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WO1996007899A1 - Procede et dispositif permettant de determiner des concentrations de gaz dans un melange gazeux - Google Patents

Procede et dispositif permettant de determiner des concentrations de gaz dans un melange gazeux Download PDF

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Publication number
WO1996007899A1
WO1996007899A1 PCT/CH1995/000197 CH9500197W WO9607899A1 WO 1996007899 A1 WO1996007899 A1 WO 1996007899A1 CH 9500197 W CH9500197 W CH 9500197W WO 9607899 A1 WO9607899 A1 WO 9607899A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
gas component
concentration
cell
acoustic resonator
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/CH1995/000197
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German (de)
English (en)
Inventor
Andreas Rüetschi
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.)
SCR CREVOISERAT SA
Original Assignee
SCR CREVOISERAT SA
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 SCR CREVOISERAT SA filed Critical SCR CREVOISERAT SA
Priority to AU32513/95A priority Critical patent/AU3251395A/en
Publication of WO1996007899A1 publication Critical patent/WO1996007899A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
    • G01N29/22—Details, e.g. general constructional or apparatus details
    • G01N29/24—Probes
    • G01N29/2418—Probes using optoacoustic interaction with the material, e.g. laser radiation, photoacoustics
    • 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
    • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
    • G01N29/02—Analysing fluids
    • G01N29/024—Analysing fluids by measuring propagation velocity or propagation time of acoustic waves
    • 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
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/01—Indexing codes associated with the measuring variable
    • G01N2291/011—Velocity or travel time
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/01—Indexing codes associated with the measuring variable
    • G01N2291/014—Resonance or resonant frequency
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/021—Gases
    • G01N2291/0212—Binary gases
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/02—Indexing codes associated with the analysed material
    • G01N2291/028—Material parameters
    • G01N2291/02809—Concentration of a compound, e.g. measured by a surface mass change
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2291/00—Indexing codes associated with group G01N29/00
    • G01N2291/10—Number of transducers
    • G01N2291/105—Number of transducers two or more emitters, two or more receivers

