WO1993006457A1 - Procede et dispositif pour la mesure quantitative et qualitative de particules de suie hydrocarburees en suspension dans des gaz - Google Patents

Procede et dispositif pour la mesure quantitative et qualitative de particules de suie hydrocarburees en suspension dans des gaz Download PDF

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Publication number
WO1993006457A1
WO1993006457A1 PCT/EP1992/002085 EP9202085W WO9306457A1 WO 1993006457 A1 WO1993006457 A1 WO 1993006457A1 EP 9202085 W EP9202085 W EP 9202085W WO 9306457 A1 WO9306457 A1 WO 9306457A1
Authority
WO
WIPO (PCT)
Prior art keywords
chamber
gas
diode laser
measurement
resonance
Prior art date
Application number
PCT/EP1992/002085
Other languages
German (de)
English (en)
Inventor
Reinhard Niessner
Andreas Petzold
Original Assignee
Giv Gesellschaft Für Innovative Verfahrenstechnik Mbh
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 Giv Gesellschaft Für Innovative Verfahrenstechnik Mbh filed Critical Giv Gesellschaft Für Innovative Verfahrenstechnik Mbh
Publication of WO1993006457A1 publication Critical patent/WO1993006457A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/1702—Systems in which incident light is modified in accordance with the properties of the material investigated with opto-acoustic detection, e.g. for gases or analysing 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
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/1702—Systems in which incident light is modified in accordance with the properties of the material investigated with opto-acoustic detection, e.g. for gases or analysing solids
    • G01N2021/1704—Systems in which incident light is modified in accordance with the properties of the material investigated with opto-acoustic detection, e.g. for gases or analysing solids in gases
    • 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
    • G01N2021/399—Diode laser

