorption irradiation light is emitted. c s is calculated,
From the gas concentration c 0 of the ozone gas (O 3 gas) supplied, the gas concentration c 3 of the measured ozone (O 3 gas), the gas concentration in the reaction consumption calculated by subtracting the, in the gas as the object of measurement Based on the gas concentration c 1 of nitrogen monoxide gas (NO gas) plus the gas concentration (c 1 + c 2 −c m ) / 2 of nitrous oxide (N 2 O 5 gas) / 2. Thus, the gas analyzer was configured to calculate the gas concentration c 1 of nitric oxide gas (NO gas) from the calculated c 0 , c m , c 3 , c 2 .
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）、二酸化窒素ガス（ＮＯ２）および二酸化硫黄ガス（ＳＯ２ガス）の３成分のガス濃度を測定するガス分析計であって、
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）をオゾンの酸化により全て二酸化窒素ガス（ＮＯ２ガス）に反応させ、さらに二酸化窒素ガス（ＮＯ２ガス）の一部をオゾンの酸化により五酸化二窒素ガス（Ｎ２Ｏ５ガス）に反応させた測定対象ガスとして出力する酸化出力と、サンプルガスを無反応のまま測定対象ガスとして出力する通常出力と、を行うガス調整部と、
二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域から可視領域までの波長のＮＯ２ガス吸光用照射光を照射するＮＯ２ガス吸光用発光部と、
オゾンガス（Ｏ３ガス）、二酸化硫黄ガス（ＳＯ２ガス）および二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域の波長のＯ３ガス吸光用照射光を照射するＯ３ガス吸光用発光部と、
ＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光の一部を反射し、残りを透過する部分反射部と、
ガス調整部からの測定対象ガスが流通する検出空間と、部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を検出空間へ入射させる光透過窓と、を有するガス流通セルと、
光透過窓を透過しガス流通セル内を伝播したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する透過光受光部と、
部分反射部で反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する基準光受光部と、
ガス調整部、ＮＯ２ガス吸光用発光部、Ｏ３ガス吸光用発光部、透過光受光部および基準光受光部と接続される信号処理・駆動制御部と、
を備え、
この信号処理・駆動制御部は、
ガス調整部を酸化出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃｍを算出し、
ガス調整部を酸化出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、オゾンガス（Ｏ３ガス）のガス濃度ｃ３および二酸化硫黄ガス（ＳＯ２ガス）のガス濃度ｃｓを算出し、
ガス調整部を通常出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃ２を算出し、
ガス調整部を通常出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化硫黄ガス（ＳＯ２ガス）のガス濃度ｃｓを算出し、
供給されるオゾンガス（Ｏ３ガス）のガス濃度ｃ０から、測定されたオゾンガス（Ｏ３ガス）のガス濃度ｃ３を、減じて算出された反応消費時のガス濃度が、測定対象ガス中の一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１に五酸化二窒素ガス（Ｎ２Ｏ５ガス）のガス濃度（ｃ１＋ｃ２－ｃｍ）／２を加えたガス濃度に等しいことに基づいて、算出されたｃ０、ｃｍ、ｃ３、ｃ２、から一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１を算出するようなガス分析計とした。 The present invention also provides:
A gas analyzer that measures the concentration of three components of nitrogen monoxide gas (NO gas), nitrogen dioxide gas (NO 2 ), and sulfur dioxide gas (SO 2 gas) contained in a sample gas,
All nitric oxide gas contained in the sample gas (NO gas) by oxidation of ozone reacted in a nitrogen dioxide gas (NO 2 gas), further pentoxide a portion of the nitrogen dioxide gas (NO 2 gas) by oxidation of ozone A gas adjustment unit that performs an oxidation output that is output as a measurement target gas reacted with dinitrogen gas (N 2 O 5 gas), and a normal output that is output as a measurement target gas without any reaction;
A light emitting part for absorbing NO 2 gas that irradiates irradiation light for absorbing NO 2 gas having a wavelength from an ultraviolet region to a visible region in which nitrogen dioxide gas (NO 2 gas) absorbs;
A light emitting part for absorbing O 3 gas that irradiates light for absorbing O 3 gas having a wavelength in the ultraviolet region where ozone gas (O 3 gas), sulfur dioxide gas (SO 2 gas) and nitrogen dioxide gas (NO 2 gas) absorb; ,
A partially reflecting portion that reflects part of the irradiation light for NO 2 gas absorption and part of the irradiation light for O 3 gas absorption and transmits the rest;
A gas having a detection space in which a measurement target gas from the gas adjustment unit flows, and a light transmission window through which the irradiation light for NO 2 gas absorption and the irradiation light for O 3 gas absorption transmitted through the partial reflection unit enter the detection space A distribution cell;
A transmitted light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas transmitted through the light transmission window and propagated in the gas flow cell;
A reference light receiving unit for receiving the reflected NO 2 irradiated light and gas absorption O 3 irradiation light gas absorption by the partially reflecting portion,
A signal processing / drive control unit connected to the gas adjusting unit, the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, the transmitted light receiving unit, and the reference light receiving unit;
With
This signal processing / drive control unit
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled by using the signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the oxidation output state and the irradiation light for NO 2 gas absorption is emitted. c m is calculated,
The gas conditioning unit by using a signal from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the oxidation output state, gas concentration c 3 of ozone (O 3 gas) And the gas concentration c s of sulfur dioxide gas (SO 2 gas),
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the irradiation light for NO 2 gas absorption is emitted. c 2 is calculated,
The gas concentration of sulfur dioxide gas (SO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the O 3 gas absorption irradiation light is emitted. c s is calculated,
From the gas concentration c 0 of the ozone gas (O 3 gas) supplied, the gas concentration c 3 of the measured ozone (O 3 gas), the gas concentration in the reaction consumption calculated by subtracting the, in the gas as the object of measurement Based on the gas concentration c 1 of nitrogen monoxide gas (NO gas) plus the gas concentration (c 1 + c 2 −c m ) / 2 of nitrous oxide (N 2 O 5 gas) / 2. Thus, the gas analyzer was configured to calculate the gas concentration c 1 of nitric oxide gas (NO gas) from the calculated c 0 , c m , c 3 , c 2 .
そして、好ましくは、
前記基準光受光部、前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部と接続される補正部を有し、
前記基準光受光部は、部分反射部により一部反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光して検出信号を補正部へ出力し、
補正部は、この検出信号に基づいて変動を抑止するような駆動電流を前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部へ出力するようなガス分析計にするとよい。 And preferably,
A correction unit connected to the reference light receiving unit, the NO 2 gas absorbing light emitting unit, and the O 3 gas absorbing light emitting unit;
The reference light receiving unit receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas partially reflected by the partial reflection unit, and outputs a detection signal to the correction unit,
The correction unit may be a gas analyzer that outputs a drive current that suppresses fluctuations based on the detection signal to the NO 2 gas absorption light emission unit and the O 3 gas absorption light emission unit.
前記基準光受光部、前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部と接続される補正部を有し、
前記基準光受光部は、部分反射部により一部反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光して検出信号を補正部へ出力し、
補正部は、この検出信号に基づいて変動を抑止するような駆動電流を前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部へ出力するようなガス分析計にするとよい。 And preferably,
A correction unit connected to the reference light receiving unit, the NO 2 gas absorbing light emitting unit, and the O 3 gas absorbing light emitting unit;
The reference light receiving unit receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas partially reflected by the partial reflection unit, and outputs a detection signal to the correction unit,
The correction unit may be a gas analyzer that outputs a drive current that suppresses fluctuations based on the detection signal to the NO 2 gas absorption light emission unit and the O 3 gas absorption light emission unit.
また、好ましくは、
前記ＮＯ２ガス吸光用発光部からのＮＯ２ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズおよび前記Ｏ３ガス吸光用発光部からのＯ３ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズを備えるようなガス分析計にするとよい。 Also preferably,
Collecting the O 3 irradiation light gas absorption from the NO 2 lens and the O 3 gas absorption for the light emitting portion condenses the NO 2 gas absorption for the irradiation light from the gas absorption for the light emitting portion is incident on the gas flow cell A gas analyzer that includes a lens that emits light and enters the gas flow cell may be used.
前記ＮＯ２ガス吸光用発光部からのＮＯ２ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズおよび前記Ｏ３ガス吸光用発光部からのＯ３ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズを備えるようなガス分析計にするとよい。 Also preferably,
Collecting the O 3 irradiation light gas absorption from the NO 2 lens and the O 3 gas absorption for the light emitting portion condenses the NO 2 gas absorption for the irradiation light from the gas absorption for the light emitting portion is incident on the gas flow cell A gas analyzer that includes a lens that emits light and enters the gas flow cell may be used.
また、好ましくは、
前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部を隣接させて一体収容した発光部と、
前記ＮＯ２ガス吸光用発光部からのＮＯ２ガス吸光用照射光および前記Ｏ３ガス吸光用発光部からのＯ３ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズと、
を備えるようなガス分析計にするとよい。 Also preferably,
A light emitting unit that integrally accommodates the NO 2 gas absorbing light emitting unit and the O 3 gas absorbing light emitting unit adjacent to each other;
A lens for incident condenses O 3 irradiation light gas absorption from the NO 2 NO 2 gas absorption irradiation light and the O 3 gas absorption for the light emitting portion of the gas absorption for the light emitting portion to the gas flow cell,
It is good to make it a gas analyzer equipped with.
前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部を隣接させて一体収容した発光部と、
前記ＮＯ２ガス吸光用発光部からのＮＯ２ガス吸光用照射光および前記Ｏ３ガス吸光用発光部からのＯ３ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズと、
を備えるようなガス分析計にするとよい。 Also preferably,
A light emitting unit that integrally accommodates the NO 2 gas absorbing light emitting unit and the O 3 gas absorbing light emitting unit adjacent to each other;
A lens for incident condenses O 3 irradiation light gas absorption from the NO 2 NO 2 gas absorption irradiation light and the O 3 gas absorption for the light emitting portion of the gas absorption for the light emitting portion to the gas flow cell,
It is good to make it a gas analyzer equipped with.
また、好ましくは、
前記ガス流通セルを透過した後のＮＯ２ガス吸光用照射光および前記ガス流通セルを透過した後のＯ３ガス吸光用照射光を集光するレンズを備えるようなガス分析計にするとよい。 Also preferably,
It is preferable that the gas analyzer has a lens for collecting the irradiation light for absorbing NO 2 gas after passing through the gas circulation cell and the irradiation light for absorbing O 3 gas after passing through the gas circulation cell.
前記ガス流通セルを透過した後のＮＯ２ガス吸光用照射光および前記ガス流通セルを透過した後のＯ３ガス吸光用照射光を集光するレンズを備えるようなガス分析計にするとよい。 Also preferably,
It is preferable that the gas analyzer has a lens for collecting the irradiation light for absorbing NO 2 gas after passing through the gas circulation cell and the irradiation light for absorbing O 3 gas after passing through the gas circulation cell.
また、好ましくは、
前記ガス流通セルは一方に光透過窓を、また、他方に反射部を備え、光透過窓を透過してＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を反射部で反射させた後に光透過窓を通過するようにして検出空間内を往復させ、前記部分反射部で反射させたＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を前記透過光受光部が検出するようなガス分析計にするとよい。 Also preferably,
The gas flow cell has a light transmission window on one side and a reflection part on the other side, and transmits the light transmission window and reflects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas at the reflection part. The transmitted light receiving unit detects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas reflected by the partial reflection unit so as to reciprocate in the detection space so as to pass through the light transmission window later. A good gas analyzer is recommended.
前記ガス流通セルは一方に光透過窓を、また、他方に反射部を備え、光透過窓を透過してＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を反射部で反射させた後に光透過窓を通過するようにして検出空間内を往復させ、前記部分反射部で反射させたＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を前記透過光受光部が検出するようなガス分析計にするとよい。 Also preferably,
The gas flow cell has a light transmission window on one side and a reflection part on the other side, and transmits the light transmission window and reflects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas at the reflection part. The transmitted light receiving unit detects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas reflected by the partial reflection unit so as to reciprocate in the detection space so as to pass through the light transmission window later. A good gas analyzer is recommended.
また、好ましくは、
前記ＮＯ２ガス吸光用発光部、前記Ｏ３ガス吸光用発光部および前記透過光受光部を隣接させて一体収容した発受光部を更に備え、
前記ガス流通セルは一方に光透過窓を、また、他方に反射部を有するようになされており、
光透過窓を透過して発受光部から発せられたＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を反射部で反射させた後に光透過窓を通過するようにして検出空間内を往復させ、前記部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を発受光部の前記透過光受光部が検出するようなガス分析計にするとよい。 Also preferably,
A light emitting / receiving unit that integrally accommodates the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, and the transmitted light receiving unit adjacent to each other;
The gas flow cell has a light transmission window on one side and a reflection part on the other side,
The NO 2 gas absorption irradiation light and the O 3 gas absorption irradiation light emitted from the light emitting / receiving section through the light transmission window are reflected by the reflection section and then pass through the light transmission window to pass through the light transmission window. The gas analyzer may be configured such that the transmitted light receiving unit of the light emitting / receiving unit detects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas transmitted through the partial reflection unit.
前記ＮＯ２ガス吸光用発光部、前記Ｏ３ガス吸光用発光部および前記透過光受光部を隣接させて一体収容した発受光部を更に備え、
前記ガス流通セルは一方に光透過窓を、また、他方に反射部を有するようになされており、
光透過窓を透過して発受光部から発せられたＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を反射部で反射させた後に光透過窓を通過するようにして検出空間内を往復させ、前記部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を発受光部の前記透過光受光部が検出するようなガス分析計にするとよい。 Also preferably,
A light emitting / receiving unit that integrally accommodates the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, and the transmitted light receiving unit adjacent to each other;
The gas flow cell has a light transmission window on one side and a reflection part on the other side,
The NO 2 gas absorption irradiation light and the O 3 gas absorption irradiation light emitted from the light emitting / receiving section through the light transmission window are reflected by the reflection section and then pass through the light transmission window to pass through the light transmission window. The gas analyzer may be configured such that the transmitted light receiving unit of the light emitting / receiving unit detects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas transmitted through the partial reflection unit.
また、好ましくは、
前記信号処理・駆動制御部は、前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部の出力と停止とを交互に行うパルスであって停止より出力が短くなるようなデューティー比の駆動電流とするようなガス分析計にするとよい。 Also preferably,
The signal processing / drive control unit is a pulse that alternately performs output and stop of the NO 2 gas absorption light-emitting unit and the O 3 gas absorption light-emitting unit, and has a duty ratio that makes the output shorter than the stop. It is better to use a gas analyzer that uses the drive current.
前記信号処理・駆動制御部は、前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部の出力と停止とを交互に行うパルスであって停止より出力が短くなるようなデューティー比の駆動電流とするようなガス分析計にするとよい。 Also preferably,
The signal processing / drive control unit is a pulse that alternately performs output and stop of the NO 2 gas absorption light-emitting unit and the O 3 gas absorption light-emitting unit, and has a duty ratio that makes the output shorter than the stop. It is better to use a gas analyzer that uses the drive current.
本発明によれば、簡易な構成でサンプルガスに含まれる少なくとも一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の２成分のガス濃度を計測可能とするガス分析計を提供することができる。
加えて、二酸化硫黄ガス（ＳＯ２ガス）、一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の３成分のガス濃度を計測可能とするガス分析計を提供することができる。 According to the present invention, there is provided a gas analyzer capable of measuring the gas concentrations of at least two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in a sample gas with a simple configuration. be able to.
In addition, it is possible to provide a gas analyzer that can measure the three component gas concentrations of sulfur dioxide gas (SO 2 gas), nitrogen monoxide gas (NO gas), and nitrogen dioxide gas (NO 2 gas).
加えて、二酸化硫黄ガス（ＳＯ２ガス）、一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の３成分のガス濃度を計測可能とするガス分析計を提供することができる。 According to the present invention, there is provided a gas analyzer capable of measuring the gas concentrations of at least two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in a sample gas with a simple configuration. be able to.
In addition, it is possible to provide a gas analyzer that can measure the three component gas concentrations of sulfur dioxide gas (SO 2 gas), nitrogen monoxide gas (NO gas), and nitrogen dioxide gas (NO 2 gas).
