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EP2585810A1 - Analyseur de gaz non dispersif - Google Patents

Analyseur de gaz non dispersif

Info

Publication number
EP2585810A1
EP2585810A1 EP11741531.5A EP11741531A EP2585810A1 EP 2585810 A1 EP2585810 A1 EP 2585810A1 EP 11741531 A EP11741531 A EP 11741531A EP 2585810 A1 EP2585810 A1 EP 2585810A1
Authority
EP
European Patent Office
Prior art keywords
light
detector
flash
gas analyzer
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11741531.5A
Other languages
German (de)
English (en)
Inventor
Ralf Bitter
Camiel Heffels
Thomas Hörner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of EP2585810A1 publication Critical patent/EP2585810A1/fr
Withdrawn legal-status Critical Current

Links

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
    • G01N21/59—Transmissivity
    • G01N21/61—Non-dispersive gas analysers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
    • G01N21/274—Calibration, base line adjustment, drift correction
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/37—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using pneumatic detection
    • 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
    • G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
    • G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G01N21/05—Flow-through cuvettes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/069—Supply of sources
    • G01N2201/0696—Pulsed

Definitions

  • a non-dispersive gas analyzer comprising a light source, whose light passes through a one to analy ⁇ sierendes measurement gas containing the sample cell to a non ⁇ selective detector with a downstream evaluation unit.
  • absorption spectrometric gas analysis predetermined components of a gas mixture (measuring gas) are quantified on the basis of their wavelength-specific absorption of light.
  • the light from a light source is passed through the measurement gas to be analyzed to a detector with a downstream evaluation device.
  • the sample gas is mastered ⁇ least in a cuvette.
  • the wavelength range of the light used depends on the components of the measurement gas to be determined and can range from the near infrared to the ultraviolet or lie therebetween.
  • no spectral decomposition of the light occurs; instead, selective, possibly tunable, light sources or selective detectors are used.
  • a non-dispersive infrared (NDIR) -Gasanaly ⁇ sator is usually a non-selective infrared radiation source and a ⁇ with the filled or components to be determined selectively optopneumatic detector.
  • a laser spectrometer includes a selective light source in the form of a wavelength tunable laser and a non-selective detector in the wavelength range of interest, e.g. B. a photodiode.
  • the light of the light source is distributed to the measuring cuvette and a reference cuvette filled with a nonabsorbing reference or zero gas is followed by a further detector and the difference signal of both detectors is evaluated in the evaluation device (J. Staab: "Indus- trielle gas analysis "R. Oldenbourg Verlag Kunststoff Vienna, 1994, page 83).
  • the light is modulated to obtain an alternating signal in the detector.
  • the light beam can be interrupted periodically with a vane or aperture wheel or the light source can be pulsed.
  • EP 0 591 758 A1 and EP 0 195 339 B1 each show a dispersive gas analyzer with a xenon flash lamp. The light is spectrally decomposed by irradiation of the measuring cuvette by means of an optical grating and on a Detek ⁇ torzeile of z. B. directed photodiodes.
  • the flash duration of a xenon flash lamp is the shortest in the ultraviolet range and the longest in the infrared range (Newport Corporation, Oriel Xenon Flash Lamps, Technical Information, found on 15.06.2010 on the Internet at:
  • the invention is based on the object with simple means ⁇ a gas analysis, in particular to enable multi-component gas ⁇ analysis.
  • the object is achieved in that in the non-dispersive gas analyzer of the type mentioned, the light source is a flash discharge lamp and that the Evaluation device for evaluating the temporal pulse profile of the light flash incident on the detector is also.
  • the invention makes advantageous use of the abovementioned property of flash discharge lamps, namely that the emitted wavelength components vary over the duration of the flash of light.
  • success light absorptions can then at Various ⁇ NEN wavelengths are determined in the ana- lysing the sample gas on the timing pulse waveform of light incident on the detector light flash.
  • the flash discharge lamp may contain different gas fillings. Flash light spectra of flash discharge lamps with different noble gas fillings can be found on the Internet at: http: // en. wikipedia. org / wiki / flashtube. Preferably, a commercially available xenon flash lamp is used.
  • a detector those in which are sufficiently sensitive to each be ⁇ sought wavelength range and with which not ⁇ manoeuvrable time resolution for the analysis of the temporal pulse course of the incident on the detector light flash in ⁇ - ⁇ ⁇ is ⁇ reached.
  • Preferred detectors are photodiode and photocell. For very wide-band detectors these suitable optical bandpass filter (interference filter) may be set before, hide the disturbing wavelength ranges outside the observed wavelengths ⁇ range.
  • the evaluation device can be designed to analyze the frequency content of the pulse shape.
  • the evaluation of the pulse progression in the time and frequency range can take place.
  • the evaluation can therefore also refer to time components.
  • this includes very simple, partly empirical methods, such as the analysis of the time shift of the time component (Ie Gradi ⁇ ducks analysis, curve discussions) pulse peaks, differentiation of the pulse waveform, integrations (area analysis), etc.