Definitions

  • the present invention relates to a method and a device for determining gas concentrations in a gas mixture in the exhaust gas monitoring of heating systems according to claims 1-8 and 9-14, as well as uses according to claims 15-17.
  • PS-EP-277622 describes a detection device for the optical-spectroscopic detection of gases by means of the photo-acoustic effect.
  • This device essentially consists of a light source, a detector designed as a gas collection cell and signal processing means. After passing through a narrowband interference filter, the light from the source is radiated into a photoacoustic gas cuvette containing the measurement gas, and the measurement is carried out with the cuvette closed or nearly closed.
  • the disadvantage here is the fact that this arrangement has no means of avoiding, or correcting or compensating, for contaminants which are deposited on the entrance window and thus significantly impair the service life.
  • a CO analysis device which essentially has a main detector and a compensation detector, as a result of which interference components are effectively eliminated.
  • This transmission process is characterized by a complicated design of the arrangement, which includes requires two sealed gas cells, which has an adverse effect on inexpensive production.
  • TF Deaton et al. a differential photoacoustic method described, which is particularly suitable for the determination of very small concentrations of methane, carbon dioxide and nitrogen dioxide (Appl. Physics Lett., Vol.26, 300-303 (1975)).
  • a disadvantage is the high experimental effort, which is primarily due to the use of a deuterium fluoride (DF) laser.
  • DF deuterium fluoride
  • the object of the present invention is to provide methods and devices with which gas concentrations in a gas mixture (carbon dioxide and carbon monoxide) are determined in combination in a measuring system and which are inexpensive to manufacture and can be used in the exhaust gas monitoring of heating systems.
  • a method is intended to ensure that the measuring system based thereon can work maintenance-free over a long period of time and has a long service life.
  • the measuring accuracy that can be achieved must be sufficient to control a heating burner so that the legal requirements, e.g. those of an Air Pollution Control Ordinance (LRV) are met.
  • FIG. 2 shows a flow diagram of a measurement method for the combined determination of gas concentrations in a gas mixture
  • FIG. 3 shows a schematic structure of a measuring system with a combined sensor system for photoacoustic and sound measurements carried out in the same measuring cell
  • the measuring system 100 consists of a sensor system 110, a control and evaluation unit 120 and the data lines 130 which connect the sensor system and the control and evaluation unit.
  • the sensor system 110 is connected via a thermally shielded line 102 to a sample chamber, for example a chimney 103, in which the exhaust gases are present as a hot gas mixture mixed with particles, in particular with soot.
  • a pump 1 For the sampling of a gas sample 104, a pump 1 is provided, which via a line 5, a filter 6, a line 7, an acoustic resonator 10, a line 9, a valve 8, a line 11 and a photoacoustic cell 20 leads the sensor system 110.
  • the gas sample is conducted out of the sensor system 110 again via a line 2, a valve 3, a line 2 ′ and a line 4.
  • the line 5, which is surrounded by a thermal shield 102 tightly connects the interior of the chimney 103 to the filter 6.
  • At the outlet of the filter 6 there is a gas mixture free of particles of any kind, in particular of soot particles, ie a cleaned gas sample 105 is available, which is fed via line 7 into resonator 10.
  • the resonator 10 there is a transmitter 41 and a receiver 42, which are located at a fixed distance from one another and thus meet the requirements for measuring the speed of sound in the cleaned gas sample 105.
  • the resonator 10 In the
  • the concentration of the first gas component is determined via the speed of sound of the gas mixture or the cleaned gas sample 105.
  • a further valve 8 is a further valve 8 with the lines 9 and
  • the compartment 11 is provided, which leads the cleaned gas sample 105 via line 11 into a compartment 21 of the photoacoustic cell 20.
  • the compartment 21 is provided with a partition 23, which has an optical window 24. Via a valve 12 and the lines 13, 14, the cleaned gas sample 105 reaches a compartment 22, which in turn is connected to the valve 3 via a line 2.
  • the compartment 21 has a further partition 25 with an interference filter 26, which is opposite the partition 23 and which on the compartment 21 opposite side in the compartment 27 has an IR source 28.
  • the compartment 22 also has a detector 29 and a microphone 31 which is attached to the side of the photoacoustic cell 20.
  • the IR source 28, the microphone 31 and the detector 29 are connected via lines 51, 51 'and 51 "to a signal processing unit 50, which in turn is connected via a line 52 to a computer unit 80.
  • the transmitter 41 and the receiver 42 are connected via lines 61 and 61 'to a signal processing unit 60, which in turn is connected via a line 62 to the computer unit 80.
  • a temperature probe 73 is connected via a line 71 to a signal processing unit 70, which in turn is connected via a line 72 is connected to the computer unit 80.
  • the measured values of the concentrations of the first and second gas concentrations are available for further use, be it for display or for documentation of any kind cher kind, but especially for the control and regulation of combustion plants.
  • the gas mixture is fed to a filter, or a soot filter, which ensures that the cleaned gas sample leaving the filter no longer has any disturbing amounts of solids due to the selected pore size.
  • This cleaning of the gas sample is of crucial importance, since the lifespan of a measuring system essentially depends on the measures taken to avoid any kind of contamination.
  • the gas line that is intended for sampling and the filter are designed so that the gas sample in the subsequent units cannot fall below the dew point until the measurement system is left. This is ensured by ⁇ appropriate thermostatting of the measuring system.
  • the cleaned gas sample After the cleaned gas sample has been fed to an acoustic resonator, it is measured there after a dwell time of a few seconds. This is done in a manner known per se by measuring the speed of sound of the cleaned gas sample.
  • the acoustic resonator In the acoustic resonator there is a transmitter and a receiver at a fixed distance.
