WO2003100392A1 - Dispositif et procede de mesure spectroscopique d'une concentration de gaz par determination d'une seule ligne d'absorption - Google Patents

Dispositif et procede de mesure spectroscopique d'une concentration de gaz par determination d'une seule ligne d'absorption Download PDF

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Publication number
WO2003100392A1
WO2003100392A1 PCT/EP2003/005296 EP0305296W WO03100392A1 WO 2003100392 A1 WO2003100392 A1 WO 2003100392A1 EP 0305296 W EP0305296 W EP 0305296W WO 03100392 A1 WO03100392 A1 WO 03100392A1
Authority
WO
WIPO (PCT)
Prior art keywords
process gas
laser
shield
beam path
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.)
Ceased
Application number
PCT/EP2003/005296
Other languages
German (de)
English (en)
Inventor
Andreas Dietrich
Peter Kasperson
Karl Henrik Haugholt
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.)
Linde GmbH
Original Assignee
Linde GmbH
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 Linde GmbH filed Critical Linde GmbH
Priority to EP03732429A priority Critical patent/EP1508030A1/fr
Priority to BR0311244-6A priority patent/BR0311244A/pt
Priority to AU2003238366A priority patent/AU2003238366A1/en
Priority to JP2004507803A priority patent/JP2005526978A/ja
Priority to KR10-2004-7018995A priority patent/KR20050013552A/ko
Publication of WO2003100392A1 publication Critical patent/WO2003100392A1/fr
Priority to US10/996,037 priority patent/US20050128486A1/en
Anticipated expiration legal-status Critical
Ceased 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
    • G01N21/25—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
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/15—Preventing contamination of the components of the optical system or obstruction of the light path
    • 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
    • G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • 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
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • 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
    • G01N21/15—Preventing contamination of the components of the optical system or obstruction of the light path
    • G01N2021/151—Gas blown
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N2021/3129—Determining multicomponents by multiwavelength light
    • G01N2021/3133—Determining multicomponents by multiwavelength light with selection of wavelengths before the sample
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
    • G01N2021/396—Type of laser source
    • 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
    • G01N21/09—Cuvette constructions adapted to resist hostile environments or corrosive or abrasive materials
    • 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
    • G01N2201/02—Mechanical
    • G01N2201/023—Controlling conditions in casing
    • G01N2201/0233—Gas purge