  • the lack of pulse components which are absorbed or scattered by the components of the measuring gas can be determined in the evaluation device by means of multivariate models from the temporal pulse progression of the light flash incident on the detector.
  • the concentrations of the individual components in the sample gas can be determined. The farther the differing in their position absorption bands of the gases of the components to be measured are spectrally separated and the more they are marked, the greater the gas specific in ⁇ pulse shaping influences and the better is the separation through the methods described herein. In this way, for example, the concentration of SO 2 , O 3 , H 2 S and O 2 could be determined quantitatively.
  • FIG. 1 shows a single-jet gas analyzer
  • FIG. 2 shows different spectral components of a xenon flash of light
  • Figure 3 shows the UV transmission spectra of some selected
  • FIG. 4 shows a double-jet gas analyzer
  • Figure 5 shows a first circuit of two photodetectors for the two-jet gas analyzer
  • FIG. 6 shows a second circuit of two photodetectors for the two-jet gas analyzer.
  • 1 shows a schematic representation of a non-dispersive gas analyzer in a single-jet design with a measuring cuvette 1 through which a measuring gas 2 to be analyzed flows.
  • the measuring gas 2 is a gas mixture of several components, one or more of which components of interest are to be determined quantitatively.
  • a light source 3 in the form of a flash discharge tube 4, in this example, a xenon flash lamp is driven by electrical pulses ⁇ 5 and generates single flashes of light 6 which are passed through the sample cell 1 through to a detector. 7
  • the detector 7 is connected downstream an evaluation device 8, which evaluates the pulse-shaped detector signal 10 generated by the detector 7 in response to the respective received light flash 9 with respect to the pulse shape and an analysis resulting ⁇ nis 11 provides.
  • Figure 2 shows various spectral components of a xenon flash 6 with its normalized output power P over time t (taken from the above-mentioned technical information of the company. Newport Corporation).
  • the wavelength range of the flash of light 6 extends from the infrared to the ultraviolet.
  • the duration of the flash of light 6 is shorter with respect to the short-wave components than with the longer-wave components.
  • a wavelength-dependent absorption of the light flash 6 takes place through the compo ⁇ components of the measurement gas 2, wherein many of interest ⁇ measuring gas components exhibit very different absorption behavior.
  • FIG. 3 shows as an example the absorption behavior ( transmittance T over the wavelength ⁇ ) of the gases H 2 S, NO 2 , SO 2 , NO and O 3 relevant in environmental measurement technology in the ultraviolet range.
  • the detector 7 ( Figure 1) is selected so that it can tektieren the Wel ⁇ lendorfn of the considered wavelength range de-. For the above-mentioned gases, this is z. As the ultraviolet range.
  • the detector 7 produces the detector signal 10 via the sum or the integral of the Wellenlän ⁇ gene; that is, the detector 7 is nonselective. Preferably, it detects the different wavelengths with more or less equal sensitivity.
  • the detector 7 is very broad band, interfering wavelength ranges can be hidden except ⁇ half of the considered wavelength range by means of an op ⁇ tables bandpass filter 12th
  • the wavelength-dependent absorption by the measured gas components also varies, with the result that the temporal pulse profile of the flash of light falling on the detector 7 is different from that of the flash of light 6 generated by the flash-discharge lamp 4.
  • the detected light flash 9 and therefore the detector signal 10 therefore contain information about the absorption in the measuring cuvette 1. If the wavelength-specific absorption bands of the sample gas components are different, ie not overlapping or only partially overlapping, the detected light flash 9 and thus the detector signal 10 also contain Information about the concentrations of the individual measuring gas components in the measuring gas 2.
  • the evaluating device 8 by evaluating the pulse progression of the signal impinging on the detector 7
  • the lightning flash 9 corresponding detector signal 10 determines the concentrations of selected measuring gas components of interest and output as the analysis result 11.
  • chemometric evaluation methods in particular multivariate statistical methods, are considered. From the above it follows that the detector 7 must enable a temporal resolution of the received flash of light 9. From Figure 2, a required time resolution in ⁇ - ⁇ ⁇ ⁇ results. This can be achieved by optopneumatic detectors, photodiodes or photocells.
  • FIG. 4 shows a schematic representation of another embodiment of the gas analyzer according to the invention in two-beam design.
  • a reference cuvette 13 is provided, which is filled with a reference or zero gas.
  • the light 6 emitted by the light source 3 is split by means of a light distributor 14, here in the form of a reflector, onto the measuring cuvette 1 and the reference cuvette 13.
  • the reference cell 13 is followed by a further detector 15 and the evaluation device 8 evaluates the temporal difference-impulse response of the incident on the detectors 7, 15 light flashes 9, 16.
  • the two detectors of two gas-filled receiver chambers are made with an intervening differential pressure or flow sensor 17, which generates a difference pulse shape of the light incident on the detectors 7, 15 flashes 9, 16 entspre ⁇ and fair detector signal 10 '.
  • Figures 5 and 6 show two known from EP 0387483 AI examples known circuit with photodiodes 18 for Realisie ⁇ tion of the detectors 7 and 15 °.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