続いて、本発明を実施するための第１の形態に係るガス分析計について、図を参照しつつ以下に説明する。図１は、本形態のガス分析計の全体構成図である。なお、本形態ではサンプルガスに一酸化窒素ガス（以下単にＮＯガスという）および二酸化窒素ガス（以下、単にＮＯ２ガスという）の２成分は含まれるが二酸化硫黄ガス（以下単にＳＯ２ガスという）は含まれないものとする。ガス分析計は、これらＮＯガスおよびＮＯ２ガスについて分析する。図１において、太い実線の矢印はガスの流通経路を、点線の矢印は光の経路を、細い実線の矢印は電気信号の経路を、それぞれ示す。
Then, the gas analyzer which concerns on the 1st form for implementing this invention is demonstrated below, referring a figure. FIG. 1 is an overall configuration diagram of a gas analyzer according to this embodiment. In this embodiment, the sample gas contains two components of nitrogen monoxide gas (hereinafter simply referred to as NO gas) and nitrogen dioxide gas (hereinafter simply referred to as NO 2 gas), but sulfur dioxide gas (hereinafter simply referred to as SO 2 gas). Shall not be included. The gas analyzer analyzes these NO gas and NO 2 gas. In FIG. 1, a thick solid arrow indicates a gas flow path, a dotted arrow indicates a light path, and a thin solid arrow indicates an electrical signal path.
まず、本形態のガス分析計１００が備える構成要素とそれらの機能について説明する。ガス分析計１００は、図１で示すように、ＮＯ２ガス吸光用発光部１１、Ｏ３ガス吸光用発光部１２、部分反射部１３、ガス流通セル２１、透過光受光部３１、基準光受光部３２、ガス調整部４１、ガス吸引部５１、信号処理・駆動制御部６１を備える。
First, the components provided in the gas analyzer 100 of this embodiment and their functions will be described. As shown in FIG. 1, the gas analyzer 100 includes an NO 2 gas absorbing light emitting unit 11, an O 3 gas absorbing light emitting unit 12, a partial reflecting unit 13, a gas flow cell 21, a transmitted light receiving unit 31, and a reference light receiving unit. Unit 32, gas adjustment unit 41, gas suction unit 51, and signal processing / drive control unit 61.
ＮＯ２ガス吸光用発光部１１は、ＮＯ２ガスが吸光する波長であって、かつＯ３ガスが吸光しない波長のＮＯ２ガス吸光用照射光を発光する発光部である。例えば、紫外光から可視光にまたがる領域の波長３５０ｎｍ～５００ｎｍに中心発光波長を有する照射光の発光ダイオード（ＬＥＤ）を選ぶことができる。図２に示されるように、この波長領域においてはＮＯ２ガスのみが吸光する。
The NO 2 gas absorption light emitting unit 11 is a light emitting unit that emits NO 2 gas absorption irradiation light having a wavelength at which NO 2 gas absorbs and a wavelength at which O 3 gas does not absorb. For example, it is possible to select a light emitting diode (LED) of irradiation light having a central emission wavelength in a wavelength range of 350 nm to 500 nm in a region extending from ultraviolet light to visible light. As shown in FIG. 2, only NO 2 gas absorbs light in this wavelength region.
Ｏ３ガス吸光用発光部１２は、Ｏ３ガスが吸光する波長のＯ３ガス吸光用照射光を発光する発光部である。例えば、紫外光領域の波長２４０ｎｍ～３３０ｎｍに中心発光波長を有する照射光の発光ダイオード（ＬＥＤ）を選ぶことができる。なお、図２に示されるように、この波長領域においてはＯ３ガスが吸光するのみならずＮＯ２ガスも吸光する。なお、ＳＯ２ガスは存在しないので考慮しない。
O 3 light-emitting unit 12 for gas absorption is a light-emitting unit that O 3 gas emits O 3 gas absorption for the irradiation light of a wavelength absorption. For example, a light emitting diode (LED) for irradiation light having a central emission wavelength in the wavelength range of 240 nm to 330 nm in the ultraviolet region can be selected. As shown in FIG. 2, not only O 3 gas but also NO 2 gas absorbs in this wavelength region. It is not taken into account because no SO 2 gas is present.
部分反射部１３はハーフミラーであり、所定透過率でＮＯ２ガス吸光用照射光やＯ３ガス吸光用照射光（以下単に照射光というときはＮＯ２ガス吸光用照射光とＯ３ガス吸光用照射光と両方を含めるものとする。なお、ＮＯ２ガス吸光用照射光とＯ３ガス吸光用照射光は同時に出力されることはなく、例えば時間別にそれぞれが単独で出力される）を透過させ、また、所定反射率で照射光を反射させる。
The partial reflection unit 13 is a half mirror, and has a predetermined transmittance for irradiation light for absorbing NO 2 gas and irradiation light for absorbing O 3 gas (hereinafter simply referred to as irradiation light for absorbing light for absorbing NO 2 gas and for absorbing O 3 gas). Both the irradiation light and the irradiation light for NO 2 gas absorption and the irradiation light for O 3 gas absorption are not output at the same time, for example, each is output separately by time). Further, the irradiation light is reflected at a predetermined reflectance.
ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２から照射された照射光は、部分反射部１３に入射する。部分反射部１３において、照射光の一部は反射し、照射光の残りは透過する。部分反射部１３で反射した照射光は基準光受光部３２へ入射される。また、部分反射部１３を透過した照射光はガス流通セル２１へ入射される。
Irradiation light emitted from the NO 2 gas absorption light-emitting unit 11 and the O 3 gas absorption light-emitting unit 12 is incident on the partial reflection unit 13. In the partial reflection unit 13, a part of the irradiation light is reflected and the rest of the irradiation light is transmitted. The irradiation light reflected by the partial reflection unit 13 enters the reference light receiving unit 32. Further, the irradiation light transmitted through the partial reflection portion 13 is incident on the gas flow cell 21.
ガス流通セル２１は、さらに管２２、光透過窓２３，２４、検出空間２５、ガス流入口２６、ガス流出口２７を備える。
The gas distribution cell 21 further includes a tube 22, light transmission windows 23 and 24, a detection space 25, a gas inlet 26, and a gas outlet 27.
管２２は、筒体である。管２２の内面は、例えば研磨されたステンレスの内面とすることができる。これにより測定対象ガスの吸着を防ぎつつ、照射光の反射率を良好に保つことができる。管２２内では、照射光は、管２２の内面により反射しつつ伝播する。
The tube 22 is a cylinder. The inner surface of the tube 22 can be, for example, a polished stainless steel inner surface. Thereby, the reflectance of irradiation light can be kept favorable, preventing adsorption of measurement object gas. In the tube 22, the irradiation light propagates while being reflected by the inner surface of the tube 22.
光透過窓２３、光透過窓２４は、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２から照射される照射光の発光波長領域において光透過性を示す材料で作られている。例えば、合成石英、フッ化カルシウムを材料とすることができる。
The light transmission window 23 and the light transmission window 24 are made of a material exhibiting light transmittance in the emission wavelength region of the irradiation light emitted from the NO 2 gas absorption light emitting portion 11 and the O 3 gas absorption light emission portion 12. . For example, synthetic quartz or calcium fluoride can be used as the material.
検出空間２５は、管２２、光透過窓２３、および、光透過窓２４により区画された閉空間である。
ガス流入口２６、ガス流出口２７はこの検出空間２５と連通する。測定対象ガスは、ガス流入口２６から検出空間２５へ流入し、ガス流出口２７から流出する。
このようなガス流通セル２１内では、流通する測定対象ガスに照射光が照射されて吸光が起こる。 Thedetection space 25 is a closed space defined by the tube 22, the light transmission window 23, and the light transmission window 24.
Thegas inlet 26 and the gas outlet 27 communicate with the detection space 25. The measurement target gas flows into the detection space 25 from the gas inlet 26 and flows out of the gas outlet 27.
In such agas flow cell 21, irradiation light is irradiated to the flowing measurement target gas, and light absorption occurs.
ガス流入口２６、ガス流出口２７はこの検出空間２５と連通する。測定対象ガスは、ガス流入口２６から検出空間２５へ流入し、ガス流出口２７から流出する。
このようなガス流通セル２１内では、流通する測定対象ガスに照射光が照射されて吸光が起こる。 The
The
In such a
透過光受光部３１は、ガス流通セル２１を透過した照射光を受光して光強度に応じた検出信号を出力する。透過光受光部３１には、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２から照射される照射光の発光波長に対して感度を有するような、フォトダイオードや光電子増倍管などを選ぶことができる。例えば、シリコンフォトダイオードを選ぶことができる。
The transmitted light receiving unit 31 receives the irradiation light transmitted through the gas flow cell 21 and outputs a detection signal corresponding to the light intensity. The transmitted light receiving unit 31 includes a photodiode or a photomultiplier tube having sensitivity to the emission wavelength of irradiation light emitted from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12. You can choose. For example, a silicon photodiode can be selected.
このような透過光受光部３１は、測定対象ガスによる吸光を検出する機能を有する。すなわち、測定対象ガスによる吸光が無い場合と比較して、吸光がある場合は透過光受光部３１で受光される照射光の光強度が減少するために、その光強度の減少量とガス濃度との相関を利用してガス濃度を測定する。
Such a transmitted light receiving unit 31 has a function of detecting light absorption by the measurement target gas. That is, compared with the case where there is no light absorption due to the measurement target gas, the light intensity of the irradiation light received by the transmitted light receiving unit 31 decreases when there is light absorption. The gas concentration is measured using the correlation.
このように部分反射部１３を透過した照射光がガス流通セル２１の一端を構成する光透過性の光透過窓２３を透過し、管２２の内部の検出空間２５を伝播し、もう一端を構成する光透過性の光透過窓２４を透過し、透過光受光部３１に入射する。
Thus, the irradiation light transmitted through the partial reflection portion 13 passes through the light-transmitting light transmission window 23 constituting one end of the gas flow cell 21, propagates through the detection space 25 inside the tube 22, and constitutes the other end. The light is transmitted through the light transmissive window 24 and enters the transmitted light receiving unit 31.
基準光受光部３２は、部分反射部１３で反射した照射光を受光するために設けられている。基準光受光部３２には、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２から照射される照射光の発光波長に対して感度を有する、フォトダイオードや光電子増倍管などを選ぶことができる。例えば、シリコンフォトダイオードを選ぶことができる。
The reference light receiving unit 32 is provided to receive the irradiation light reflected by the partial reflection unit 13. The reference light receiving unit 32 includes a photodiode, a photomultiplier tube, or the like that is sensitive to the emission wavelength of the irradiation light emitted from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12. You can choose. For example, a silicon photodiode can be selected.
基準光受光部３２は、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２から照射される照射光の変動を検出する機能を有する。照射光の変動がある場合には基準光受光部３２で受光される照射光の光強度が変動する。この光強度の変動量を利用してガス濃度の補正が行われる。
The reference light receiving unit 32 has a function of detecting fluctuations in irradiation light emitted from the NO 2 gas absorbing light emitting unit 11 and the O 3 gas absorbing light emitting unit 12. When the irradiation light varies, the light intensity of the irradiation light received by the reference light receiving unit 32 varies. The gas concentration is corrected using the fluctuation amount of the light intensity.
ガス調整部４１は、さらにオゾン発生部４２、ガス混合部４３を備えている。
The gas adjustment unit 41 further includes an ozone generation unit 42 and a gas mixing unit 43.
オゾン発生部４２は、オゾンガスを発生する機能を有する。オゾン発生部４２に酸素を含む大気、計装空気、または、酸素ガス（Ｏ２ガス）などの原料ガスＧＯが流入する。オゾン発生部４２は、信号処理・駆動制御部６１により動作制御がなされている。オゾン発生部４２の動作時では、オゾン発生部４２は、無声放電などの電気的な手段により、原料ガスＧＯのＯ２ガスを用いてＯ３ガスを生成し、Ｏ３ガスを充分に含む原料ガスＧＯを流出させる。不動作時では、オゾン発生部４２は、Ｏ３ガスを生成せずに原料ガスＧＯをそのまま通過させる。このように信号処理・駆動制御部６１が、オゾン発生部４２の動作・不動作の動作制御を行う。
The ozone generator 42 has a function of generating ozone gas. Atmosphere containing oxygen to the ozone generator 42, instrument air, or the raw material gas G O such as oxygen gas (O 2 gas) flows. The operation of the ozone generator 42 is controlled by a signal processing / drive controller 61. In operation of the ozone generator 42, ozone generator 42, by electrical means, such as silent discharge, using an O 2 gas of the raw material gas G O generates O 3 gas, sufficiently containing the O 3 gas The source gas GO is caused to flow out. In an off-state, the ozone generator 42 is directly passing the raw material gas G O without generating the O 3 gas. In this way, the signal processing / drive control unit 61 controls the operation / non-operation of the ozone generation unit 42.
ガス混合部４３は、サンプルガスＧＳとオゾン発生部４２からの原料ガスＧＯ（動作時ではＯ３ガスを大量に含む原料ガスＧＯであり、また、不動作時ではＯ３ガスを含まない原料ガスＧＯである）を混合するために設けられている。
Gas mixing unit 43, at the time the raw material gas G O (operation from the sample gas G S and ozone generator 42 is a raw material gas G O containing O 3 gas in large quantities, also in an off-state free of O 3 gas is provided to mix the free feed gas is G O).
オゾン発生部４２の動作時には、後述するがガス混合部４３においてＯ３ガスの一部とサンプルガスＧＳの一部とで化学反応が発生して反応ガスが生成され、この反応ガス、余剰のＯ３ガス、余剰の原料ガスＧＯおよび余剰のサンプルガスＧＳを測定対象ガスとして流出させる。
During operation of the ozone generator 42, a part with a chemical reaction occurs reactive gas partial and sample gas G S of the O 3 gas in the gas mixing portion 43 will be described later is produced, the reaction gas, the excess O 3 gas, thereby discharging the material gas G O and excess sample gas G S surplus as a measurement target gas.
また、オゾン発生部４２の不動作時には、オゾン発生部４２からの原料ガスＧＯとサンプルガスＧＳとをそのまま混合して流出させる。
Also, when not in operation of the ozone generator 42 is allowed to flow out by mixing it with a raw material gas G O and the sample gas G S from the ozone generator 42.
また、後述するが、ガス混合部４３は、ゼロガスＧＺＥＲＯやスパンガスＧＳＰＡＮが流入したとき、そのまま測定対象ガスとして流出させる。このガス混合部４３から流出した測定対象ガスは、ガス流入口２６からガス流通セル２１内の検出空間２５を流通し、ガス流出口２７から流出する。
As will be described later, when the zero gas G ZERO or the span gas G SPAN flows in, the gas mixing unit 43 causes the gas mixing unit 43 to directly flow out as a measurement target gas. The measurement target gas flowing out from the gas mixing unit 43 flows through the detection space 25 in the gas flow cell 21 from the gas inlet 26 and flows out from the gas outlet 27.
ガス吸引部５１は、ガスを吸引する機能を有している。ガス流通セル２１の検出空間２５内を排気することで検出空間２５内へガス混合部４３からの測定対象ガスを引き入れる。なお、このガス吸引部５１は、ガス混合部４３とガス流入口２６との間に設けることもできる。
The gas suction unit 51 has a function of sucking gas. The measurement target gas from the gas mixing unit 43 is drawn into the detection space 25 by exhausting the detection space 25 of the gas flow cell 21. The gas suction part 51 can also be provided between the gas mixing part 43 and the gas inlet 26.
信号処理・駆動制御部６１は、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２を発光させるために必要な駆動電流を供給する機能を有する。また、信号処理・駆動制御部６１は、透過光受光部３１および基準光受光部３２からの受光信号に基づいてガス濃度を算出するための受光信号処理機能を有する。また、信号処理・駆動制御部６１は、オゾン発生部４２の動作・不動作を切り替える制御機能を有する。
ガス分析計１００の構成はこのようなものである。 The signal processing /drive control unit 61 has a function of supplying a driving current necessary for causing the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 to emit light. Further, the signal processing / drive control unit 61 has a received light signal processing function for calculating the gas concentration based on the received light signals from the transmitted light receiving unit 31 and the reference light receiving unit 32. Further, the signal processing / drive control unit 61 has a control function for switching operation / non-operation of the ozone generation unit 42.