Definitions

  • the invention relates to a method according to the preamble of claim 1 and a device for highly sensitive quantitative determination of hydrocarbon-containing soot aerosols, as typically used in incomplete combustion processes, for. B. in diesel engines.
  • the method is intended on the one hand to record the graphitic part alone and on the other hand to record the graphitic hydrocarbonaceous part of a combustion aerosol.
  • the measurement and determination of diesel and soot aerosols in emissions and immissions is mainly carried out by enriching, integrating collection of the total aerosol using a membrane or quartz filter.
  • the determination of the separated aerosol can now be done by targeted Pyrolysis with subsequent determination of the escaping C02 (coulometric, conductometric, photoacoustic).
  • the blackening of the filter caused by soot particles can be used for the measurement spectroscopically (reflectometrically or by transmission measurement).
  • the first developments to an on-line measurement technology are the use of IR absorption in an optical extinction measurement according to Prempl et al. (SAE Technical Paper 850269 from 1985).
  • the diesel exhaust gas aerosol is analyzed on line at wavelengths of 3 to 4 ⁇ m for accumulated hydrocarbons and at 6 ⁇ m for graphitic soot in a transmission measurement.
  • the detection limits are 1 mg / m 3 for organic insoluble mass (mainly graphite) and 5 mg / m 3 given for the total hydrocarbon. This enables continuous measurement in the highly polluted emission range, but not in the immission concentration range.
  • Photoacoustic soot detection according to Adams et al. Represents a much more powerful on-line measurement technique that partially fulfills the conditions. (Atmos. Environ. 23 (1989), p. 693).
  • a voluminous Ar ion laser with a mechanical chopper wheel is used in order to absorb light by soot particles in a resonantly operated, photoacoustic measuring cell at 514.4 nm to measure proportional heating of the surrounding gas and thus a pressure increase in the cell.
  • the measurement signal here the gas pressure in the cell
  • the measurement signal is proportional to the incident light intensity and that with a high power of the laser, the lowest light absorption by soot can still be detected.
  • the object of the invention is to provide a method and a device which overcome these disadvantages.
  • the semiconductor diode laser illuminates at least a part of the chamber and emits wavelengths at an absorption minimum of water vapor and an absorption maximum of long-chain hydrocarbons or elemental carbon and its ' intensity can be modulated in that the chamber as a resonant photoacoustic cell is designed and the pressure transducer is attached to it at the location of a pressure maximum of a resonance, that the measurement is carried out at a harmonic of the cell resonance and thus with the exclusion of low-frequency interference and that the gas feed pump produces an adjustable air flow from the gas inlet to the gas outlet.
  • Semiconductor diode lasers with an emission range at 800 nm largely reduce the influences of high N03 concentrations, as can be found in diesel exhaust gas, since N03 has a much smaller absorption cross section in the near IR range than at about 514.5 nm Water vapor on the measurement signal is not significantly higher in this wavelength range than at 514.5 nm, so that the invention represents a compact and mobile measurement system that can be used both for emission measurements on the running engine and for immission measurements.
  • a plurality of lasers preferably irradiate the soot aerosol at different wavelengths.
  • a size-selecting inlet system defines the particle spectrum to be examined.
  • a device for carrying out the method, consisting of a closed chamber with gas inlet and outlet, to which a pressure sensor, a modulatable semiconductor diode laser and a gas feed pump are attached, it is provided that the semiconductor diode laser illuminates at least a part of the chamber and has wavelengths at an absorption minimum of water vapor and an absorption maximum of long-chain hydrocarbons or elemental carbon and its intensity can be modulated, that the chamber is designed as a resonant photoacoustic cell and the pressure transducer is attached to it at the location of a pressure maximum of a resonance that the measurement at a harmonic of the cell resonance and thus under exclusion of low-frequency interference and that the Gas feed pump produces an adjustable air flow from the gas inlet to the gas outlet.
  • the aerosol conveyed by the gas pump 4, enters the resonant photoacoustic cell 1 with the pressure transducer "la.
  • a modulated diode laser 2 which emits at 300 nm, is flanged on.
  • the aerosol in the cell is irradiated via suitable optics 3 Now that on the one hand not the first resonant mode is excited, but that the resonance frequency of the next higher mode is used to modulate the diode laser.
  • the detection limit is currently around 50 g of particulate soot per m air.
  • soot aerosols by measurement has hitherto been carried out either by enriching the total aerosol on filters, IR extinction measurements or by photoacoustic soot detection using an Ar ion laser. Neither of the first two methods is able to guarantee good time resolution at low detection limits.
  • the photoacoustic soot detection can neither lead to measurements at high Environmental noise (engine test bench) are used, still differentiate between elemental and organically bound carbon.
  • the photoacoustic soot detector uses a modulatable semiconductor diode laser as the light source. This makes a commonly used mechanical chopper superfluous and, due to its small size, leads to a compact and mobile soot detector. The influence of ambient noise is minimized by the measurement with a higher resonance of the photoacoustic cell. This eliminates low-frequency interference.
  • the organically bound carbon is detected by a second diode laser, which emits in the range between 3 and 4 ⁇ .
  • the photoacoustic soot detector can be used for emission monitoring on an engine test bench or for immission measurements.

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  • Physics & Mathematics (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)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

Pour une détection photoacoustique extrêmement sensible de particules de graphite ou de suie sur lesquelles s'est fixé un hydrocarbure, dans des gaz, en particulier dans l'air, on utilise une chambre fermée comportant une entrée et une sortie de gaz, à laquelle sont associés un capteur de pression (1a), un laser modulable à diode à semiconducteur (2) et une pompe d'alimentation en gaz (4). Le laser à diode à semiconducteur (2) éclaire au moins une partie de la chambre. Il rayonne avec des longueurs d'onde correspondant à une absorption minimum de la vapeur d'eau et à une absorption maximum d'hydrocarbures à chaîne longue ou du carbone élémentaire et il est modulable en intensité. La chambre est conçue comme une cellule photoacoustique résonante (1) et le capteur de pression (1a) est disposé à l'emplacement correspondant à une pression maximum d'une résonance. La mesure est effectuée au niveau d'une harmonique de la résonance de la cellule et donc sans perturbations basse fréquence. La pompe d'alimentation en gaz (4) produit un flux d'air réglable allant de l'entrée de gaz à la sortie de gaz.
PCT/EP1992/002085 1991-09-14 1992-09-10 Procede et dispositif pour la mesure quantitative et qualitative de particules de suie hydrocarburees en suspension dans des gaz WO1993006457A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914130639 DE4130639A1 (de) 1991-09-14 1991-09-14 Verfahren zur quantitativen und qualitativen erfassung von kohlenwasserstoffhaltigen russschwebeteilchen in gasen
DEP4130639.2 1991-09-14

