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WO2003027667A1 - Procede et detecteur pour detecter des gaz - Google Patents

Procede et detecteur pour detecter des gaz Download PDF

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Publication number
WO2003027667A1
WO2003027667A1 PCT/DE2002/003504 DE0203504W WO03027667A1 WO 2003027667 A1 WO2003027667 A1 WO 2003027667A1 DE 0203504 W DE0203504 W DE 0203504W WO 03027667 A1 WO03027667 A1 WO 03027667A1
Authority
WO
WIPO (PCT)
Prior art keywords
sensor array
sensors
sensor
gas
sampling unit
Prior art date
Application number
PCT/DE2002/003504
Other languages
German (de)
English (en)
Inventor
Andreas Walte
Wolf MÜNCHMEYER
Original Assignee
Wma Airsense Analysentechnik 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 Wma Airsense Analysentechnik Gmbh filed Critical Wma Airsense Analysentechnik Gmbh
Priority to EP02772065A priority Critical patent/EP1428020A1/fr
Publication of WO2003027667A1 publication Critical patent/WO2003027667A1/fr

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N1/2226—Sampling from a closed space, e.g. food package, head space
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0029—Cleaning of the detector
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0031—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array
    • G01N33/0034—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array comprising neural networks or related mathematical techniques
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0078—Testing material properties on manufactured objects
    • G01N33/0081—Containers; Packages; Bottles
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N1/24—Suction devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
    • G01N2001/222—Other features
    • G01N2001/2223—Other features aerosol sampling devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N1/2226—Sampling from a closed space, e.g. food package, head space
    • G01N2001/2229—Headspace sampling, i.e. vapour over liquid

Definitions

  • the invention relates to a method for determining gases according to the features of the preamble of claim 1 and a corresponding detector for carrying out the method according to the features of the preamble of claim 10.
  • Such methods and the corresponding detectors are used both for the identification of gaseous mixtures and for the detection of deviations in the composition of the mixtures in the chemical industry and in particular in food chemistry for quality control. It is now of great importance that food containers or containers are checked for the presence of contaminants before they are used. Especially before filling with products such as Such measurements are necessary for drinks, luxury foods or food in a new container or before or after using a recycled container.
  • the contamination in the containers can be detected with appropriate gas detectors.
  • suitable gas detectors For example, US 5523565, DE 4302657 Cl and DE 4306833 C2 describe how contaminations in containers, such as plastic bottles, are determined using mass spectrometric methods.
  • mass spectrometers are very costly to procure.
  • these are very sensitive devices that can only be operated and serviced by specialists. Due to the necessary pump system and the dirt-prone ionization techniques, frequent service intervals are necessary.
  • the above-mentioned patents or patent applications also describe combinations with detectors, such as, for example, a photoionization detector (PID), for preselecting containers.
  • PID photoionization detector
  • the determination of contamination can be improved by combining not very selective gas sensors and sometimes also with selective sensors to form a sensor array.
  • the measurement signals of the individual sensors can then be compared with previously measured or also stored signals and the measured state can be described.
  • Such detectors have been known for a long time.
  • Some of these systems, in which several sensors with cross sensitivity in the form of sensor arrays are used, have been known under the name “electronic noses” for some years.
  • These devices consist of an arrangement of several sensors, for example the “cold” sensors, such as quartz crystals, or conductive polymers or the "hot” sensors, such as semiconductor gas sensors and control and evaluation electronics, or evaluation computers.
  • the systems are often combined with a gas sampling unit. For example, DE 19807658 C1 describes the combination of sensor arrays with a sampling device.
  • sensor arrays can also be used to detect residual odors or gases in the interior of plastic bottles or containers. None of these publications describes how gaseous compounds are measured in the presence of liquids. Another disadvantage is that very often, such as if contamination in containers is detected, the response time of the system is too long. Another disadvantage is that sensor drift also occurs with simple sensors, which has a negative effect on repeatability and reproducibility.
  • the invention is therefore based on the object of developing a generic method and a corresponding detector for the determination of gases, in which the sampling is carried out in a simple manner and the determination of the contamination is carried out quickly, and the smallest contaminations are to be detected as well be differentiated enough to ensure the detection of individual connections in the presence of other connections and in addition the sensor drift should be limited and at the same time the life of the sensors should be improved.
  • the new method and the new detector for determining gases eliminate the disadvantages of the prior art mentioned.
  • Fig. 1 is a schematic representation of the device for performing the method and Fig. 2 shows an exemplary sensor signal of a metal oxide sensor at fast
  • the device for carrying out the method for determining contamination in containers mainly consists of a sampling unit 1, which expediently separates gaseous compounds from liquids or particles, and a sensor array system 2, which consists of a combination of gas sensors.
  • the container 3 to be examined is sucked through a sampling tube 4 or special hose by means of a pump 5 if there is no overpressure in the system.
  • the content reaches a separator 6, in which any liquids or dust particles that are also conveyed are separated from the gas phase.
  • the liquid can also be atomized if necessary via a suitable shape of the pipe end 7, to promote the transition from contamination in the liquid to the gas phase by enlarging the surface.
  • the measuring gas reaches the detector via a further line, the detector feed line 8.
  • the liquid is disposed of via a drain hose 9.
  • the separator can be cleaned via a cleaning line 10 with the valve 11.
  • the cleaning line can also be fed to an optional valve on the sampling tube 4 if required.
  • the detector essentially consists of an arrangement of gas sensors, also called sensor array 12, a feed pump for gases 13 and a further optional fresh air supply line 14 with valve 15.
  • the control and evaluation takes place via a computer 16.
  • the flushing of the separator 6 via the cleaning line 10 is necessary in order to enable fast measuring cycles. Carryover of the samples is avoided by cleaning.
  • cleaning e.g. Oil-free compressed air or, if necessary, water or steam can be used.
  • the separator 6 can also be heated in order to avoid carryover of the samples.
  • the sensors in the detector are flushed through the fresh air supply.
  • the flushing of the separator 6 is time-controlled, but is also carried out as a function of the measurement signal from a gas sensor or a plurality of selected sensors. From a threshold of the sensor signal to be set, the purging is activated via the computer 16 and it is prevented that excessive concentrations of the gases or contaminations reach the sensors. This allows the sensors to return to their output signal faster after a deflection and are faster ready for the next measurement. Overloading of the sensors is additionally prevented, which also leads to a lower sensor drift and to a longer service life of the sensors. To accelerate the return of the sensor to the initial value, it can also be flushed with cleaning gases such as oxygen or ozone. In addition, the working temperature of the sensor can be increased during the rinsing process.
  • FIG. 2 shows an example of a sensor signal from a metal oxide sensor during fast measuring cycles.
  • the curve profile 17 shows the response behavior of a sensor when it is exposed to a gas once. At a threshold 18, fresh air is flushed.
  • the curve profile 19 shows the response behavior when the impulses are repeated quickly. The course of the curve and the behavior of the different sensors change when the gas composition changes.
  • the curve shape can be used for the subsequent pattern recognition or, as shown in Figure 2, fixed time ranges 20 of the curve shape.
  • Subsequent pattern recognition compares previously measured sensor signals with currently measured ones. This allows mixtures or contaminations to be recorded. Unknown contaminations are also recognized by using suitable mathematical methods such as distance classifiers, discriminatory analysis methods or Kohonen or back propagation networks to identify deviations from the normal. In order to take into account sensor drift, ie long-term changes in the response behavior of the sensors, mathematical methods for drift compensation can also be used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Immunology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Artificial Intelligence (AREA)
  • Evolutionary Computation (AREA)
  • Mathematical Physics (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