The configuration of thegas analyzer 100 is as described above.
ガス分析計１００の構成はこのようなものである。 The signal processing /
The configuration of the
続いて、ガス分析計１００による分析について説明する。まず、吸光による測定の原理について説明する。測定の原理は、下記のランベルト－ベールの法則に基づく吸光法である。
Subsequently, analysis by the gas analyzer 100 will be described. First, the principle of measurement by absorption will be described. The principle of measurement is an absorption method based on the following Lambert-Beer law.
［数１］
Ｐ１＝Ｐ０・ｅｘｐ（－ε・ｃ・Ｌ） [Equation 1]
P 1 = P 0 · exp (−ε · c · L)
Ｐ１＝Ｐ０・ｅｘｐ（－ε・ｃ・Ｌ） [Equation 1]
P 1 = P 0 · exp (−ε · c · L)
ここで、Ｐ１は検出空間２５内を流通する測定対象ガスを透過した透過光の出力強度、Ｐ０は測定対象ガスを透過する前の基準光の出力強度、εはモル吸光係数、ｃはガス濃度、Ｌは光路長を表す。モル吸光係数εはガスの種類と光源の波長とを決めると一意に決まり、また、光路長Ｌは一定であるため、出力強度Ｐ１とＰ０の比はガス濃度ｃの指数関数となる。出力強度Ｐ１とＰ０とを測定し、上記の数１によりガス濃度を検出するというものである。
Here, P 1 is the output intensity of the transmitted light that has passed through the measurement target gas flowing in the detection space 25, P 0 is the output intensity of the reference light before passing through the measurement target gas, ε is the molar extinction coefficient, and c is The gas concentration, L, represents the optical path length. The molar extinction coefficient ε is uniquely determined by determining the type of gas and the wavelength of the light source, and since the optical path length L is constant, the ratio between the output intensities P 1 and P 0 is an exponential function of the gas concentration c. The output intensities P 1 and P 0 are measured, and the gas concentration is detected by the above equation ( 1).
ガス分析計１００においてＮＯ２ガス吸光用照射光かＯ３ガス吸光用照射光かいずれか一方である照射光が照射される。このときの照射光の一部は、部分反射部１３によって既知の一定の反射率で反射し、基準光受光部３２に入射する。この基準光受光部３２の信号から基準光による出力強度Ｐ０を求めることができる。また、照射光の一部は、部分反射部１３を既知の一定の透過率で透過し、光透過窓２３を経て検出空間２５を伝播し、吸光を受けた後に光透過窓２４を経て透過光受光部３１に入射する。この透過光受光部３１の信号から透過光による出力強度Ｐ１を求めることができる。したがって、出力強度Ｐ１とＰ０の比からガス濃度ｃを求めることができる。この原理は、ＮＯ２ガス吸光用照射光による分析とＯ３ガス吸光用照射光による分析との両方に適用できる。検出原理はこのようなものとなる。
The gas analyzer 100 emits irradiation light that is either NO 2 gas absorption irradiation light or O 3 gas absorption irradiation light. A part of the irradiation light at this time is reflected by the partial reflection unit 13 with a known constant reflectance and is incident on the reference light receiving unit 32. The output intensity P 0 by the reference light can be obtained from the signal of the reference light receiving unit 32. Further, a part of the irradiation light is transmitted through the partial reflection unit 13 with a known constant transmittance, propagates through the detection space 25 through the light transmission window 23, and is transmitted through the light transmission window 24 after being absorbed. The light enters the light receiving unit 31. The output intensity P 1 by the transmitted light can be obtained from the signal of the transmitted light receiving unit 31. Therefore, the gas concentration c can be obtained from the ratio between the output intensities P 1 and P 0 . This principle can be applied to both the analysis using the irradiation light for absorbing NO 2 gas and the analysis using the irradiation light for absorbing O 3 gas. The detection principle is like this.
なお、透過光受光部３１および基準光受光部３２は、ＮＯ２ガス濃度およびＯ３ガス濃度の測定時に共通に利用される。したがって、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２が同時に発光すると、受光信号が両者の和になってしまい分離できなくなる。
The transmitted light receiving unit 31 and the reference light receiving unit 32 are commonly used when measuring the NO 2 gas concentration and the O 3 gas concentration. Therefore, if the NO 2 gas absorption light-emitting unit 11 and the O 3 gas absorption light-emitting unit 12 emit light at the same time, the light reception signal becomes the sum of the two and cannot be separated.
そこで、信号処理・駆動制御部６１は、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２を同時には発光させないで、交互に発光させるように制御する。また、受光信号の測定および処理も上記の発光期間に同期するように行うことで、信号を分離している。吸光による測定はこのようなものである。
Therefore, the signal processing / drive control unit 61 controls the NO 2 gas absorption light-emitting unit 11 and the O 3 gas absorption light-emitting unit 12 to alternately emit light without simultaneously emitting light. Further, the measurement and processing of the received light signal are also performed in synchronization with the light emission period, thereby separating the signals. Measurement by absorption is like this.
このような測定は、オゾン発生部４２を動作状態としてガス調整部４１を酸化出力としたときと、オゾン発生部４２を不動作状態としてガス調整部４１を通常出力としたときと、でそれぞれ行われる。したがって、このようなガス分析計１００は、
（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析、
（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析、
（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析、
（ｄ）通常出力時のＯ３ガス吸光用照射光による分析、
という４種類の分析が可能である。 Such measurement is performed when theozone generation unit 42 is in an operating state and the gas adjustment unit 41 is in an oxidized output, and when the ozone generation unit 42 is in a non-operational state and the gas adjustment unit 41 is in a normal output. Is called. Therefore, such a gas analyzer 100 is
(A) Analysis with irradiation light for absorbing NO 2 gas at the time of oxidation output,
(B) Analysis by irradiation light for absorbing O 3 gas at the time of oxidation output,
(C) Analysis with irradiation light for absorbing NO 2 gas at normal output,
(D) Normal analysis by the O 3 gas absorption for the irradiation light at the time of output,
Four types of analysis are possible.
（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析、
（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析、
（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析、
（ｄ）通常出力時のＯ３ガス吸光用照射光による分析、
という４種類の分析が可能である。 Such measurement is performed when the
(A) Analysis with irradiation light for absorbing NO 2 gas at the time of oxidation output,
(B) Analysis by irradiation light for absorbing O 3 gas at the time of oxidation output,
(C) Analysis with irradiation light for absorbing NO 2 gas at normal output,
(D) Normal analysis by the O 3 gas absorption for the irradiation light at the time of output,
Four types of analysis are possible.
次に、このガス分析計１００によってサンプルガスＧＳ中に含まれるＮＯガス、ＮＯ２ガスの２成分のガス濃度を測定する方法について説明する。ＮＯガス、ＮＯ２ガスの２成分のガス濃度を計測する場合は、上記の（ａ）、（ｂ）、（ｃ）の分析を行い、これらで得た測定値を用いてガス濃度を算出する。
Next, NO gas contained by the gas analyzer 100 in the sample gas G S, the method for measuring the gas concentration of the two components of the NO 2 gas will be described. When measuring the gas concentrations of the two components of NO gas and NO 2 gas, the analysis of the above (a), (b), and (c) is performed, and the gas concentration is calculated using the measured values obtained by these analyzes. .
まず、（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析を行うものとして説明する。オゾン発生部４２を動作状態としてガス調整部４１を酸化出力させた上での測定である。この際に、酸化出力時のＮＯ２ガス濃度ｃｍを求める。
First, description will be made on the assumption that (a) analysis is performed using irradiation light for absorbing NO 2 gas at the time of oxidation output. This is a measurement after the ozone generating section 42 is in an operating state and the gas adjusting section 41 is oxidized and output. At this time, the NO 2 gas concentration cm at the oxidation output is obtained.
オゾン発生部４２は動作状態である。このとき、オゾン発生部４２は、大気、計装エア、または酸素ガスなどの原料ガスＧ０に含まれているＯ２ガスからオゾンガス（以下、単にＯ３ガスという）を生成する。Ｏ３ガスの発生量は、適宜定めることができるが、少なくともＮＯガスの測定濃度レンジにおける最大量よりも過剰に供給する。オゾン発生部４２からガス混合部４３へ、Ｏ３ガスを充分に含む原料ガスＧＯを供給する。
The ozone generator 42 is in an operating state. At this time, the ozone generating unit 42 generates ozone gas (hereinafter simply referred to as O 3 gas) from O 2 gas contained in the source gas G 0 such as the atmosphere, instrument air, or oxygen gas. Although the generation amount of O 3 gas can be determined as appropriate, it is supplied in excess of at least the maximum amount in the measured concentration range of NO gas. From the ozone generator 42 to the gas mixing unit 43 supplies the raw material gas G O containing O 3 gas sufficiently.
ガス混合部４３においてＯ３ガスを充分に含む原料ガスＧＯとサンプルガスＧＳとが混合される。ここで、サンプルガスＧＳ中の全てのＮＯガスと、一部のＯ３ガスと、が以下のような化学反応を起こす。
And the raw material gas G O and the sample gas G S containing O 3 gas sufficiently is mixed in the gas mixing portion 43. Here, causing all of the NO gas in the sample gas G S, and a part of the O 3 gas, but the chemical reactions described below.
［化１］
ＮＯ＋Ｏ３ → ＮＯ２＋Ｏ２ ・・・化学反応式（１） [Chemical 1]
NO + O 3 → NO 2 + O 2 ... Chemical reaction formula (1)
ＮＯ＋Ｏ３ → ＮＯ２＋Ｏ２ ・・・化学反応式（１） [Chemical 1]
NO + O 3 → NO 2 + O 2 ... Chemical reaction formula (1)
オゾン発生部４２から供給するＯ３ガス量が、サンプルガスＧＳ中のＮＯガス量に対して過剰であることから、サンプルガスＧＳ中のＮＯガスは、化学反応式（１）にしたがって、全てＮＯ２ガスに変換される。
O 3 gas amount supplied from the ozone generator 42 is, because it is excessive relative to NO gas amount in the sample gas G S, NO gas in the sample gas G S is according to the chemical reaction formula (1), All are converted to NO 2 gas.
さらに、この化学反応式（１）で使用されなかった余剰のＯ３ガスは、サンプルガスＧＳ中に元より含まれていたＮＯ２ガスの一部、および、化学反応式（１）にしたがって生成したＮＯ２ガスの一部、と以下のような化学反応を起こす。
Moreover, excess O 3 gas not used in the chemical reaction formula (1), the sample gas G S portion of the NO 2 gas contained than the original in, and, according to the chemical reaction formula (1) The following chemical reaction occurs with a part of the generated NO 2 gas.
［化２］
２ＮＯ２＋Ｏ３ → Ｎ２Ｏ５＋Ｏ２ ・・・化学反応式（２） [Chemical formula 2]
2NO 2 + O 3 → N 2 O 5 + O 2 ... Chemical reaction formula (2)
２ＮＯ２＋Ｏ３ → Ｎ２Ｏ５＋Ｏ２ ・・・化学反応式（２） [Chemical formula 2]
2NO 2 + O 3 → N 2 O 5 + O 2 ... Chemical reaction formula (2)
このように、ガス混合部４３において、サンプルガスＧＳ中のＮＯガスは全てＮＯ２ガスに変換される。さらに、サンプルガスＧＳ中のＮＯ２ガスの一部、および、化学反応式（１）によって生成したＮＯ２ガスの一部はＮ２Ｏ５ガスに変換される。したがって、ＮＯ２ガスのガス量は、サンプルガスＧＳ中のＮＯより生成したＮＯ２ガスのガス量と、サンプルガスＧＳ中のＮＯ２ガスのガス量との和から、さらにＮ２Ｏ５ガスのガス量の２倍を減じたものとなっている。これは化学反応式（２）により、反応後のＮ２Ｏ５ガス量がＮＯ２ガスのガス量の半分になるためである。さらに余剰のＯ３ガスが一部残留している。
Thus, in the gas mixing unit 43, and converted all NO gas in the sample gas G S is the NO 2 gas. In addition, some of the NO 2 gas in the sample gas G S, and, in some NO 2 gas produced by a chemical reaction formula (1) is converted to N 2 O 5 gas. Therefore, the amount of gas NO 2 gas, and NO 2 gas in the gas amount produced from NO in the sample gas G S, the sum of the amount of gas NO 2 gas in the sample gas G S, further N 2 O 5 The amount of gas is reduced by twice the amount of gas. This is because the amount of N 2 O 5 gas after the reaction is half of the amount of NO 2 gas according to the chemical reaction formula (2). Furthermore, a part of the surplus O 3 gas remains.
このようにガス調整部４１は、サンプルガスＧＳに含まれるＮＯガスをＯ３ガスにより酸化して全てＮＯ２ガスに反応させた測定対象ガスとして出力する酸化出力を行う。これらのようなＮＯ２ガス、Ｎ２Ｏ５ガス、余剰のＯ３ガス、余剰の原料ガスＧＯおよび余剰のサンプルガスＧＳを含む測定対象ガスがガス流通セル２１へ導入される。
The gas conditioning unit 41 as performs oxidation output for outputting a NO gas contained in the sample gas G S as a measurement object gas reacted to all oxidized NO 2 gas by the O 3 gas. Such as these NO 2 gas, N 2 O 5 gas, excess O 3 gas, the measurement object gas containing the raw material gas G O and excess sample gas G S excess is introduced into the gas flow cell 21.
続いて、酸化出力時におけるガス分析計１００のＮＯ２ガス濃度ｃｍの算出について説明する。ＮＯ２ガス濃度測定時ではＮＯ２ガス吸光用発光部１１のみ発光する。ＮＯ２ガス吸光用発光部１１からのＮＯ２ガス吸光用照射光は、部分反射部１３によって既知の一定の反射率によって反射され、基準光受光部３２に入射する。したがって基準光受光部３２の信号から出力強度Ｐ０を求めることができる
Next, calculation of the NO 2 gas concentration cm of the gas analyzer 100 at the time of oxidation output will be described. At the time of measuring the NO 2 gas concentration, only the NO 2 gas absorption light emitting unit 11 emits light. NO 2 irradiation light gas absorption from NO 2 gas absorption for the light emitting unit 11 is reflected by the known constant reflectivity by the partial reflection unit 13 and enters the reference light receiving unit 32. Therefore, the output intensity P 0 can be obtained from the signal of the reference light receiving unit 32.
また、部分反射部１３を透過して光透過窓２３を経てガス流通セル２１内の検出空間２５に入射したＮＯ２ガス吸光用照射光は、検出空間２５を伝播しながら、ＮＯ２ガスによって吸光される。このような吸光されたＮＯ２ガス吸光用照射光が、光透過窓２４を透過し、透過光受光部３１に入射する。したがって、透過光受光部３１の信号から出力強度Ｐ１を求めることができる。
Further, NO 2 irradiation light gas absorption incident on the detection space 25 of the passes through the partial reflection unit 13 light transmissive window 23 via a gas flow cell 21, while propagating the detection space 25, absorption by NO 2 gas Is done. Such absorbed light for absorbing NO 2 gas passes through the light transmission window 24 and enters the transmitted light receiving unit 31. Therefore, the output intensity P 1 can be obtained from the signal of the transmitted light receiving unit 31.
なお、このように受光素子として透過光受光部３１および基準光受光部３２を用いることにより、単に濃度を測定できるだけでなく、ＮＯ２ガス吸光用発光部１１の出力がさまざまな要因で変動しても、２個の受光信号の比を算出することにより濃度測定の誤差を低減できるという効果がある。
By using the transmitted light receiving unit 31 and the reference light receiving unit 32 as the light receiving elements in this way, not only can the concentration be measured, but also the output of the NO 2 gas absorbing light emitting unit 11 varies due to various factors. Also, there is an effect that an error in density measurement can be reduced by calculating the ratio of the two received light signals.