Definitions

  • the invention relates to a device and a method for measuring a concentration of at least one component of a process gas with a laser, the beam path of the laser crossing a volume containing the process gas.
  • Measuring methods and devices are known for determining the concentration of individual components of a gas mixture, which are determined using a laser for laser spectroscopic measurements.
  • the present invention is therefore based on the object of an improved method and an improved device for carrying out laser spectroscopic measurements of the concentration of the components of a
  • the suitability of the invention being particularly important for large volumes of dust-laden process gases.
  • the object is achieved in that the beam path partly leads freely through the process gas and partly shields itself from the process gas, with only the part of the beam path that leads freely through the process gas being provided as a measuring section for a spectroscopic measurement of exactly one absorption line.
  • This has the advantage that, compared to a spectroscopic measurement that measures an area (scanning method), the accuracy of the measurement is significantly increased.
  • a so-called single-line spectroscopy is used. Therefore, a laser is advantageously used, the wavelength of which is fixed or can be fixed to a specific, selected value, which is also precisely observed.
  • an infrared laser with a precisely defined wavelength is used to determine carbon monoxide.
  • scanning lasers that is to say lasers which measure (scan) a wavelength range according to a predetermined sequence, are not suitable for the high accuracy which is an object of the present invention. Due to the definition of only one frequency, continuous automatic calibration of the laser is possible without any other aids. In contrast, scanning lasers require one or more reference gas cells in order to continuously calibrate the laser using these gases.
  • the shielding of the beam path is preferably designed as a hollow body.
  • Means are particularly preferably provided in the area of the shielding for feeding in a purge gas which serves to displace the process gas from the shielding, in particular from the interior of the hollow body.
  • a purge gas which serves to displace the process gas from the shielding, in particular from the interior of the hollow body.
  • Nitrogen for example, is very suitable as the purge gas.
  • Inert gases are also generally considered suitable. The suitability of a gas as a purge gas depends u. a. depending on which component of the process gas the concentration is to be determined.
  • the shield is tubular.
  • the shielding is particularly advantageous as a water-cooled lance executed. This embodiment enables the device according to the invention for measuring the concentration to be used without problems even in process gases which have a very high temperature.
  • the shield has a heat-resistant and / or acid-resistant material.
  • the shield preferably has a ceramic material. These materials also enable problem-free use of the device according to the invention under difficult conditions, for example in the presence of acidic components in the process gas.
  • the shield is attached to the laser at the beginning of the beam path and in front of a detector which is hit by the laser radiation, as a result of which the measuring path is limited by the shield from both sides.
  • This configuration has the advantage, among other things, that any existing edge effects (effects in the edge region of a gas volume) are hidden from the measurement. Disruptive edge effects can occur, for example, in a flowing process gas.
  • the task is solved in that the beam path leads partly freely through the process gas and partly shields itself from the process gas, whereby only the part of the beam path that leads freely through the process gas is referred to as the measuring section and for a spectroscopic measurement of the concentration with the help of the laser, in which exactly one absorption line is determined.
  • the method designed in this way enables a reliable measurement with high accuracy even over large measuring distances and in process gases which are contaminated with dust or are otherwise contaminated or generally mixed with particles.
  • the process gases can easily have a high temperature, since the spectral bands of the water vapor to be expected at higher temperatures do not have a disruptive influence on the measurement of a single absorptine line (single-line spectroscopy) according to the invention.
  • the shield is advantageously flushed with a purge gas.
  • Nitrogen is particularly advantageously used as the purge gas.
  • This is advantageously located inside the Shielding is a clean gas known in its composition, through which the laser beam experiences almost no weakening of its intensity and which behaves neutrally for the concentration measurement, ie does not make a contribution unless the concentration of a nitrogen compound is to be measured.
  • the suitability of a gas as a purge gas depends on which component of the process gas the concentration is to be determined.
  • a purge gas is preferably selected which differs significantly from the gas whose concentration is to be determined with regard to spectroscopy.
  • Inert gases can also advantageously be used as purge gases.
  • the particular advantage of inert gases is that a chemical reaction between the purge gas and the process gas can be excluded.
  • ambient air is drawn in and used as the purge gas. This configuration primarily offers the
  • Process gas nitrogen preferred as purge gas is
  • the invention also has the advantage that a laser with low power can be used to measure the concentration, since the measuring distance is shortened by the shielding according to the invention in comparison to a measurement without shielding.
  • the use of a laser with low power also advantageously reduces the risk of undesired changes in the process gas, which could be triggered by the energy of the laser radiation in the process gas.
  • FIG. 1 a cross section through a volume containing the process gas
  • a tubular volume 1 containing the process gas is shown in the figure, which has on one side a laser 2a and on the opposite side a detector 2b which registers the laser radiation passing through the volume 1 and incident on the detector 2b.
  • the beam path of the laser 2a is partially surrounded by the shield 3, which delimits the measuring section 4 on both sides, both in the direction of the laser 2a and in the direction of the detector 2b.
  • Means for feeding a purge gas such as nitrogen are advantageously provided on the shield 3. These means are not shown in the figure.
  • Volume 1 is filled, for example, with a hot process gas (e.g. the exhaust gas from a steelworks furnace), which has a temperature of 800 ° C or higher and whose content of carbon monoxide is to be determined.
  • a shield 3 is used, which has two water-cooled ceramic tubes 3. Gaseous nitrogen is used as the flushing gas, which displaces the process gas from the interior of the ceramic tubes 3, which are cooled, for example, by tube coils (not shown) carrying cooling water.
  • a shield 3 advantageously has dimensions such that the measuring section 4 is, for example, a length of 10 cm to 30 cm.
  • a measuring section 4 of approximately 20 cm has proven to be particularly advantageous.
  • the laser used is, for example, a tunable laser that is operated according to the invention at a single frequency selected before the measurements.
  • a tunable laser has the advantage that the frequency (or wavelength) that can be well absorbed by the gas component to be determined can be selected from its possible frequency range.
  • the weakening of the selected absorption line is a measure of the concentration of the gas components to be determined in the process gas.
  • a single-mode laser that has a frequency that matches the gas component to be determined.
  • the laser measurements can be carried out with particular advantage as continuous measurements. In a further embodiment of the invention, however, discontinuous measurement methods can also be used successfully.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Optics & Photonics (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Optical Measuring Cells (AREA)