L'invention concerne un analyseur de gaz non dispersif comprenant une source lumineuse (3) dont la lumière (6) traverse une cuvette de mesure (1) contenant le gaz de mesure à analyser pour entrer dans un détecteur non sélectif (7) en aval duquel est disposé un dispositif d'évaluation (8). Dans ce cadre, il est possible avec des moyens simples d'effectuer une analyse de gaz multicomposants, en utilisant comme source lumineuse (3) une lampe à éclairs (4) et en configurant le dispositif d'évaluation (8) pour qu'il évalue l'allure impulsionnelle dans le temps de l'éclair de lumière (9) entrant dans le détecteur (8). L'invention utilise la propriété des lampes à éclairs de posséder des composantes des longueurs d'ondes émises qui varient sur la durée de l'éclair (6).
EP11741531.5A 2010-06-25 2011-06-22 Analyseur de gaz non dispersif Withdrawn EP2585810A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010030549.9A DE102010030549B4 (de) 2010-06-25 2010-06-25 Nichtdispersiver Gasanalysator
PCT/EP2011/060402 WO2011161137A1 (fr) 2010-06-25 2011-06-22 Analyseur de gaz non dispersif

Publications (1)

Publication Number Publication Date
EP2585810A1 true EP2585810A1 (fr) 2013-05-01

Family

ID=44630009

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11741531.5A Withdrawn EP2585810A1 (fr) 2010-06-25 2011-06-22 Analyseur de gaz non dispersif

Country Status (4)

Country Link
US (1) US9030666B2 (fr)
EP (1) EP2585810A1 (fr)
DE (1) DE102010030549B4 (fr)
WO (1) WO2011161137A1 (fr)

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DE102015106373B4 (de) * 2015-04-24 2023-03-02 Infineon Technologies Ag Photoakustisches gassensormodul mit lichtemittereinheit und einer detektoreinheit
DE202021104857U1 (de) 2021-09-09 2022-12-20 Sick Ag Analysevorrichtung

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Also Published As

Publication number Publication date
WO2011161137A1 (fr) 2011-12-29
US20130208280A1 (en) 2013-08-15
DE102010030549B4 (de) 2016-04-28
DE102010030549A1 (de) 2011-12-29
US9030666B2 (en) 2015-05-12

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