透過光受光部３１、基準光受光部３２からの出力信号は、信号処理・駆動制御部６１に伝送される。信号処理・駆動制御部６１は、上記の数式１に基づいて、ガス流通セル２１の検出空間２５内におけるＮＯ２ガス濃度を算出する。なお、Ｏ３ガスを生成するための原料ガスＧＯがガス混合部４３において混合されているため、ＮＯ２ガス濃度は原料ガスＧＯとサンプルガスＧＳの流量混合比に応じて希釈されている。そこで、ガス混合部４３での流量混合比を乗じることにより、サンプルガスＧＳに含まれているＮＯ２ガス濃度ｃｍを算出する。
Output signals from the transmitted light receiving unit 31 and the reference light receiving unit 32 are transmitted to the signal processing / drive control unit 61. The signal processing / drive control unit 61 calculates the NO 2 gas concentration in the detection space 25 of the gas flow cell 21 based on the above mathematical formula 1. Since the raw material gas G O for producing O 3 gas is mixed in the gas mixing unit 43, NO 2 gas concentration is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S Yes. Therefore, by multiplying the flow mixing ratio of a gas mixing section 43, calculates the NO 2 gas concentration c m contained in the sample gas G S.
次に、ガス分析計１００による反応後に残留するＯ３ガス濃度ｃ３の算出について説明する。これは（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析である。酸化出力時では、上記のようなＮＯ２ガス、Ｎ２Ｏ５ガス、余剰のＯ３ガス、余剰の原料ガスＧＯおよび余剰のサンプルガスＧＳを含む測定対象ガスがガス流通セル２１へ導入される。
Next, calculation of the O 3 gas concentration c 3 remaining after the reaction by the gas analyzer 100 will be described. This is (b) analysis with irradiation light for absorbing O 3 gas at the time of oxidation output. In the oxidation output, introduced NO 2 gas as described above, N 2 O 5 gas, excess O 3 gas, the measurement object gas containing the raw material gas G O and excess sample gas G S surplus to gas flow cell 21 Is done.
Ｏ３ガス濃度測定時ではＯ３ガス吸光用発光部１２のみ発光する。Ｏ３ガス吸光用発光部１２からのＯ３ガス吸光用照射光は、部分反射部１３によって既知の一定の反射率によって反射され、基準光受光部３２に入射する。したがって基準光受光部３２の信号から出力強度Ｐ０を求めることができる。
At the time of measuring the O 3 gas concentration, only the O 3 gas absorption light emitting unit 12 emits light. Irradiation light for absorbing O 3 gas from the light emitting unit 12 for absorbing O 3 gas is reflected by the partial reflection unit 13 with a known constant reflectance and enters the reference light receiving unit 32. Therefore, the output intensity P 0 can be obtained from the signal from the reference light receiving unit 32.
また、部分反射部１３を透過して光透過窓２３を経てガス流通セル２１内の検出空間２５に入射したＯ３ガス吸光用照射光は、検出空間２５を伝播しながら、Ｏ３ガスおよびＮＯ２ガスによって吸光される。このような吸光されたＯ３ガス吸光用照射光が、光透過窓２４を透過し、透過光受光部３１に入射する。したがって、透過光受光部３１の信号から出力強度Ｐ１を求めることができる。ただし、この出力強度Ｐ１はＮＯ２ガスによる吸光も含んでいる。
In addition, the irradiation light for absorbing O 3 gas that has passed through the partial reflection portion 13 and entered the detection space 25 in the gas flow cell 21 through the light transmission window 23 propagates through the detection space 25, while O 3 gas and NO. Absorbed by two gases. Such absorbed light for absorbing O 3 gas is transmitted through the light transmission window 24 and enters the transmitted light receiving unit 31. Therefore, it is possible to determine the output intensity P 1 from the signal of the transmitted light receiving unit 31. However, the output intensity P 1 includes light absorption by NO 2 gas.
なお、このように受光素子として透過光受光部３１および基準光受光部３２を用いることにより、単に濃度を測定できるだけでなく、Ｏ３ガス吸光用発光部１２の出力がさまざまな要因で変動しても、２個の受光信号の比を算出することにより濃度測定の誤差を低減できるという効果がある。
In addition, by using the transmitted light receiving unit 31 and the reference light receiving unit 32 as the light receiving elements in this way, not only can the concentration be measured, but the output of the light emitting unit 12 for absorbing O 3 gas varies due to various factors. Also, there is an effect that an error in density measurement can be reduced by calculating the ratio of the two received light signals.
透過光受光部３１、基準光受光部３２からの出力信号は、信号処理・駆動制御部６１に伝送される。信号処理・駆動制御部６１では出力強度Ｐ０、Ｐ１を算出し、数式１に基づいて、Ｏ３ガス濃度＋ＮＯ２ガス濃度を算出し、さらにガス混合部４３での流量混合比を乗じることにより、サンプルガスＧＳに含まれているＯ３ガス濃度ｃ３＋ＮＯ２ガス濃度ｃｍを算出する。
Output signals from the transmitted light receiving unit 31 and the reference light receiving unit 32 are transmitted to the signal processing / drive control unit 61. The signal processing / drive control unit 61 calculates the output intensities P 0 and P 1 , calculates the O 3 gas concentration + NO 2 gas concentration based on Equation 1, and multiplies the flow rate mixing ratio in the gas mixing unit 43. by, O 3 calculates the gas concentration c 3 + NO 2 gas concentration c m contained in the sample gas G S.
続いて、オゾン発生部４２を不動作状態としてガス調整部４１を通常出力させた上での測定である。この際に、サンプルガスＧＳに含まれるＮＯ２ガス濃度ｃ２を求める。これは上記の（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析である。
Subsequently, the measurement is performed after the ozone generating unit 42 is in an inoperative state and the gas adjusting unit 41 is normally output. In this case, determining the NO 2 gas concentration c 2 in the sample gas G S. This is (c) the analysis by the irradiation light for absorbing NO 2 gas at the normal output.
オゾン発生部４２は不動作状態である。このとき、前述のように原料ガスＧＯがオゾン発生部４２をそのまま通過し、ガス混合部４３においてサンプルガスＧＳと混合される。Ｏ３ガスが存在しないため化学反応が起きることはなく、無反応の原料ガスＧＯとサンプルガスＧＳとがそのままガス混合部４３から流出する。ガス調整部４１は無反応のサンプルガスＧＳと原料ガスＧＯとを測定対象ガスとして出力するという通常出力を行う。
The ozone generator 42 is in an inoperative state. At this time, the raw material gas G O is passes through the ozone generator 42 as described above, is mixed with the sample gas G S in the gas mixing portion 43. O 3 never since the gas is not present chemical reaction occurs, and the raw material gas G O and the sample gas G S-free reaction as it flows out from the gas mixing unit 43. Gas conditioning unit 41 performs a normal output that outputs the sample gas G S and the raw material gas G O unresponsive as a measurement target gas.
このようにＯ３ガスが存在しないために、ガス混合部４３で化学反応式（１）および化学反応式（２）で示される化学反応式は起きない。
Since there is no O 3 gas in this way, the chemical reaction formulas represented by the chemical reaction formula (1) and the chemical reaction formula (2) do not occur in the gas mixing unit 43.
この結果、ガス流通セル２１に流通するサンプルガスＧＳに含まれるガスの状態は、サンプルガスＧＳに含まれていたＮＯガス、ＮＯ２ガスが全てそのままの状態となっている。また、原料ガスがガス混合部４３において混合されているため、ＮＯガス、ＮＯ２ガスの各濃度は原料ガスＧＯとサンプルガスＧＳの流量混合比に応じて希釈されている。このような原料ガスＧＯとサンプルガスＧＳとがガス流通セル２１へ導入される。
As a result, the state of gas in the sample gas G S that circulates in the gas flow cell 21, NO gas contained in the sample gas G S, NO 2 gas has become all intact. Further, since the raw material gas is mixed in the gas mixing unit 43, NO gas, the concentration of NO 2 gas is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S. And such feed gas G O and the sample gas G S is introduced into the gas flow cell 21.
そしてガス濃度の検出自体は先に説明したオゾン発生部４２の動作時（酸化出力時）と同様にして求められる。このようにしてＮＯ２ガス濃度ｃ２が算出される。
The detection of the gas concentration itself is obtained in the same manner as the operation of the ozone generator 42 described above (during oxidation output). In this way, the NO 2 gas concentration c 2 is calculated.
次に、オゾン発生部４２の動作時で酸化出力時のガス濃度と、不動作時で通常出力時のガス濃度と、の組み合わせにより、サンプルガスＧＳ中のＮＯガス濃度ｃ１を算出する。
先に説明したように、
（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃｍ、
（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析で算出されたＯ３ガス濃度ｃ３＋ＮＯ２ガス濃度ｃｍ
（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃ２、
が測定されている。ここで、ＮＯ２ガス濃度ｃｍが判別しているため、Ｏ３ガス濃度ｃ３も判別している。 Then, it calculates the gas concentration upon oxidation output operation of theozone generator 42, and the gas concentration at the time of normal output in an off-state, the combination of a NO gas concentration c 1 in the sample gas G S.
As explained earlier,
(A) NO 2 gas concentration cm calculated by analysis with irradiation light for absorbing NO 2 gas during oxidation output,
(B) O 3 gas concentration c 3 + NO 2 gas concentration cm calculated by analysis with irradiation light for O 3 gas absorption at oxidation output
(C) NO 2 gas concentration c 2 calculated by analysis with irradiation light for absorbing NO 2 gas at normal output,
Has been measured. Here, since the NO 2 gas concentration cm is determined, the O 3 gas concentration c 3 is also determined.
先に説明したように、
（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃｍ、
（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析で算出されたＯ３ガス濃度ｃ３＋ＮＯ２ガス濃度ｃｍ
（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃ２、
が測定されている。ここで、ＮＯ２ガス濃度ｃｍが判別しているため、Ｏ３ガス濃度ｃ３も判別している。 Then, it calculates the gas concentration upon oxidation output operation of the
As explained earlier,
(A) NO 2 gas concentration cm calculated by analysis with irradiation light for absorbing NO 2 gas during oxidation output,
(B) O 3 gas concentration c 3 + NO 2 gas concentration cm calculated by analysis with irradiation light for O 3 gas absorption at oxidation output
(C) NO 2 gas concentration c 2 calculated by analysis with irradiation light for absorbing NO 2 gas at normal output,
Has been measured. Here, since the NO 2 gas concentration cm is determined, the O 3 gas concentration c 3 is also determined.
ここで、酸化出力状態のＮＯ２ガス濃度ｃｍは、測定対象ガスのうちで、サンプルガスＧＳに含まれていた元のＮＯガス濃度ｃ１及び元のＮＯ２ガス濃度ｃ２の和から、Ｎ２Ｏ５ガス濃度の２倍を減じた濃度である。Ｎ２Ｏ５の生成には、２個のＮＯ２が必要なためである。換言すれば、Ｎ２Ｏ５ガス濃度は元のＮＯガス濃度ｃ１及び元のＮＯ２ガス濃度ｃ２の和から、ＮＯ２ガス濃度ｃｍを減じた濃度の１／２である。なお、オゾン発生部４２により供給されるＯ３ガス濃度は、オゾン発生部４２が内蔵するオゾン計等により予め知ることができ、その値をｃ０とする。
Here, the NO 2 gas concentration c m oxidation output state, of the measurement target gas, from the sum of the sample gas G of the original that was included in the S NO gas concentration c 1 and the original NO 2 gas concentration c 2 , The concentration obtained by subtracting twice the N 2 O 5 gas concentration. This is because the production of N 2 O 5 requires two NO 2 . In other words, the N 2 O 5 gas concentration is ½ of the concentration obtained by subtracting the NO 2 gas concentration cm from the sum of the original NO gas concentration c 1 and the original NO 2 gas concentration c 2 . Note that the O 3 gas concentration supplied by the ozone generator 42 can be known in advance by an ozone meter or the like built in the ozone generator 42, and the value is c 0 .
ここで、ｃ０、ｃ１、ｃ２、ｃ３、ｃｍの関係は、次式のようになる。
Here, the relationship between c 0 , c 1 , c 2 , c 3 , and cm is as follows.
［数２］
反応で消費されたＯ３ガス濃度
＝供給されるＯ３ガス濃度－測定されたＯ３ガス濃度
＝ｃ０－ｃ３ [Equation 2]
O 3 gas concentration which has been consumed in the reaction = O 3 gas concentration is supplied - measured O 3 gas concentration = c 0 -c 3
反応で消費されたＯ３ガス濃度
＝供給されるＯ３ガス濃度－測定されたＯ３ガス濃度
＝ｃ０－ｃ３ [Equation 2]
O 3 gas concentration which has been consumed in the reaction = O 3 gas concentration is supplied - measured O 3 gas concentration = c 0 -c 3
ここで反応により消費されるＯ３ガスは、ＮＯガスからＮＯ２ガスへの反応に用いられ、さらにＮＯ２ガスからＮ２Ｏ５ガスへの反応に用いられる。従って、次式のようになる。
Here, the O 3 gas consumed by the reaction is used for a reaction from NO gas to NO 2 gas, and further used for a reaction from NO 2 gas to N 2 O 5 gas. Therefore, the following equation is obtained.
［数３］
反応で消費されたＯ３ガス濃度
＝測定対象ガス中のＮＯガス濃度＋測定対象ガス中のＮ２Ｏ５ガス濃度
＝ｃ１＋（ｃ１＋ｃ２－ｃｍ）／２ [Equation 3]
Concentration of O 3 gas consumed in the reaction
= NO gas concentration in measurement target gas + N 2 O 5 gas concentration in measurement target gas
= C 1 + (c 1 + c 2 −c m ) / 2
反応で消費されたＯ３ガス濃度
＝測定対象ガス中のＮＯガス濃度＋測定対象ガス中のＮ２Ｏ５ガス濃度
＝ｃ１＋（ｃ１＋ｃ２－ｃｍ）／２ [Equation 3]
Concentration of O 3 gas consumed in the reaction
= NO gas concentration in measurement target gas + N 2 O 5 gas concentration in measurement target gas
= C 1 + (c 1 + c 2 −c m ) / 2
この二式は等しいため以下の式のようになる。
Since these two formulas are equal, the following formula is obtained.
［数４］
ｃ０－ｃ３ ＝ｃ１＋（ｃ１＋ｃ２－ｃｍ）／２ [Equation 4]
c 0 −c 3 = c 1 + (c 1 + c 2 −c m ) / 2
ｃ０－ｃ３ ＝ｃ１＋（ｃ１＋ｃ２－ｃｍ）／２ [Equation 4]
c 0 −c 3 = c 1 + (c 1 + c 2 −c m ) / 2
したがって、ＮＯガス濃度ｃ１は次式のようになる。
Therefore, the NO gas concentration c 1 is expressed by the following equation.
［数５］
ｃ１＝｛２（ｃ０－ｃ３）－（ｃ２－ｃｍ）｝／３ [Equation 5]
c 1 = {2 (c 0 -c 3 )-(c 2 -c m )} / 3
ｃ１＝｛２（ｃ０－ｃ３）－（ｃ２－ｃｍ）｝／３ [Equation 5]
c 1 = {2 (c 0 -c 3 )-(c 2 -c m )} / 3
上記（ａ）によりｃｍが、上記（ｂ）によりｃ３が、上記（ｃ）によりｃ２が、それぞれ測定により算出される。また、ｃ０は予め知り得ている。
これにより、ＮＯガス濃度ｃ１を算出することができる。 (A) above by c m is the c 3 is a (b), the c 2 is the (c), is calculated by the respective measurements. In addition, c 0 is getting to know in advance.
Thus, we are possible to calculate the NO gas concentration c 1.
これにより、ＮＯガス濃度ｃ１を算出することができる。 (A) above by c m is the c 3 is a (b), the c 2 is the (c), is calculated by the respective measurements. In addition, c 0 is getting to know in advance.
Thus, we are possible to calculate the NO gas concentration c 1.
このようにして、ＮＯガス濃度ｃ１、ＮＯ２ガス濃度ｃ２を測定することができる。
これらの測定方法を組み合わせることにより、ＮＯガス、ＮＯ２のガス濃度を測定することができる。 In this way, the NO gas concentration c 1 and the NO 2 gas concentration c 2 can be measured.
By combining these measurement methods, the gas concentrations of NO gas and NO 2 can be measured.
これらの測定方法を組み合わせることにより、ＮＯガス、ＮＯ２のガス濃度を測定することができる。 In this way, the NO gas concentration c 1 and the NO 2 gas concentration c 2 can be measured.