  • the transmitter frequency is now determined in such a way that the electrical receiver signal is in phase with the electrical transmitter signal.
  • This frequency is a measure of the speed of sound, from which the concentration of the first gas component, for example the CO 2 concentration tration, is determined. This measurement technique is not discussed in more detail here (BA Younglove, NV Frederik, Int.Journal of Thermophysics, Vol. 11/5, 897-905 (1990)).
  • a CO concentration that may be present in the cleaned gas sample can practically not influence the measurement accuracy, because on the one hand the CO concentrations are in the range of 0-1000 ppm, ie 0-0.1%, and on the other hand because the carbon monoxide and the nitrogen, which is present in large excess, has practically identical molecular weights.
  • the concentration of the first gas component for example the CO 2 concentration, is thus determined undisturbed in addition to the carbon monoxide.
  • a frequency proportional to the concentration of the first gas component for example the C0 2 concentration, is used, which is further processed in process step 4.
  • the frequency proportional to the concentration of the first gas component, for example the C0 2 concentration, and that to the con- Concentration of the second gas component, for example the CO concentration, a measurement signal having a linear relationship are each fed to a signal processing unit and electronically processed such that signals are present at the output of these signal processing units which can be supplied to the computer unit.
  • the measurement signal of the photoacoustic cell is recorded once with the valve closed and once with the valve open.
  • the two amplitude values of the measurement signal change in different ways with the concentrations of the gas components, for example with the concentrations of the CO or the CO 2 .
  • the measurement signals are processed in the computer unit in such a way that digital signals are present at the output, which can be supplied, for example, to a display, or which are kept available for any other use. Operations such as linearizations, offset corrections, smoothing and averaging of any kind are possible.
  • the possibilities for determining the concentrations of the first and second gas components, for example the CO 2 and CO concentrations, set out in process steps 3.1 and 3.2 represent only one type of problem solution. Furthermore, this method can be simplified, for example that the two gas concentrations are supplied to a single measuring cell, which on the one hand has the properties of the acoustic resonator, and on the other hand that of a photoacoustic cell. This naturally simplifies the necessary supply and discharge lines for the cleaned gas sample and the requirements for the control, both of which have an advantageous effect on the production costs. It is also advantageous to omit one measuring system, but for that remaining something becomes more complex.
  • the measuring system 100 consists of a sensor system 110, a control and evaluation unit 120 and the data lines 130, which connects the sensor system and the control and evaluation unit.
  • the sensor system 110 is connected via a thermal shield 102 to a sample space, for example a chimney 103, in which the exhaust gases are present as a hot gas mixture mixed with particles, in particular with soot.
  • a pump 1 is provided, which leads the gas sample into the sensor system 110 via a line 5, a filter 6, a line 7 and a measuring cell 30.
  • the gas sample is conducted out of the sensor system 110 again via a line 2, a valve 3, a line 2 ′ and a line 4.
  • a gas mixture free of particles of any kind, in particular of soot particles, ie a cleaned gas sample 105 Available which is led via the line 7 and an opening 153 into a compartment 121 of the measuring cell 30.
  • the compartment 121 is provided with a partition 123 which has an optical window 124.
  • the compartment 121 has a further partition 125 with an interference filter 126 or an IR bandpass filter, which is opposite the partition 123.
  • the compartment 121 is equipped with a transmitter 152 and a receiver 151, which are at a fixed distance from one another, and thus meet the requirements for measuring the speed of sound in the cleaned gas sample 105.
  • the line 7 ends with the opening 153, which is embedded in the receiver 152; it is chosen so small that it cannot interfere with the sound measurement. Of course, it can also be attached to another location in the compartment 121.
  • the speed of sound of the cleaned gas sample 105 for example the C0 2 concentration, determined.
  • a valve 112 and the lines 113, 114 are provided on the compartment 121 of the measuring cell 30, via which the cleaned gas sample 105 reaches a compartment 122, which in turn is connected to the valve 3 via a line 2 and adjoins the compartment 121 .
  • the compartment 122 also has a detector 129 and a microphone 131, which is attached to the side of the measuring cell 30.
  • the IR source 128, the microphone 131 and the detector 129 are connected via lines 51, 51 'and 51 "to a signal processing unit 50, which in turn is connected via a line 52 to a computer unit 80.
  • the transmitter 151 and the receiver 152 are connected via lines 61 and 61 'to a signal processing unit 60, which in turn is connected to the computer unit 80 via a line 62.
  • a temperature probe 73 is connected via a line 71 to a signal processing unit 70, which in turn is connected via a line 72 to is connected to the computer unit 80.
  • the measured values of the concentrations of the first and second gas components for example the CO 2 and CO concentrations, are available for further use, be it for a display or for Documentation of any kind, but especially for the control and regulation of heating systems.
  • this method is not limited to the determination of carbon dioxide and carbon monoxide. Rather, there are a number of further gas combinations which can be determined using the described method or the corresponding devices. For example, in addition to C0 2 also determine NO and other nitrogen oxides; or methane (CH 4 ), ethane (C 2 H ⁇ ), ethene (C 2 H 4 ), ethine (C 2 H 2 ), water and ammonia (NH 3 ).
  • the gas mixture in the sensor system (110) is converted into the concentration of the first gas component, for example the CO 2 concentration, in an acoustic resonator (10) and the concentration of the second gas component, for example the CO concentration, in a photoacoustic cell (20).
  • concentration of the first gas component for example the CO 2 concentration
  • concentration of the second gas component for example the CO concentration