Abstract

L'invention concerne un dispositif et un procédé de mesure d'une concentration d'au moins un composant d'un gaz de processus faisant appel à un laser (2a), le chemin du faisceau du laser (2a) traversant un volume (1) contenant ledit gaz de processus. L'invention se caractérise en ce que le chemin du faisceau passe partiellement librement à travers le gaz de processus et est partiellement protégé du gaz de processus, seule la partie du chemin du faisceau passant librement à travers le gaz de processus constituant la section de mesure (4) et étant prise en compte pour une mesure spectroscopique par laser de la concentration, au cours de laquelle précisément une ligne d'absorption est déterminée.
PCT/EP2003/005296 2002-04-24 2003-05-20 Dispositif et procede de mesure spectroscopique d'une concentration de gaz par determination d'une seule ligne d'absorption Ceased WO2003100392A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP03732429A EP1508030A1 (fr) 2002-05-24 2003-05-20 Dispositif et procede de mesure spectroscopique d'une concentration de gaz par determination d'une seule ligne d'absorption
BR0311244-6A BR0311244A (pt) 2002-05-24 2003-05-20 Dispositivo e processo para a medição espectrocópica de uma concentração de gás através da determinação de uma única linha de absorção
AU2003238366A AU2003238366A1 (en) 2002-05-24 2003-05-20 Device and method for spectroscopically measuring a gas concentration by determining a single absorption line
JP2004507803A JP2005526978A (ja) 2002-05-24 2003-05-20 単一吸収線測定による気体濃度分光測定装置及び方法
KR10-2004-7018995A KR20050013552A (ko) 2002-05-24 2003-05-20 분광법을 이용하여 단일 흡수선을 결정함으로써 가스농도를 측정하기 위한 장치 및 방법
US10/996,037 US20050128486A1 (en) 2002-04-24 2004-11-24 Device and method for spectroscopically measuring a gas concentration by determining a single absorption line

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10223239A DE10223239A1 (de) 2002-05-24 2002-05-24 Vorrichtung und Verfahren zur spektroskopischen Messung einer Gaskonzentration durch Bestimmung einer einzelnen Absorptionslinie
DE10223239.3 2002-05-24

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/996,037 Continuation US20050128486A1 (en) 2002-04-24 2004-11-24 Device and method for spectroscopically measuring a gas concentration by determining a single absorption line

Publications (1)

Publication Number Publication Date
WO2003100392A1 true WO2003100392A1 (fr) 2003-12-04

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Application Number Title Priority Date Filing Date
PCT/EP2003/005296 Ceased WO2003100392A1 (fr) 2002-04-24 2003-05-20 Dispositif et procede de mesure spectroscopique d'une concentration de gaz par determination d'une seule ligne d'absorption

Country Status (9)

Country Link
EP (1) EP1508030A1 (fr)
JP (1) JP2005526978A (fr)
KR (1) KR20050013552A (fr)
AU (1) AU2003238366A1 (fr)
BR (1) BR0311244A (fr)
DE (1) DE10223239A1 (fr)
RU (1) RU2004138074A (fr)
WO (1) WO2003100392A1 (fr)
ZA (1) ZA200410367B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5972760B2 (ja) * 2012-11-09 2016-08-17 三菱重工業株式会社 排ガス脱硝システム、排ガス脱硝装置の再生方法及び排ガス脱硝装置の触媒交換方法
JP6000083B2 (ja) * 2012-11-16 2016-09-28 三菱重工業株式会社 排ガス脱硝システム

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3838925A (en) * 1972-12-07 1974-10-01 Baldwin Electronics Inc Photoelectric opacity measuring system
GB1453938A (en) * 1972-10-26 1976-10-27 Bailey Meter Co Monitoring of a gas stream
US4076425A (en) * 1976-02-17 1978-02-28 Julian Saltz Opacity measuring apparatus
US4225243A (en) * 1978-06-26 1980-09-30 Measurex Corporation Gas measuring apparatus with standardization means, and method therefor
US4247205A (en) * 1979-02-02 1981-01-27 Measurex Corporation Gas measuring apparatus with standardization means, and method therefor
GB2066947A (en) * 1980-01-09 1981-07-15 Measurex Corp Gas measuring apparatus with adjustable path length, and method for operation and standardization therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1453938A (en) * 1972-10-26 1976-10-27 Bailey Meter Co Monitoring of a gas stream
US3838925A (en) * 1972-12-07 1974-10-01 Baldwin Electronics Inc Photoelectric opacity measuring system
US4076425A (en) * 1976-02-17 1978-02-28 Julian Saltz Opacity measuring apparatus
US4225243A (en) * 1978-06-26 1980-09-30 Measurex Corporation Gas measuring apparatus with standardization means, and method therefor
US4247205A (en) * 1979-02-02 1981-01-27 Measurex Corporation Gas measuring apparatus with standardization means, and method therefor
GB2066947A (en) * 1980-01-09 1981-07-15 Measurex Corp Gas measuring apparatus with adjustable path length, and method for operation and standardization therefor

Also Published As

Publication number Publication date
EP1508030A1 (fr) 2005-02-23
KR20050013552A (ko) 2005-02-04
JP2005526978A (ja) 2005-09-08
BR0311244A (pt) 2005-03-15
AU2003238366A1 (en) 2003-12-12
ZA200410367B (en) 2006-06-28
RU2004138074A (ru) 2005-09-10
DE10223239A1 (de) 2003-12-04

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