By combining these measurement methods, the gas concentrations of NO gas and NO 2 can be measured.
また、ガス濃度の校正のために、ゼロガスＧＺＥＲＯまたはスパンガスＧＳＰＡＮを用いることができる。ゼロガスＧＺＥＲＯは、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２が吸光を示さないガス、例えば窒素ガス（Ｎ２ガス）である。スパンガスＧＳＰＡＮは、所望の測定レンジの最大濃度値で校正されたガスで、例えばＮＯガス、ＮＯ２ガスが用いられる。
Also, zero gas G ZERO or span gas G SPAN can be used for gas concentration calibration. The zero gas G ZERO is a gas in which the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 do not absorb light, for example, nitrogen gas (N 2 gas). Span gas G SPAN is a gas that has been calibrated at a maximum concentration value of the desired measurement range, such as NO gas, NO 2 gas is used.
サンプルガスＧＳの供給を止め、その後にゼロガスＧＺＥＲＯの供給を行ってゼロガスＧＺＥＲＯ流通時の受光信号を測定して校正し、または、スパンガスＧＳＰＡＮの供給を行ってスパンガスＧＳＰＡＮ流通時の吸光された受光信号を測定して校正を行うことができる。この校正は随時実施できるが、構成部品の経年変化によってガス濃度指示値が変動することが想定される場合に行われ、正確な値を指示させる。
ガス分析計１００はこのようなものである。 Stopping the supply of the sample gas G S, followed by performing the supply of the zero gas G ZERO calibrated by measuring the light signal at the zero gas G ZERO distribution, or at the time span G SPAN flow by performing the supply of the span gas G SPAN Calibration can be performed by measuring the absorbed light-receiving signal. Although this calibration can be performed at any time, it is performed when it is assumed that the gas concentration indicating value fluctuates due to aging of the component parts, and an accurate value is indicated.
Thegas analyzer 100 is like this.
ガス分析計１００はこのようなものである。 Stopping the supply of the sample gas G S, followed by performing the supply of the zero gas G ZERO calibrated by measuring the light signal at the zero gas G ZERO distribution, or at the time span G SPAN flow by performing the supply of the span gas G SPAN Calibration can be performed by measuring the absorbed light-receiving signal. Although this calibration can be performed at any time, it is performed when it is assumed that the gas concentration indicating value fluctuates due to aging of the component parts, and an accurate value is indicated.
The
続いて他の第２形態について説明する。本形態ではガス分析計としての構成は図１を用いて説明した先の第１形態と同じであるが分析対象が相違している。先の第１形態ではＮＯガス濃度ｃ１、ＮＯ２ガス濃度ｃ２を算出したが、以上の測定と同時にＳＯ２ガス濃度ｃＳの測定を併せて行う。本形態では、サンプルガスがＮＯガス、ＮＯ２ガス、ＳＯ２ガスを含み、これらのＮＯガス濃度ｃ１、ＮＯ２ガス濃度ｃ２、ＳＯ２ガス濃度ｃＳを測定するものである。
Next, another second embodiment will be described. In this embodiment, the configuration as a gas analyzer is the same as that of the first embodiment described with reference to FIG. 1, but the analysis object is different. In the first embodiment, the NO gas concentration c 1 and the NO 2 gas concentration c 2 are calculated, but the SO 2 gas concentration c S is measured simultaneously with the above measurement. In this embodiment, the sample gas contains NO gas, NO 2 gas, and SO 2 gas, and these NO gas concentration c 1 , NO 2 gas concentration c 2 , and SO 2 gas concentration c S are measured.
ＳＯ２ガスの紫外線吸収スペクトルは、図２に示すように２７０ｎｍ～３１０ｎｍ付近であり、Ｏ３ガスの紫外線吸収スペクトルと重なっている。Ｏ３ガス吸光用発光部１２の中心波長を２８０ｎｍ付近とすることにより、ＳＯ２ガスの吸収信号を得ることが可能となる。
UV absorption spectrum of the SO 2 gas is near 270 nm ~ 310 nm, as shown in FIG. 2, overlaps the ultraviolet absorption spectrum of the O 3 gas. By setting the central wavelength of the O 3 gas light-absorbing light emitting portion 12 to be around 280 nm, an SO 2 gas absorption signal can be obtained.
このような測定は、オゾン発生部４２を動作状態としてガス調整部４１を酸化出力としたときと、オゾン発生部４２を不動作状態としてガス調整部４１を通常出力としたときと、でそれぞれ行われる。したがって、このようなガス分析計１００は、
（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析、
（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析、
（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析、
（ｄ）通常出力時のＯ３ガス吸光用照射光による分析、
という４種類の分析が可能であり、（ａ）、（ｂ）、（ｃ）、（ｄ）の全ての分析を行い、これらで得た測定値を用いてガス濃度を算出する。 Such measurement is performed when theozone generation unit 42 is in an operating state and the gas adjustment unit 41 is in an oxidized output, and when the ozone generation unit 42 is in a non-operational state and the gas adjustment unit 41 is in a normal output. Is called. Therefore, such a gas analyzer 100 is
(A) Analysis with irradiation light for absorbing NO 2 gas at the time of oxidation output,
(B) analysis by the O 3 gas absorption for the irradiation light at the time of oxidation output,
(C) Analysis with irradiation light for absorbing NO 2 gas at normal output,
(D) Analysis with irradiation light for absorbing O 3 gas at normal output,
The following four types of analysis are possible: (a), (b), (c), and (d) are all analyzed, and the gas concentration is calculated using the measured values obtained by these.
（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析、
（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析、
（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析、
（ｄ）通常出力時のＯ３ガス吸光用照射光による分析、
という４種類の分析が可能であり、（ａ）、（ｂ）、（ｃ）、（ｄ）の全ての分析を行い、これらで得た測定値を用いてガス濃度を算出する。 Such measurement is performed when the
(A) Analysis with irradiation light for absorbing NO 2 gas at the time of oxidation output,
(B) analysis by the O 3 gas absorption for the irradiation light at the time of oxidation output,
(C) Analysis with irradiation light for absorbing NO 2 gas at normal output,
(D) Analysis with irradiation light for absorbing O 3 gas at normal output,
The following four types of analysis are possible: (a), (b), (c), and (d) are all analyzed, and the gas concentration is calculated using the measured values obtained by these.
次に、このガス分析計１００によってサンプルガスＧＳ中に含まれるＮＯガス、ＮＯ２ガスおよびＳＯ２ガスの３成分のガス濃度を測定する方法について説明する。
Next, a method for measuring the gas concentration of the three components of NO gas, NO 2 gas and SO 2 gas contained by the gas analyzer 100 in the sample gas G S.
まず、（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析を行うものとして説明する。オゾン発生部４２を動作状態としてガス調整部４１を酸化出力させた上での測定である。この際に、酸化出力時のＮＯ２ガス濃度ｃｍを求める。
First, description will be made on the assumption that (a) analysis is performed using irradiation light for absorbing NO 2 gas at the time of oxidation output. This is a measurement after the ozone generating section 42 is in an operating state and the gas adjusting section 41 is oxidized and output. At this time, the NO 2 gas concentration cm at the oxidation output is obtained.
オゾン発生部４２は動作状態である。このときは上記のようにガス調整部４１は、サンプルガスＧＳに含まれるＮＯガスをＯ３ガスにより酸化して全てＮＯ２ガスに反応させた測定対象ガスとして出力する酸化出力を行う。なお、ＳＯ２ガスとＯ３ガスとは化学反応を起こさない。これらのようなＳＯ２ガス、ＮＯ２ガス、Ｎ２Ｏ５ガス、余剰のＯ３ガス、余剰の原料ガスＧＯおよび余剰のサンプルガスＧＳを含む測定対象ガスがガス流通セル２１へ導入される。
The ozone generator 42 is in an operating state. Gas conditioning unit 41 as described above this time, an oxidation output for outputting a NO gas contained in the sample gas G S as a measurement object gas reacted to all oxidized NO 2 gas by the O 3 gas. The SO 2 gas and the O 3 gas do not cause a chemical reaction. Such as these SO 2 gas, NO 2 gas, is introduced into the N 2 O 5 gas, excess O 3 gas, the excess of the raw material gas G O and excess sample gas G S measurement target gas is gas flow cell 21 comprising The
続いて、酸化出力時におけるガス分析計１００のＮＯ２ガス濃度ｃｍの算出について説明する。ＮＯ２ガス濃度測定時ではＮＯ２ガス吸光用発光部１１のみ発光する。ＮＯ２ガス吸光用発光部１１からのＮＯ２ガス吸光用照射光は、部分反射部１３によって既知の一定の反射率によって反射され、基準光受光部３２に入射する。したがって基準光受光部３２の信号から出力強度Ｐ０を求めることができる。
Next, calculation of the NO 2 gas concentration cm of the gas analyzer 100 at the time of oxidation output will be described. Than when NO 2 gas concentration measurement emits light only NO 2 gas absorption for the light emitting unit 11. NO 2 irradiation light gas absorption from NO 2 gas absorption for the light emitting unit 11 is reflected by the known constant reflectivity by the partial reflection unit 13 and enters the reference light receiving unit 32. Therefore, the output intensity P 0 can be obtained from the signal from the reference light receiving unit 32.
また、部分反射部１３を透過して光透過窓２３を経てガス流通セル２１内の検出空間２５に入射したＮＯ２ガス吸光用照射光は、検出空間２５を伝播しながら、ＮＯ２ガスによって吸光される。このような吸光されたＮＯ２ガス吸光用照射光が、光透過窓２４を透過し、透過光受光部３１に入射する。したがって、透過光受光部３１の信号から出力強度Ｐ１を求めることができる。
Further, NO 2 irradiation light gas absorption incident on the detection space 25 of the passes through the partial reflection unit 13 light transmissive window 23 via a gas flow cell 21, while propagating the detection space 25, absorption by NO 2 gas Is done. Such absorbed light for absorbing NO 2 gas passes through the light transmission window 24 and enters the transmitted light receiving unit 31. Therefore, the output intensity P 1 can be obtained from the signal of the transmitted light receiving unit 31.
透過光受光部３１、基準光受光部３２からの出力信号は、信号処理・駆動制御部６１に伝送される。信号処理・駆動制御部６１は、上記の数式１に基づいて、ガス流通セル２１の検出空間２５内におけるＮＯ２ガス濃度を算出する。なお、Ｏ３ガスを生成するための原料ガスＧＯがガス混合部４３において混合されているため、ＮＯ２ガス濃度は原料ガスＧＯとサンプルガスＧＳの流量混合比に応じて希釈されている。そこで、ガス混合部４３での流量混合比を乗じることにより、サンプルガスＧＳに含まれているＮＯ２ガス濃度ｃｍを算出する。
Output signals from the transmitted light receiving unit 31 and the reference light receiving unit 32 are transmitted to the signal processing / drive control unit 61. The signal processing / drive control unit 61 calculates the NO 2 gas concentration in the detection space 25 of the gas flow cell 21 based on the above mathematical formula 1. Since the raw material gas G O for producing O 3 gas is mixed in the gas mixing unit 43, NO 2 gas concentration is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S Yes. Therefore, by multiplying the flow mixing ratio of a gas mixing section 43, calculates the NO 2 gas concentration c m contained in the sample gas G S.
次に、ガス分析計１００による反応後に残留するＯ３ガス濃度ｃ３およびＳＯ２ガス濃度ｃＳの算出について説明する。これは（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析である。酸化出力時では、上記のようなＳＯ２ガス、ＮＯ２ガス、Ｎ２Ｏ５ガス、余剰のＯ３ガス、余剰の原料ガスＧＯおよび余剰のサンプルガスＧＳを含む測定対象ガスがガス流通セル２１へ導入される。なお、ＳＯ２ガスは酸化出力時でも無反応でそのままである。
Next, calculation of the O 3 gas concentration c 3 and the SO 2 gas concentration c S remaining after the reaction by the gas analyzer 100 will be described. This is (b) analysis with irradiation light for absorbing O 3 gas at the time of oxidation output. In the oxidation output, SO 2 gas, as described above, NO 2 gas, N 2 O 5 gas, excess O 3 gas, the measurement object gas containing the raw material gas G O and excess sample gas G S of excess gas flow It is introduced into the cell 21. Note that the SO 2 gas remains unreacted even at the time of oxidation output.
Ｏ３ガス濃度測定時ではＯ３ガス吸光用発光部１２のみ発光する。Ｏ３ガス吸光用発光部１２からのＯ３ガス吸光用照射光は、部分反射部１３によって既知の一定の反射率によって反射され、基準光受光部３２に入射する。したがって基準光受光部３２の信号から出力強度Ｐ０を求めることができる。
At the time of measuring the O 3 gas concentration, only the O 3 gas absorption light emitting unit 12 emits light. Irradiation light for absorbing O 3 gas from the light emitting unit 12 for absorbing O 3 gas is reflected by the partial reflection unit 13 with a known constant reflectance and enters the reference light receiving unit 32. Therefore, the output intensity P 0 can be obtained from the signal from the reference light receiving unit 32.
また、部分反射部１３を透過して光透過窓２３を経てガス流通セル２１内の検出空間２５に入射したＯ３ガス吸光用照射光は、検出空間２５を伝播しながら、ＳＯ２ガス、Ｏ３ガスおよびＮＯ２ガスによって吸光される。このような吸光されたＯ３ガス吸光用照射光が、光透過窓２４を透過し、透過光受光部３１に入射する。したがって、透過光受光部３１の信号から出力強度Ｐ１を求めることができる。当然に出力強度Ｐ１はＳＯ２ガス、Ｏ３ガスおよびＮＯ２ガスによる吸光を含んでいる。
Further, O 3 irradiation light gas absorption incident on the detection space 25 in the gas flow cell 21 passes through the partial reflection unit 13 through the light transmission window 23, while propagating the detection space 25, SO 2 gas, O Absorbed by 3 gas and NO 2 gas. Such absorbed light for absorbing O 3 gas is transmitted through the light transmission window 24 and enters the transmitted light receiving unit 31. Therefore, the output intensity P 1 can be obtained from the signal of the transmitted light receiving unit 31. Naturally, the output intensity P 1 includes light absorption by SO 2 gas, O 3 gas and NO 2 gas.
透過光受光部３１、基準光受光部３２からの出力信号は、信号処理・駆動制御部６１に伝送される。信号処理・駆動制御部６１では出力強度Ｐ０、Ｐ１を算出し、数式１に基づいて、Ｏ３ガス濃度＋ＳＯ２ガス濃度＋ＮＯ２ガス濃度を算出し、さらにガス混合部４３での流量混合比を乗じることにより、サンプルガスＧＳに含まれているＯ３ガス濃度ｃ３＋ＳＯ２ガス濃度ｃＳ＋ＮＯ２ガス濃度ｃｍを算出する。
Output signals from the transmitted light receiving unit 31 and the reference light receiving unit 32 are transmitted to the signal processing / drive control unit 61. The signal processing / drive control unit 61 calculates the output intensities P 0 and P 1 , calculates the O 3 gas concentration + SO 2 gas concentration + NO 2 gas concentration based on Equation 1, and further mixes the flow rate in the gas mixing unit 43. by multiplying the ratio to calculate the sample gas G O 3 gas concentration is being included in the S c 3 + SO 2 gas concentration c S + NO 2 gas concentration c m.
続いて、オゾン発生部４２を不動作状態としてガス調整部４１を通常出力させた上での測定である。この際に、サンプルガスＧＳに含まれるＮＯ２ガス濃度ｃ２を求める。これは上記の（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析である。
Subsequently, the measurement is performed after the ozone generating unit 42 is in an inoperative state and the gas adjusting unit 41 is normally output. In this case, determining the NO 2 gas concentration c 2 in the sample gas G S. This is (c) the analysis by the irradiation light for absorbing NO 2 gas at the normal output.