Publications (1)

Publication Number Publication Date
WO1993006457A1 true WO1993006457A1 (fr) 1993-04-01

Family

ID=6440630

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/002085 WO1993006457A1 (fr) 1991-09-14 1992-09-10 Procede et dispositif pour la mesure quantitative et qualitative de particules de suie hydrocarburees en suspension dans des gaz

Country Status (2)

Country Link
DE (1) DE4130639A1 (fr)
WO (1) WO1993006457A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6570655B1 (en) 1999-11-26 2003-05-27 Avl List Gmbh Process and apparatus for measuring the opacity in gases
US8848191B2 (en) 2012-03-14 2014-09-30 Honeywell International Inc. Photoacoustic sensor with mirror

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4415852A1 (de) * 1994-05-05 1995-11-09 Gerhart Schroff Verfahren und Anordnung zur Dichtheitsprüfung
US5900533A (en) * 1995-08-03 1999-05-04 Trw Inc. System and method for isotope ratio analysis and gas detection by photoacoustics
DE19735205A1 (de) * 1997-08-14 1999-02-25 Gustav Prof Dr Techn Schweiger Verfahren zur spektroskopischen Rußmessung
DE19744500A1 (de) * 1997-10-09 1999-04-15 Abb Research Ltd Photoakustische Freifall-Messzelle
RU172629U1 (ru) * 2016-04-18 2017-07-17 Федеральное государственное бюджетное учреждение науки Института общей физики им. А.М. Прохорова Российской академии наук Фотоакустический газоанализатор
RU2646420C1 (ru) * 2016-11-23 2018-03-05 федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский национальный исследовательский университет информационных технологий, механики и оптики" (Университет ИТМО) Способ частотно-импульсной модуляции полупроводникового лазерного источника оптического излучения для опроса оптических интерферометрических датчиков
EP3945305A1 (fr) 2020-07-29 2022-02-02 Hahn-Schickard-Gesellschaft für angewandte Forschung e.V. Procédé de détection des particules d'aérosol dans un air ambiant

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4557137A (en) * 1982-09-10 1985-12-10 Hitachi, Ltd. Photoacoustic analyzer
US4722602A (en) * 1985-08-14 1988-02-02 Hitachi, Ltd. Apparatus and method for analyzing particles in a medium

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4492862A (en) * 1981-08-07 1985-01-08 Mathematical Sciences Northwest, Inc. Method and apparatus for analyzing components of hydrocarbon gases recovered from oil, natural gas and coal drilling operations
JPS595939A (ja) * 1982-07-03 1984-01-12 Horiba Ltd パ−テイキユレ−ト連続測定装置
JPH0621861B2 (ja) * 1987-09-28 1994-03-23 株式会社日立製作所 光音響分光装置
CH679076A5 (fr) * 1989-06-13 1991-12-13 Oscar Dr Sc Nat Oehler

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4557137A (en) * 1982-09-10 1985-12-10 Hitachi, Ltd. Photoacoustic analyzer
US4722602A (en) * 1985-08-14 1988-02-02 Hitachi, Ltd. Apparatus and method for analyzing particles in a medium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
APPLIED OPTICS, Band. 30, Nr. 12, April 1991 Charles W. Bruce et al: "Trans-spectral absorption and scattering of electromagnetic radiation by diesel soot ", *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6570655B1 (en) 1999-11-26 2003-05-27 Avl List Gmbh Process and apparatus for measuring the opacity in gases
US8848191B2 (en) 2012-03-14 2014-09-30 Honeywell International Inc. Photoacoustic sensor with mirror

Also Published As

Publication number Publication date
DE4130639A1 (de) 1993-03-18

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