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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)
  • Optics & Photonics (AREA)
  • Acoustics & Sound (AREA)
  • Investigating Or Analyzing Materials By The Use Of Ultrasonic Waves (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

L'invention concerne un procédé permettant de déterminer des concentrations de gaz dans des mélanges gazeux lors du contrôle des gaz brûlés d'installations de chauffage. Selon ledit procédé, on détermine dans un système de mesure (100) comprenant un système de détection (110), une unité de commande et d'évaluation (120) et des lignes de données (130), à partir d'un mélange gazeux situé dans le système de détection (110), la concentration d'un premier constituant gazeux, notamment la concentration en CO2, dans un résonateur (10) acoustique, et la concentration d'un second constituant gazeux, notamment la concentration en CO, dans une cellule photoacoustique (20). La commande du système de détection s'effectue à l'aide d'une unité informatique (80) dans laquelle les signaux de mesure (52, 62, 72) sont acheminés pour être évalués, après mise en forme correspondante dans des unités de traitement des signaux (50, 60, 70). L'unité informatique fournit les valeurs mesurées (81) de la concentration en gaz, notamment la concentration en CO2 et la concentration en CO, en vue de leur affichage ou d'une utilisation ultérieure. L'invention concerne également des systèmes de mesure permettant de mettre ledit procédé en oeuvre. Dans un de ces systèmes de mesure, il est prévu d'intégrer le résonateur (10) acoustique et la cellule photoacoustique (20) dans une seule cellule de mesure. Ce mode de réalisation présente une structure compacte et sa construction est simple. Ce procédé et ce dispositif s'utilisent dans le contrôle des gaz brûlés, et plus particulièrement dans la régulation d'installations de chauffage.
PCT/CH1995/000197 1994-09-07 1995-09-07 Procede et dispositif permettant de determiner des concentrations de gaz dans un melange gazeux Ceased WO1996007899A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU32513/95A AU3251395A (en) 1994-09-07 1995-09-07 Process and device for determining gas concentrations in a gas mixture

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH273294A CH685889A5 (de) 1994-09-07 1994-09-07 Verfahren und Vorrichtung zur Bestimmung von Gaskonzentrationen in einem Gasgemisch
CH2732/94-9 1994-09-07

Publications (1)

Publication Number Publication Date
WO1996007899A1 true WO1996007899A1 (fr) 1996-03-14

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Application Number Title Priority Date Filing Date
PCT/CH1995/000197 Ceased WO1996007899A1 (fr) 1994-09-07 1995-09-07 Procede et dispositif permettant de determiner des concentrations de gaz dans un melange gazeux

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AU (1) AU3251395A (fr)
CH (1) CH685889A5 (fr)
WO (1) WO1996007899A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT6119U3 (de) * 2003-01-29 2003-12-29 Avl List Gmbh Verfahren zur photoakustischen messung von fremdstoffen in gasen

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102596030B (zh) * 2009-11-03 2015-12-09 皇家飞利浦电子股份有限公司 用于测量呼出气中特定气体的水平的设备
EP3561487B1 (fr) 2018-04-25 2023-01-18 ABB Schweiz AG Dispositif de mesure destiné à l'analyse d'une composition d'un gaz de combustion pourvu d'une chambre filtrante disposée devant un détecteur

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2945172A1 (de) * 1979-11-08 1981-05-21 Erwin Sick Gmbh Optik-Elektronik, 7808 Waldkirch Verfahren und geraet zur bestimmung der konzentration eines gases in einem gasgemisch, insbesondere des kohlendioxidgehaltes
FR2491623A1 (fr) * 1980-10-07 1982-04-09 Toyo Soda Mfg Co Ltd Detecteur photoacoustique a circulation pour analyse de solutions
DE4018393A1 (de) * 1989-06-13 1990-12-20 Oehler Oscar Verfahren und vorrichtung zum messen von photosynthese-austauschgasen
WO1991014176A1 (fr) * 1990-03-05 1991-09-19 Fls Airloq A/S Procede et appareil de transmission d'un signal acoustique dans une cellule photoacoustique
US5129255A (en) * 1989-10-06 1992-07-14 The Aerospace Corporation Photoacoustic detection and tracking apparatus

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2945172A1 (de) * 1979-11-08 1981-05-21 Erwin Sick Gmbh Optik-Elektronik, 7808 Waldkirch Verfahren und geraet zur bestimmung der konzentration eines gases in einem gasgemisch, insbesondere des kohlendioxidgehaltes
FR2491623A1 (fr) * 1980-10-07 1982-04-09 Toyo Soda Mfg Co Ltd Detecteur photoacoustique a circulation pour analyse de solutions
DE4018393A1 (de) * 1989-06-13 1990-12-20 Oehler Oscar Verfahren und vorrichtung zum messen von photosynthese-austauschgasen
US5129255A (en) * 1989-10-06 1992-07-14 The Aerospace Corporation Photoacoustic detection and tracking apparatus
WO1991014176A1 (fr) * 1990-03-05 1991-09-19 Fls Airloq A/S Procede et appareil de transmission d'un signal acoustique dans une cellule photoacoustique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT6119U3 (de) * 2003-01-29 2003-12-29 Avl List Gmbh Verfahren zur photoakustischen messung von fremdstoffen in gasen

Also Published As

Publication number Publication date
AU3251395A (en) 1996-03-27
CH685889A5 (de) 1995-10-31

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