オゾン発生部４２は不動作状態である。このときガス流通セル２１に流通するサンプルガスＧＳに含まれるガスの状態は、サンプルガスＧＳに含まれていたＮＯガス、ＮＯ２ガス、ＳＯ２ガスが全てそのままの状態となっている。また、原料ガスＧＯがガス混合部４３において混合されているため、ＮＯガス、ＮＯ２ガス、ＳＯ２ガスの各濃度は原料ガスＧＯとサンプルガスＧＳの流量混合比に応じて希釈されている。このような原料ガスＧＯとサンプルガスＧＳとがガス流通セル２１へ導入される。
The ozone generator 42 is in an inoperative state. This state gas contained in the sample gas G S that circulates in the gas flow cell 21, NO gas contained in the sample gas G S, NO 2 gas, SO 2 gas has become all intact state. Further, since the raw material gas G O are mixed in the gas mixing portion 43, the concentration of NO gas, NO 2 gas, SO 2 gas is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S ing. And such feed gas G O and the sample gas G S is introduced into the gas flow cell 21.
そして、ガス濃度の検出自体は先に説明したオゾン発生部４２の動作時（酸化出力時）と同様にして求められるものであり、ＮＯ２ガス濃度が算出される。さらにガス混合部４３での流量混合比を乗じることにより、サンプルガスＧＳに含まれているＮＯ２ガス濃度ｃ２を算出する。
The gas concentration detection itself is obtained in the same manner as the operation of the ozone generator 42 described above (at the time of oxidation output), and the NO 2 gas concentration is calculated. Further, by multiplying the flow mixing ratio of a gas mixing section 43, it calculates the NO 2 gas concentration c 2 contained in the sample gas G S.
続いて、オゾン発生部４２を不動作状態としてガス調整部４１を通常出力させた上での測定である。この際に、サンプルガスＧＳに含まれるＳＯ２ガス濃度ｃＳ＋ＮＯ２ガス濃度ｃ２を求める。これは上記の（ｄ）通常出力時のＯ３ガス吸光用照射光による分析である。
Subsequently, the measurement is performed after the ozone generating unit 42 is in an inoperative state and the gas adjusting unit 41 is normally output. At this time, obtaining the SO 2 gas concentration c S + NO 2 gas concentration c 2 in the sample gas G S. This is the analysis by the above (d) irradiation light for absorbing O 3 gas at normal output.
オゾン発生部４２は不動作状態である。このときガス流通セル２１に流通するサンプルガスＧＳに含まれるガスの状態は、サンプルガスＧＳに含まれていたＮＯガス、ＮＯ２ガス、ＳＯ２ガスが全てそのままの状態となっている。また、原料ガスＧＯがガス混合部４３において混合されているため、ＮＯガス、ＮＯ２ガス、ＳＯ２ガスの各濃度は原料ガスＧＯとサンプルガスＧＳの流量混合比に応じて希釈されている。このような原料ガスＧＯとサンプルガスＧＳとがガス流通セル２１へ導入される。
The ozone generator 42 is in an inoperative state. This state gas contained in the sample gas G S that circulates in the gas flow cell 21, NO gas contained in the sample gas G S, NO 2 gas, SO 2 gas has become all intact state. Further, since the raw material gas G O are mixed in the gas mixing portion 43, the concentration of NO gas, NO 2 gas, SO 2 gas is diluted in accordance with the flow mixing ratio of the raw material gas G O and the sample gas G S ing. And such feed gas G O and the sample gas G S is introduced into the gas flow cell 21.
そして、ガス濃度の検出自体は先の説明と同様にして求められるものであり、ＳＯ２ガス濃度＋ＮＯ２ガス濃度が算出される。さらにガス混合部４３での流量混合比を乗じることにより、サンプルガスＧＳに含まれているＳＯ２ガス濃度ｃＳ＋ＮＯ２ガス濃度ｃ２を算出する。
The gas concentration detection itself is obtained in the same manner as described above, and the SO 2 gas concentration + NO 2 gas concentration is calculated. Further, by multiplying the flow mixing ratio of a gas mixing section 43, and calculates the SO 2 gas concentration c S + NO 2 gas concentration c 2 contained in the sample gas G S.
次に、オゾン発生部４２の動作時で酸化出力時のガス濃度と、不動作時で通常出力時のガス濃度と、の組み合わせにより、サンプルガスＧＳ中のＮＯガス濃度ｃ１を算出する。
先に説明したように、
（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃｍ、
（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析で算出されたＯ３ガス濃度ｃ３＋ＮＯ２ガス濃度ｃｍ＋ＳＯ２ガス濃度ｃＳ
（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃ２、
（ｄ）通常出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃ２＋ＳＯ２ガス濃度ｃＳ、
が測定されている。 Then, it calculates the gas concentration upon oxidation output operation of theozone generator 42, and the gas concentration at the time of normal output in an off-state, the combination of a NO gas concentration c 1 in the sample gas G S.
As explained earlier,
(A) NO 2 gas concentration cm calculated by analysis with irradiation light for absorbing NO 2 gas during oxidation output,
(B) O 3 gas concentration c 3 + NO 2 gas concentration c m + SO 2 gas concentration c S calculated by analysis with O 3 gas absorption irradiation light during oxidation output
(C) NO 2 gas concentration c 2 calculated by analysis with irradiation light for absorbing NO 2 gas at normal output,
(D) NO 2 gas concentration c 2 + SO 2 gas concentration c S calculated by analysis with irradiation light for absorbing NO 2 gas at normal output,
Has been measured.
先に説明したように、
（ａ）酸化出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃｍ、
（ｂ）酸化出力時のＯ３ガス吸光用照射光による分析で算出されたＯ３ガス濃度ｃ３＋ＮＯ２ガス濃度ｃｍ＋ＳＯ２ガス濃度ｃＳ
（ｃ）通常出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃ２、
（ｄ）通常出力時のＮＯ２ガス吸光用照射光による分析で算出されたＮＯ２ガス濃度ｃ２＋ＳＯ２ガス濃度ｃＳ、
が測定されている。 Then, it calculates the gas concentration upon oxidation output operation of the
As explained earlier,
(A) NO 2 gas concentration cm calculated by analysis with irradiation light for absorbing NO 2 gas during oxidation output,
(B) O 3 gas concentration c 3 + NO 2 gas concentration c m + SO 2 gas concentration c S calculated by analysis with O 3 gas absorption irradiation light during oxidation output
(C) NO 2 gas concentration c 2 calculated by analysis with irradiation light for absorbing NO 2 gas at normal output,
(D) NO 2 gas concentration c 2 + SO 2 gas concentration c S calculated by analysis with irradiation light for absorbing NO 2 gas at normal output,
Has been measured.
ここで、通常出力時のＮＯ２ガス濃度ｃ２が判別しているため、ＳＯ２ガス濃度ｃＳが判別している。また、酸化出力時のＮＯ２ガス濃度ｃｍが判別しているため、Ｏ３ガス濃度ｃ３が判別している。また、ＮＯガス濃度ｃ１も上記した［数５］で表される。
Here, since the NO 2 gas concentration c 2 at the normal output is determined, the SO 2 gas concentration c S is determined. Further, since the NO 2 gas concentration cm at the time of oxidation output is determined, the O 3 gas concentration c 3 is determined. Further, the NO gas concentration c 1 is also expressed by the above [Equation 5].
このようにして、ＮＯガス濃度ｃ１、ＮＯ２ガス濃度ｃ２、ＳＯ２ガス濃度ｃＳを測定することができる。
これらの測定方法を組み合わせることにより、ＮＯガス、ＮＯ２ガス、ＳＯ２ガスのガス濃度を測定することができる。 In this way, the NO gas concentration c 1 , the NO 2 gas concentration c 2 , and the SO 2 gas concentration c S can be measured.
By combining these measurement methods, the gas concentrations of NO gas, NO 2 gas, and SO 2 gas can be measured.
これらの測定方法を組み合わせることにより、ＮＯガス、ＮＯ２ガス、ＳＯ２ガスのガス濃度を測定することができる。 In this way, the NO gas concentration c 1 , the NO 2 gas concentration c 2 , and the SO 2 gas concentration c S can be measured.
By combining these measurement methods, the gas concentrations of NO gas, NO 2 gas, and SO 2 gas can be measured.
また、ガス濃度の校正のために、ゼロガスＧＺＥＲＯまたはスパンガスＧＳＰＡＮを用いることができる。ゼロガスＧＺＥＲＯは、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２が吸光を示さないガス、例えば窒素ガスである。スパンガスＧＳＰＡＮは、所望の測定レンジの最大濃度値で校正されたガスで、例えばＮＯ、ＮＯ２、ＳＯ２ガスが用いられる。
Also, zero gas G ZERO or span gas G SPAN can be used for gas concentration calibration. Zero gas G ZERO is a gas, for example, nitrogen gas, in which the NO 2 gas absorption light-emitting unit 11 and the O 3 gas absorption light-emitting unit 12 do not absorb light. The span gas G SPAN is a gas calibrated with the maximum concentration value of a desired measurement range, and for example, NO, NO 2 , SO 2 gas is used.
サンプルガスＧＳの供給を止め、その後にゼロガスＧＺＥＲＯの供給を行ってゼロガスＧＺＥＲＯ流通時の受光信号を測定して校正し、または、スパンガスＧＳＰＡＮの供給を行ってスパンガスＧＳＰＡＮ流通時の吸光された受光信号を測定して校正を行うことができる。この校正は随時実施できるが、構成部品の経年変化によってガス濃度指示値が変動することが想定される場合に行われ、正確な値を指示させる。
ガス分析計１００はこのようなものである。 Stopping the supply of the sample gas G S, followed by performing the supply of the zero gas G ZERO calibrated by measuring the light signal at the zero gas G ZERO distribution, or at the time span G SPAN flow by performing the supply of the span gas G SPAN Calibration can be performed by measuring the absorbed light-receiving signal. Although this calibration can be performed at any time, it is performed when it is assumed that the gas concentration indicating value fluctuates due to aging of the component parts, and an accurate value is indicated.
Thegas analyzer 100 is like this.
ガス分析計１００はこのようなものである。 Stopping the supply of the sample gas G S, followed by performing the supply of the zero gas G ZERO calibrated by measuring the light signal at the zero gas G ZERO distribution, or at the time span G SPAN flow by performing the supply of the span gas G SPAN Calibration can be performed by measuring the absorbed light-receiving signal. Although this calibration can be performed at any time, it is performed when it is assumed that the gas concentration indicating value fluctuates due to aging of the component parts, and an accurate value is indicated.
The
従って、装置構成を変更することなく、ＳＯ２濃度測定機能を付加することが可能である。ガス分析計１００はこのようにして分析を行う。
本発明によれば、簡易な構成で、ＮＯガス、ＮＯ２ガス、ＳＯ２ガスのガス濃度を精度よく測定することができる。 Therefore, it is possible to add the SO 2 concentration measurement function without changing the device configuration. Thegas analyzer 100 performs the analysis in this way.
According to the present invention, the gas concentrations of NO gas, NO 2 gas, and SO 2 gas can be accurately measured with a simple configuration.
本発明によれば、簡易な構成で、ＮＯガス、ＮＯ２ガス、ＳＯ２ガスのガス濃度を精度よく測定することができる。 Therefore, it is possible to add the SO 2 concentration measurement function without changing the device configuration. The
According to the present invention, the gas concentrations of NO gas, NO 2 gas, and SO 2 gas can be accurately measured with a simple configuration.
続いて第３の形態について図３を参照しつつ説明する。ガス分析計２００は、図３で示すように、ＮＯ２ガス吸光用発光部１１、Ｏ３ガス吸光用発光部１２、部分反射部１３、ガス流通セル２１、透過光受光部３１、基準光受光部３２、ガス調整部４１、ガス吸引部５１、信号処理・駆動制御部６１、補正部７１を備える。
Next, a third embodiment will be described with reference to FIG. As shown in FIG. 3, the gas analyzer 200 includes a light emitting unit 11 for absorbing NO 2 gas, a light emitting unit 12 for absorbing O 3 gas, a partial reflecting unit 13, a gas flow cell 21, a transmitted light receiving unit 31, and a reference light receiving unit. Unit 32, gas adjustment unit 41, gas suction unit 51, signal processing / drive control unit 61, and correction unit 71.
図１を用いて説明した上記の第１、第２の形態と比較すると、特に補正部７１が追加された点が相違する。ここでは補正部７１およびその動作について重点的に説明するとともに他の構成については同じ番号を付すとともに重複する説明を省略する。
Compared with the first and second embodiments described above with reference to FIG. 1, the difference is that a correction unit 71 is added. Here, the correction unit 71 and its operation will be described with emphasis, and the other components will be assigned the same numbers and redundant description will be omitted.
補正部７１は、基準光受光部３２、信号処理・駆動制御部６１、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２と接続され、特に基準光受光部３２からの信号に基づいてＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２を駆動させる電流を補正する機能を有する。
The correction unit 71 is connected to the reference light receiving unit 32, the signal processing / drive control unit 61, the NO 2 gas absorption light emitting unit 11, and the O 3 gas absorption light emitting unit 12. Based on this, it has a function of correcting the current for driving the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12.
基準光受光部３２がＮＯ２ガス吸光用発光部１１からのＮＯ２ガス吸光用照射光による基準光を受光してその強度信号を出力する。補正部７１は、強度信号に基づき、出力強度が一定になるように発光ダイオード駆動電流である駆動信号を補正した上で出力する。
同様に、基準光受光部３２がＯ３ガス吸光用発光部１２からのＯ３ガス吸光用照射光による基準光を受光してその強度信号を出力する。補正部７１は、強度信号に基づき、出力強度が一定になるように発光ダイオード駆動電流である駆動信号を補正した上で出力する。 Reference-light receiving part 32 by receiving the reference light by NO 2 gas absorption for the irradiation light from the NO 2 gas absorption for the light emitting unit 11 and outputs the intensity signal. Based on the intensity signal, the correction unit 71 corrects and outputs the drive signal, which is a light emitting diode drive current, so that the output intensity is constant.
Similarly, the referencelight receiving unit 32 by receiving the reference light by the O 3 gas absorption for the irradiation light from the O 3 gas absorption for the light emitting unit 12 and outputs the intensity signal. Based on the intensity signal, the correction unit 71 corrects and outputs the drive signal, which is a light emitting diode drive current, so that the output intensity is constant.
同様に、基準光受光部３２がＯ３ガス吸光用発光部１２からのＯ３ガス吸光用照射光による基準光を受光してその強度信号を出力する。補正部７１は、強度信号に基づき、出力強度が一定になるように発光ダイオード駆動電流である駆動信号を補正した上で出力する。 Reference-
Similarly, the reference
このような補正部７１を追加した構成とすることで、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２から出力される照射光の変動が少なくなっており、検出精度を向上させることができる。
By adopting a configuration in which such a correction unit 71 is added, fluctuations in irradiation light output from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 are reduced, and detection accuracy is improved. Can be made.
続いて、上記の第１、第２、第３形態をそれぞれ改良する第４形態について図を参照しつつ説明する。図４では、先に説明した第１、第２、第３形態のガス分析計の構成に加え、さらに、ＮＯ２ガス吸光用発光部１１の光軸上にレンズ１４を備え、また、Ｏ３ガス吸光用発光部１２の光軸上にレンズ１５を備えたものである。
Next, a fourth embodiment that improves the first, second, and third embodiments will be described with reference to the drawings. In FIG. 4, in addition to the configuration of the gas analyzer of the first, second, and third embodiments described above, a lens 14 is further provided on the optical axis of the NO 2 gas absorption light emitting unit 11, and O 3 A lens 15 is provided on the optical axis of the gas absorption light emitting unit 12.
一般に、発光ダイオードからの発光は指向性が弱く拡散する。そのため、光透過窓２３を通じてガス流通セル２１の検出空間２５内に入射する光の割合が低下するという問題がある。そこで、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２から拡散しつつ照射される照射光の指向性を、レンズ１４、レンズ１５により鋭く高めている。これにより、光透過窓２３を通じてガス流通セル２１の検出空間２５内に入射する光の割合を増やしている。その結果、信号強度を増加させ、ひいてはガス濃度測定の精度や安定性を改善する効果がある。
In general, light emitted from a light emitting diode is diffused with low directivity. Therefore, there is a problem that the ratio of the light that enters the detection space 25 of the gas flow cell 21 through the light transmission window 23 decreases. Therefore, the directivity of the irradiation light irradiated while diffusing from the NO 2 gas absorbing light emitting portion 11 and the O 3 gas absorbing light emitting portion 12 is sharply enhanced by the lens 14 and the lens 15. Thereby, the ratio of the light which enters into the detection space 25 of the gas distribution cell 21 through the light transmission window 23 is increased. As a result, there is an effect that the signal intensity is increased, and consequently the accuracy and stability of the gas concentration measurement are improved.
なお、ＮＯ２ガス吸光用発光部１１とレンズ１４とがモジュール化により一体に構成され、また、Ｏ３ガス吸光用発光部１２とレンズ１５とがモジュール化により一体に構成されていてもよい。
Note that the NO 2 gas light-absorbing light-emitting unit 11 and the lens 14 may be integrally configured by modularization, and the O 3 gas light-absorbing light-emitting unit 12 and the lens 15 may be integrally configured by modularization.
続いて、上記の第１、第２、第３形態を改良する第５形態について図を参照しつつ説明する。図５に示すように、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２に代えて発光部１６が配置されている。この発光部１６は、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２を近接させて一体化した発光ダイオードアレイである。さらに、この発光部１６のＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２の光軸上にレンズ１７を配置している。
Next, a fifth embodiment that improves the first, second, and third embodiments will be described with reference to the drawings. As shown in FIG. 5, the light emitting portion 16 is arranged in place of NO 2 gas absorption for the light emitting portion 11 and the O 3 light-emitting unit 12 for gas absorption. The light emitting unit 16 is a light emitting diode array in which the NO 2 gas absorbing light emitting unit 11 and the O 3 gas absorbing light emitting unit 12 are integrated in close proximity. Further, a lens 17 is disposed on the optical axis of the light emitting unit 11 for absorbing NO 2 gas and the light emitting unit 12 for absorbing O 3 gas.
これにより、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２の光軸が近接するため、指向性を高めるためのレンズ１７が１個で良い。また、光軸が近接しているため基準光受光部３２への入射効率も向上する。その結果、信号強度を増加させ、ひいてはガス濃度測定の精度や安定性を改善する効果がある。
As a result, the optical axes of the NO 2 gas absorbing light emitting portion 11 and the O 3 gas absorbing light emitting portion 12 are close to each other, so that only one lens 17 for enhancing directivity is required. Further, since the optical axes are close to each other, the incident efficiency to the reference light receiving unit 32 is also improved. As a result, there is an effect that the signal intensity is increased, and consequently the accuracy and stability of the gas concentration measurement are improved.
続いて、上記の第１、第２、第３、第４、第５形態をそれぞれ改良する第６形態について図を参照しつつ説明する。図６では、先に説明した第１、第２、第３、第４、第５形態のガス分析計の構成に加え、さらに、光透過窓２４と透過光受光部３１の間にレンズ１８を配置したものである。レンズ１８により、光透過窓２４を透過してきたＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を集光し、効率よく透過光受光部３１に入射させる。その結果、信号強度を増加させ、ひいてはガス濃度測定の精度や安定性を改善する効果がある。
Next, a sixth embodiment that improves the first, second, third, fourth, and fifth embodiments will be described with reference to the drawings. In FIG. 6, in addition to the configuration of the first, second, third, fourth, and fifth gas analyzers described above, the lens 18 is further disposed between the light transmitting window 24 and the transmitted light receiving unit 31. It is arranged. The lens 18 collects the NO 2 gas absorption irradiation light and the O 3 gas absorption irradiation light transmitted through the light transmission window 24, and efficiently enters the transmitted light receiving unit 31. As a result, there is an effect that the signal intensity is increased, and consequently the accuracy and stability of the gas concentration measurement are improved.
なお、光透過窓２４とレンズ１８とがモジュール化により一体に構成されていてもよい。さらには、光透過窓２４自体を、光透過性があり、集光効果がある凸面形状のレンズ１８とし、このレンズ１８を管２２に固着してガス流通セル２１を構成してもよい。
In addition, the light transmission window 24 and the lens 18 may be integrally configured by modularization. Furthermore, the light transmission window 24 itself may be a convex lens 18 that is light transmissive and has a light collecting effect, and the gas flow cell 21 may be configured by fixing the lens 18 to the tube 22.
続いて、上記の第１、第２、第３形態を改良する第６形態について図７を参照しつつ説明する。これは、ガス流通セル２１の光透過窓２４を反射部２８に置き換え、また、透過光受光部３１を部分反射部１３で復路光が反射する位置に配置したものである。
Subsequently, a sixth embodiment that improves the first, second, and third embodiments will be described with reference to FIG. In this case, the light transmission window 24 of the gas flow cell 21 is replaced with a reflection part 28, and the transmitted light receiving part 31 is arranged at a position where the return light is reflected by the partial reflection part 13.
この構成においては、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２から照射される照射光である往路光が光透過窓２３を透過し、管２２の検出空間２５内を伝播し、反射部２８において反射され、復路光となる。反射された復路光は管２２の検出空間２５内を反対向きに伝播し、光透過窓２３から出射し、部分反射部１３で反射して、透過光受光部３１に入射する。
In this configuration, forward light that is irradiation light emitted from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 passes through the light transmission window 23 and propagates in the detection space 25 of the tube 22. Then, the light is reflected by the reflecting portion 28 and becomes return path light. The reflected return light propagates in the detection space 25 of the tube 22 in the opposite direction, exits from the light transmission window 23, is reflected by the partial reflection unit 13, and enters the transmitted light receiving unit 31.
この構成によれば、図１、図３の第１、第２、第３形態と比較して、ガスによる吸光のある光路長が２倍に伸びるため、吸光信号の向上、ガス濃度測定の精度や安定性を改善する効果が期待できる。
According to this configuration, compared with the first, second, and third embodiments of FIGS. 1 and 3, the optical path length with light absorption by gas is doubled, so that the light absorption signal is improved and the gas concentration measurement accuracy is improved. And can improve the stability.
続いて、上記の第１、第２、第３形態を改良する第７形態について図８を参照しつつ説明する。これは、ＮＯ２ガス吸光用発光部１１、Ｏ３ガス吸光用発光部１２および透過光受光部３１を近接させつつモジュール化により一体化した発受光部１９を備えたものである。さらに、ガス流通セル２１の光透過窓２４を反射部２８に置き換え、また、透過光受光部３１を部分反射部１３で復路光が透過する位置に配置したものである。
Then, the 7th form which improves said 1st, 2nd, 3rd form is demonstrated, referring FIG. This is provided with a light emitting / receiving part 19 integrated by modularization while bringing the NO 2 gas absorbing light emitting part 11, the O 3 gas absorbing light emitting part 12 and the transmitted light receiving part 31 close to each other. Further, the light transmission window 24 of the gas flow cell 21 is replaced with the reflection portion 28, and the transmitted light receiving portion 31 is disposed at a position where the return light is transmitted by the partial reflection portion 13.
これによれば、レンズ１７はＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２からの照射光の指向性を高める機能と、透過光受光部３１に入射する照射光を集光する機能を兼ね備えることとなる。また、ガスによる吸光のある光路長が２倍に伸びるため、吸光信号の向上、ガス濃度測定の精度や安定性を改善する効果が期待できる。
According to this, the lens 17 condenses the irradiation light incident on the transmitted light receiving unit 31 and the function of increasing the directivity of the irradiation light from the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12. It will have the function to do. Further, since the optical path length with light absorption by gas is doubled, it is possible to expect the effect of improving the light absorption signal and improving the accuracy and stability of gas concentration measurement.
続いて、上記の第１、第２、第３、第４、第５、第６、第７形態を改良する第８形態について図を参照しつつ説明する。図９は発光ダイオードのデューティー比－許容電流特性図である。本形態は先に説明した第１、第２、第３、第４、第５、第６、第７形態のガス分析計の測定精度をさらに向上させるものである。
Subsequently, an eighth embodiment that improves the first, second, third, fourth, fifth, sixth, and seventh embodiments will be described with reference to the drawings. FIG. 9 is a duty ratio-allowable current characteristic diagram of the light emitting diode. This embodiment further improves the measurement accuracy of the gas analyzers of the first, second, third, fourth, fifth, sixth, and seventh embodiments described above.
まず原理について説明する。図９に示すように、発光ダイオードの許容電流は、一般にデューティー比を小さくして出力期間が短いほど、電流値を大きく確保できるという特徴がある。そこで、ＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２の駆動電流を、図１０に示すように大きいデューティー比から、図１１に示すように小さいデューティー比（出力期間が停止期間よりも短い）とする。この際、図１１に示すように出力時間は短くなるが駆動電流値を大きくすることができる。したがって、照射光の出力強度を高めて信号レベルを高く確保でき、相対的にノイズに対する信号レベルが高くなり、安定的なガス濃度値を算出することができる。
First, the principle will be described. As shown in FIG. 9, the allowable current of the light emitting diode is characterized in that, generally, the smaller the duty ratio and the shorter the output period, the larger the current value can be secured. Therefore, the drive current of the NO 2 gas absorption light emitting unit 11 and the O 3 gas absorption light emitting unit 12 is changed from a large duty ratio as shown in FIG. 10 to a small duty ratio as shown in FIG. Shorter). At this time, the output time is shortened as shown in FIG. 11, but the drive current value can be increased. Therefore, the output intensity of the irradiation light can be increased to ensure a high signal level, the signal level against noise is relatively high, and a stable gas concentration value can be calculated.
さらに、発光ダイオードであるＮＯ２ガス吸光用発光部１１およびＯ３ガス吸光用発光部１２の発光時間を短くすることができるため、熱等による劣化を抑制し、連続発光と比較して寿命を長く保つことが可能となる。
Furthermore, since the light emission time of the light emitting diode 11 for absorbing NO 2 gas and the light emitting portion 12 for absorbing O 3 gas can be shortened, deterioration due to heat or the like is suppressed, and the lifetime is longer than that of continuous light emission. It becomes possible to keep for a long time.
このような本発明のガス分析計は、一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２）の２成分、または、一酸化窒素ガス（ＮＯガス）、二酸化窒素ガス（ＮＯ２）および二酸化硫黄ガス（ＳＯ２）の３成分を測定する分析に良好であり、例えば、ボイラ、ゴミ焼却等の燃焼排ガス測定用として最適である。その他、鉄鋼用ガス分析［高炉、転炉、熱処理炉、焼結（ペレット設備）、コークス炉］、青果貯蔵及び熟成、生化学（微生物）［発酵］、大気汚染［焼却炉、排煙脱硫・脱硝］、自動車・船等の内燃機関の排ガス（除テスタ）、防災［爆発性ガス検知、有毒ガス検知、新建築材燃焼ガス分析］、植物育成用、化学用分析［石油精製プラント、石油化学プラント、ガス発生プラント］、環境用［着地濃度、トンネル内濃度、駐車場、ビル管理］、理化学各種実験用などの分析計としても有用である。
Such a gas analyzer of the present invention comprises two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 ), or nitrogen monoxide gas (NO gas), nitrogen dioxide gas (NO 2 ) and It is good for analysis for measuring three components of sulfur dioxide gas (SO 2 ), and is optimal for measurement of combustion exhaust gas such as boiler and garbage incineration. In addition, gas analysis for steel [blast furnace, converter, heat treatment furnace, sintering (pellet equipment), coke oven], fruit and vegetable storage and ripening, biochemistry (microorganism) [fermentation], air pollution [incinerator, flue gas desulfurization / Denitration], exhaust gas (removal tester) of internal combustion engines such as automobiles and ships, disaster prevention [explosive gas detection, toxic gas detection, new building material combustion gas analysis], plant growth, chemical analysis [oil refinery plant, petrochemical Plants, gas generation plants], environmental [landing concentration, concentration in tunnels, parking lots, building management], and analytical instruments for various physics and chemistry experiments.
１００、２００：ガス分析計
１１：ＮＯ２ガス吸光用発光部
１２：Ｏ３ガス吸光用発光部
１３：部分反射部
１４：レンズ
１５：レンズ
１６：発光部
１７：レンズ
１８：レンズ
１９：受発光部
２１：ガス流通セル
２２：管
２３、２４：光透過窓
２５：検出空間
２６：ガス流入口
２７：ガス流出口
２８：反射部
３１：透過光受光部
３２：基準光受光部
４１：ガス調整部
４２：オゾン発生部
４３：ガス混合部
５１：ガス吸引部
６１：信号処理・駆動制御部
７１：補正部 100, 200: Gas analyzer 11: NO 2 gas absorption light emitting unit 12: O 3 gas absorption light emitting unit 13: Partial reflection unit 14: Lens 15: Lens 16: Light emission unit 17: Lens 18: Lens 19: Light reception / emission Unit 21: Gas flow cell 22:Pipe 23, 24: Light transmission window 25: Detection space 26: Gas inlet 27: Gas outlet 28: Reflector 31: Transmitted light receiver 32: Reference light receiver 41: Gas adjustment Unit 42: ozone generation unit 43: gas mixing unit 51: gas suction unit 61: signal processing / drive control unit 71: correction unit
１１：ＮＯ２ガス吸光用発光部
１２：Ｏ３ガス吸光用発光部
１３：部分反射部
１４：レンズ
１５：レンズ
１６：発光部
１７：レンズ
１８：レンズ
１９：受発光部
２１：ガス流通セル
２２：管
２３、２４：光透過窓
２５：検出空間
２６：ガス流入口
２７：ガス流出口
２８：反射部
３１：透過光受光部
３２：基準光受光部
４１：ガス調整部
４２：オゾン発生部
４３：ガス混合部
５１：ガス吸引部
６１：信号処理・駆動制御部
７１：補正部 100, 200: Gas analyzer 11: NO 2 gas absorption light emitting unit 12: O 3 gas absorption light emitting unit 13: Partial reflection unit 14: Lens 15: Lens 16: Light emission unit 17: Lens 18: Lens 19: Light reception / emission Unit 21: Gas flow cell 22:
Claims (9)
- サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）および二酸化窒素ガス（ＮＯ２ガス）の２成分のガス濃度を測定するガス分析計であって、
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）をオゾンの酸化により全て二酸化窒素ガス（ＮＯ２ガス）に反応させ、さらに二酸化窒素ガス（ＮＯ２ガス）の一部をオゾンの酸化により五酸化二窒素ガス（Ｎ２Ｏ５ガス）に反応させた測定対象ガスとして出力する酸化出力と、サンプルガスを無反応のまま測定対象ガスとして出力する通常出力と、を行うガス調整部と、
二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域から可視領域までの波長のＮＯ２ガス吸光用照射光を照射するＮＯ２ガス吸光用発光部と、
オゾンガス（Ｏ３ガス）および二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域の波長のＯ３ガス吸光用照射光を照射するＯ３ガス吸光用発光部と、
ＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光の一部を反射し、残りを透過する部分反射部と、
ガス調整部からの測定対象ガスが流通する検出空間と、部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を検出空間へ入射させる光透過窓と、を有するガス流通セルと、
光透過窓を透過しガス流通セル内を伝播したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する透過光受光部と、
部分反射部で反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する基準光受光部と、
ガス調整部、ＮＯ２ガス吸光用発光部、Ｏ３ガス吸光用発光部、透過光受光部および基準光受光部と接続される信号処理・駆動制御部と、
を備え、
この信号処理・駆動制御部は、
ガス調整部を酸化出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃｍを算出し、
ガス調整部を酸化出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、オゾンガス（Ｏ３ガス）のガス濃度ｃ３を算出し、
ガス調整部を通常出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃ２を算出し、
供給されるオゾンガス（Ｏ３ガス）のガス濃度ｃ０から、測定されたオゾンガス（Ｏ３ガス）のガス濃度ｃ３を、減じて算出された反応消費時のガス濃度が、測定対象ガス中の一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１に五酸化二窒素ガス（Ｎ２Ｏ５ガス）のガス濃度（ｃ１＋ｃ２－ｃｍ）／２を加えたガス濃度に等しいことに基づいて、算出されたｃ０、ｃｍ、ｃ３、ｃ２、から一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１を算出することを特徴とするガス分析計。 A gas analyzer that measures the gas concentrations of two components of nitrogen monoxide gas (NO gas) and nitrogen dioxide gas (NO 2 gas) contained in a sample gas,
All nitric oxide gas contained in the sample gas (NO gas) by oxidation of ozone reacted in a nitrogen dioxide gas (NO 2 gas), further pentoxide a portion of the nitrogen dioxide gas (NO 2 gas) by oxidation of ozone A gas adjustment unit that performs an oxidation output that is output as a measurement target gas reacted with dinitrogen gas (N 2 O 5 gas), and a normal output that is output as a measurement target gas without any reaction;
A light emitting part for absorbing NO 2 gas that irradiates irradiation light for absorbing NO 2 gas having a wavelength from an ultraviolet region to a visible region in which nitrogen dioxide gas (NO 2 gas) absorbs;
A light emitting part for absorbing O 3 gas that irradiates irradiation light for absorbing O 3 gas having a wavelength in the ultraviolet region where ozone gas (O 3 gas) and nitrogen dioxide gas (NO 2 gas) absorb;
A partially reflecting portion that reflects part of the irradiation light for NO 2 gas absorption and part of the irradiation light for O 3 gas absorption and transmits the rest;
A gas having a detection space in which a measurement target gas from the gas adjustment unit flows, and a light transmission window through which the irradiation light for NO 2 gas absorption and the irradiation light for O 3 gas absorption transmitted through the partial reflection unit enter the detection space A distribution cell;
A transmitted light receiving unit for receiving the light transmission window transmitting irradiated light and a NO 2 gas absorption propagated in the gas flow cell O 3 irradiation light gas absorption,
A reference light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas reflected by the partial reflection unit;
A signal processing / drive control unit connected to the gas adjusting unit, the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, the transmitted light receiving unit, and the reference light receiving unit;
With
This signal processing / drive control unit
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled by using the signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the oxidation output state and the irradiation light for NO 2 gas absorption is emitted. c m is calculated,
The gas conditioning unit by using a signal from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the oxidation output state, gas concentration c 3 of ozone (O 3 gas) To calculate
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the irradiation light for NO 2 gas absorption is emitted. c 2 is calculated,
From the gas concentration c 0 of the ozone gas (O 3 gas) supplied, the gas concentration c 3 of the measured ozone (O 3 gas), the gas concentration in the reaction consumption calculated by subtracting the, in the gas as the object of measurement Based on the gas concentration c 1 of nitrogen monoxide gas (NO gas) plus the gas concentration (c 1 + c 2 −c m ) / 2 of nitrous oxide (N 2 O 5 gas) / 2. Te, c 0 calculated, c m, c 3, c 2, gas analyzer and calculates the gas concentration c 1 of nitric oxide gas (NO gas) from. - サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）、二酸化窒素ガス（ＮＯ２）および二酸化硫黄ガス（ＳＯ２ガス）の３成分のガス濃度を測定するガス分析計であって、
サンプルガスに含まれる一酸化窒素ガス（ＮＯガス）をオゾンの酸化により全て二酸化窒素ガス（ＮＯ２ガス）に反応させ、さらに二酸化窒素ガス（ＮＯ２ガス）の一部をオゾンの酸化により五酸化二窒素ガス（Ｎ２Ｏ５ガス）に反応させた測定対象ガスとして出力する酸化出力と、サンプルガスを無反応のまま測定対象ガスとして出力する通常出力と、を行うガス調整部と、
二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域から可視領域までの波長のＮＯ２ガス吸光用照射光を照射するＮＯ２ガス吸光用発光部と、
オゾンガス（Ｏ３ガス）、二酸化硫黄ガス（ＳＯ２ガス）および二酸化窒素ガス（ＮＯ２ガス）が吸光する紫外領域の波長のＯ３ガス吸光用照射光を照射するＯ３ガス吸光用発光部と、
ＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光の一部を反射し、残りを透過する部分反射部と、
ガス調整部からの測定対象ガスが流通する検出空間と、部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を検出空間へ入射させる光透過窓と、を有するガス流通セルと、
光透過窓を透過しガス流通セル内を伝播したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する透過光受光部と、
部分反射部で反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光する基準光受光部と、
ガス調整部、ＮＯ２ガス吸光用発光部、Ｏ３ガス吸光用発光部、透過光受光部および基準光受光部と接続される信号処理・駆動制御部と、
を備え、
この信号処理・駆動制御部は、
ガス調整部を酸化出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃｍを算出し、
ガス調整部を酸化出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、オゾンガス（Ｏ３ガス）のガス濃度ｃ３および二酸化硫黄ガス（ＳＯ２ガス）のガス濃度ｃｓを算出し、
ガス調整部を通常出力状態に制御してＮＯ２ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化窒素ガス（ＮＯ２ガス）のガス濃度ｃ２を算出し、
ガス調整部を通常出力状態に制御してＯ３ガス吸光用照射光を発光したときの透過光受光部および基準光受光部からの信号を用いて、二酸化硫黄ガス（ＳＯ２ガス）のガス濃度ｃｓを算出し、
供給されるオゾンガス（Ｏ３ガス）のガス濃度ｃ０から、測定されたオゾンガス（Ｏ３ガス）のガス濃度ｃ３を、減じて算出された反応消費時のガス濃度が、測定対象ガス中の一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１に五酸化二窒素ガス（Ｎ２Ｏ５ガス）のガス濃度（ｃ１＋ｃ２－ｃｍ）／２を加えたガス濃度に等しいことに基づいて、算出されたｃ０、ｃｍ、ｃ３、ｃ２、から一酸化窒素ガス（ＮＯガス）のガス濃度ｃ１を算出することを特徴とするガス分析計。 A gas analyzer that measures the concentration of three components of nitrogen monoxide gas (NO gas), nitrogen dioxide gas (NO 2 ), and sulfur dioxide gas (SO 2 gas) contained in a sample gas,
All nitric oxide gas contained in the sample gas (NO gas) by oxidation of ozone reacted in a nitrogen dioxide gas (NO 2 gas), further pentoxide a portion of the nitrogen dioxide gas (NO 2 gas) by oxidation of ozone A gas adjustment unit that performs an oxidation output that is output as a measurement target gas reacted with dinitrogen gas (N 2 O 5 gas), and a normal output that is output as a measurement target gas without any reaction;
A light emitting part for absorbing NO 2 gas that irradiates irradiation light for absorbing NO 2 gas having a wavelength from an ultraviolet region to a visible region in which nitrogen dioxide gas (NO 2 gas) absorbs;
A light emitting part for absorbing O 3 gas that irradiates light for absorbing O 3 gas having a wavelength in the ultraviolet region where ozone gas (O 3 gas), sulfur dioxide gas (SO 2 gas) and nitrogen dioxide gas (NO 2 gas) absorb; ,
A partially reflecting portion that reflects part of the irradiation light for NO 2 gas absorption and part of the irradiation light for O 3 gas absorption and transmits the rest;
A gas having a detection space in which a measurement target gas from the gas adjustment unit flows, and a light transmission window through which the irradiation light for NO 2 gas absorption and the irradiation light for O 3 gas absorption transmitted through the partial reflection unit enter the detection space A distribution cell;
A transmitted light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas transmitted through the light transmission window and propagated in the gas flow cell;
A reference light receiving unit that receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas reflected by the partial reflection unit;
A signal processing / drive control unit connected to the gas adjusting unit, the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, the transmitted light receiving unit, and the reference light receiving unit;
With
This signal processing / drive control unit
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled by using the signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the oxidation output state and the irradiation light for NO 2 gas absorption is emitted. c m is calculated,
The gas conditioning unit by using a signal from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the oxidation output state, gas concentration c 3 of ozone (O 3 gas) And the gas concentration c s of sulfur dioxide gas (SO 2 gas),
The gas concentration of the nitrogen dioxide gas (NO 2 gas) is controlled using signals from the transmitted light receiving unit and the reference light receiving unit when the gas adjusting unit is controlled to the normal output state and the irradiation light for NO 2 gas absorption is emitted. c 2 is calculated,
Using signals from the transmitted light receiving unit and the reference light receiving unit when the emitting O 3 irradiation light gas absorption by controlling the gas adjusting unit to the normal output state, the gas concentration of sulfur dioxide gas (SO 2 gas) c s is calculated,
From the gas concentration c 0 of the ozone gas (O 3 gas) supplied, the gas concentration c 3 of the measured ozone (O 3 gas), the gas concentration in the reaction consumption calculated by subtracting the, in the gas as the object of measurement Based on the gas concentration c 1 of nitrogen monoxide gas (NO gas) plus the gas concentration (c 1 + c 2 −c m ) / 2 of nitrous oxide (N 2 O 5 gas) / 2. And calculating a gas concentration c 1 of nitric oxide gas (NO gas) from the calculated c 0 , c m , c 3 , c 2 . - 請求項１または請求項２に記載のガス分析計において、
前記基準光受光部、前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部と接続される補正部を有し、
前記基準光受光部は、部分反射部により一部反射したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を受光して検出信号を補正部へ出力し、
補正部は、この検出信号に基づいて変動を抑止するような駆動電流を前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部へ出力することを特徴とするガス分析計。 The gas analyzer according to claim 1 or 2,
A correction unit connected to the reference light receiving unit, the NO 2 gas absorbing light emitting unit, and the O 3 gas absorbing light emitting unit;
The reference light receiving unit receives the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas partially reflected by the partial reflection unit, and outputs a detection signal to the correction unit,
The correction unit outputs a driving current that suppresses fluctuations based on the detection signal to the NO 2 gas absorption light emission unit and the O 3 gas absorption light emission unit. - 請求項１または請求項２に記載のガス分析計において、
前記ＮＯ２ガス吸光用発光部からのＮＯ２ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズおよび前記Ｏ３ガス吸光用発光部からのＯ３ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズを備えることを特徴とするガス分析計。 The gas analyzer according to claim 1 or 2,
Collecting the O 3 irradiation light gas absorption from the NO 2 lens and the O 3 gas absorption for the light emitting portion condenses the NO 2 gas absorption for the irradiation light from the gas absorption for the light emitting portion is incident on the gas flow cell A gas analyzer comprising a lens that emits light and enters the gas flow cell. - 請求項１または請求項２に記載のガス分析計において、
前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部を隣接させて一体収容した発光部と、
前記ＮＯ２ガス吸光用発光部からのＮＯ２ガス吸光用照射光および前記Ｏ３ガス吸光用発光部からのＯ３ガス吸光用照射光を集光して前記ガス流通セルへ入射させるレンズと、
を備えることを特徴とするガス分析計。 The gas analyzer according to claim 1 or 2,
A light emitting unit that integrally accommodates the NO 2 gas absorbing light emitting unit and the O 3 gas absorbing light emitting unit adjacent to each other;
A lens for incident condenses O 3 irradiation light gas absorption from the NO 2 NO 2 gas absorption irradiation light and the O 3 gas absorption for the light emitting portion of the gas absorption for the light emitting portion to the gas flow cell,
A gas analyzer comprising: - 請求項１または請求項２に記載のガス分析計において、
前記ガス流通セルを透過した後のＮＯ２ガス吸光用照射光および前記ガス流通セルを透過した後のＯ３ガス吸光用照射光を集光するレンズを備えることを特徴とするガス分析計。 The gas analyzer according to claim 1 or 2,
A gas analyzer comprising a lens for collecting the irradiation light for absorbing NO 2 gas after passing through the gas flow cell and the irradiation light for absorbing O 3 gas after passing through the gas flow cell. - 請求項１または請求項２に記載のガス分析計において、
前記ガス流通セルは一方に光透過窓を、また、他方に反射部を備え、光透過窓を透過してＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を反射部で反射させた後に光透過窓を通過するようにして検出空間内を往復させ、前記部分反射部で反射させたＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を前記透過光受光部が検出することを特徴とするガス分析計。 The gas analyzer according to claim 1 or 2,
The gas flow cell has a light transmission window on one side and a reflection part on the other side, and transmits the light transmission window and reflects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas at the reflection part. The transmitted light receiving part detects the irradiation light for absorbing NO 2 gas and the irradiation light for absorbing O 3 gas reflected by the partial reflection part by reciprocating in the detection space so as to pass through the light transmission window later. Gas analyzer characterized by. - 請求項１または請求項２に記載のガス分析計において、
前記ＮＯ２ガス吸光用発光部、前記Ｏ３ガス吸光用発光部および前記透過光受光部を隣接させて一体収容した発受光部を更に備え、
前記ガス流通セルは一方に光透過窓を、また、他方に反射部を有するようになされており、
光透過窓を透過して発受光部から発せられたＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を反射部で反射させた後に光透過窓を通過するようにして検出空間内を往復させ、前記部分反射部を透過したＮＯ２ガス吸光用照射光およびＯ３ガス吸光用照射光を発受光部の前記透過光受光部が検出することを特徴とするガス分析計。 The gas analyzer according to claim 1 or 2,
A light emitting / receiving unit that integrally accommodates the NO 2 gas absorbing light emitting unit, the O 3 gas absorbing light emitting unit, and the transmitted light receiving unit adjacent to each other;
The gas flow cell has a light transmission window on one side and a reflection part on the other side,
The NO 2 gas absorption irradiation light and the O 3 gas absorption irradiation light emitted from the light emitting / receiving section through the light transmission window are reflected by the reflection section and then pass through the light transmission window to pass through the light transmission window. A gas analyzer, wherein the transmitted light receiving unit of the light emitting / receiving unit detects the irradiation light for NO 2 gas absorption and the irradiation light for O 3 gas absorption which are reciprocated and transmitted through the partial reflection unit. - 請求項１または請求項２に記載のガス分析計において、
前記信号処理・駆動制御部は、前記ＮＯ２ガス吸光用発光部および前記Ｏ３ガス吸光用発光部の出力と停止とを交互に行うパルスであって停止より出力が短くなるようなデューティー比の駆動電流とすることを特徴とするガス分析計。 The gas analyzer according to claim 1 or 2,
The signal processing / drive control unit is a pulse that alternately performs output and stop of the NO 2 gas absorption light-emitting unit and the O 3 gas absorption light-emitting unit, and has a duty ratio that makes the output shorter than the stop. A gas analyzer characterized by a driving current.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/JP2014/063926 WO2015181879A1 (en) | 2014-05-27 | 2014-05-27 | Gas analyzer |
| CN201480050835.6A CN105556284B (en) | 2014-05-27 | 2014-05-27 | Gas analyzer |
| JP2016523000A JP6024856B2 (en) | 2014-05-27 | 2014-05-27 | Gas analyzer |
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| PCT/JP2014/063926 WO2015181879A1 (en) | 2014-05-27 | 2014-05-27 | Gas analyzer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106290163A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院化学研究所 | Dinitrogen pentoxide and concentration of nitric acid on-line monitoring system and monitoring method in a kind of air |
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| EP3553499A1 (en) * | 2018-04-13 | 2019-10-16 | Siemens Aktiengesellschaft | Gas analysis system and method for measuring nitrogen oxides in a waste gas |
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| CN106290163A (en) * | 2016-07-21 | 2017-01-04 | 中国科学院化学研究所 | Dinitrogen pentoxide and concentration of nitric acid on-line monitoring system and monitoring method in a kind of air |
| WO2019025186A1 (en) * | 2017-07-31 | 2019-02-07 | Siemens Aktiengesellschaft | Gas analyzer for measuring nitrogen oxides and sulfur dioxide in exhaust gases |
| US11237141B2 (en) | 2017-07-31 | 2022-02-01 | Siemens Aktiengesellschaft | Gas analyzer for measuring nitrogen oxides and sulfur dioxide in exhaust gases |
| US10871443B2 (en) * | 2017-08-10 | 2020-12-22 | Siemens Aktiengesellschaft | Gas analyzer for measuring nitrogen oxides and least one further component of an exhaust gas |
| EP3553499A1 (en) * | 2018-04-13 | 2019-10-16 | Siemens Aktiengesellschaft | Gas analysis system and method for measuring nitrogen oxides in a waste gas |
| US11226322B2 (en) | 2018-04-13 | 2022-01-18 | Siemens Aktiengesellschaft | Optical gas analyzer and method for measuring nitrogen oxides in an exhaust gas |
| CN114002177A (en) * | 2021-12-06 | 2022-02-01 | 国网江苏省电力有限公司检修分公司 | SF6 decomposition product detection system based on ultraviolet spectroscopy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105556284B (en) | 2018-01-02 |
| JPWO2015181879A1 (en) | 2017-04-20 |
| CN105556284A (en) | 2016-05-04 |
| JP6024856B2 (en) | 2016-11-16 |
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