Il est de grande importance que les conteneurs de produits alimentaires ou récipients soient inspectés, avant leur utilisation, quant à la présence de contaminations. Les techniques de mesure connues sont imprécises et les appareils utilisés à cet effet sont très chers. Ainsi, l'invention concerne un procédé et un détecteur correspondant permettant la détection de gaz, une prise d'échantillon étant réalisée de façon simple, et la détection de la contamination s'effectuant rapidement. L'invention doit permettre la reconnaissance de contaminations même très limitées et une différenciation de celles-ci de manière suffisamment sélective pour garantir la mise en évidence de composés individuels en la présence d'autres composés. A cet effet, différents types de détecteurs sont combinés sur un réseau de détection (12), lesdits détecteurs étant nettoyés à la fois par intervalles de temps fixes et en fonction de l'intensité des signaux de détection, et le système de réseau de détection (12) pouvant être entraîné à partir des signaux de mesure. Des procédé de ce type et les détecteurs correspondants sont utilisés pour identifier des mélanges gazeux dans la chimie des produits alimentaires pour réaliser des contrôles de qualité.
PCT/DE2002/003504 2001-09-20 2002-09-19 Procede et detecteur pour detecter des gaz WO2003027667A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02772065A EP1428020A1 (fr) 2001-09-20 2002-09-19 Procede et detecteur pour detecter des gaz

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10146434A DE10146434B4 (de) 2001-09-20 2001-09-20 Vorrichtung zur Identifikation kontaminierter Behälter
DE10146434.7 2001-09-20

Publications (1)

Publication Number Publication Date
WO2003027667A1 true WO2003027667A1 (fr) 2003-04-03

Family

ID=7699708

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2002/003504 WO2003027667A1 (fr) 2001-09-20 2002-09-19 Procede et detecteur pour detecter des gaz

Country Status (3)

Country Link
EP (1) EP1428020A1 (fr)
DE (1) DE10146434B4 (fr)
WO (1) WO2003027667A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009038237A1 (de) * 2009-08-20 2011-03-03 Siemens Aktiengesellschaft Probenentnahmesystem für ein Gerät zur Atemgasanalyse
DE102011007665A1 (de) * 2011-04-19 2012-10-25 Siemens Aktiengesellschaft Detektion und Analyse von ölbasierten Kontaminanten in organischem Material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3126647A1 (de) * 1981-07-07 1983-01-20 Hans Dr. 2000 Hamburg Fuhrmann "verfahren zur kalibrierung von gas-halbleitern fuer messzwecke, die vermittels kalibriereinrichtungen automatisch in bestimmten zeitabstaenden geprueft bzw. nachjustiert werden"
US4723436A (en) * 1985-06-15 1988-02-09 Dragerwerk Aktiengesellschaft Process for calibrating a gas metering instrument
EP0571783A2 (fr) * 1992-05-29 1993-12-01 Msi Elektronik Gmbh Méthode et appareil pour la calibration de détecteurs de gaz dans des appareils de mesure pour l'analyse de gaz, l'analyse de gaz de fumée et/ou la détermination de l'efficacité des installations de combustion et appareil de mesure pour la réalisation de cette méthode
WO1996006345A1 (fr) * 1994-08-18 1996-02-29 Msa (Britain) Limited Detecteur a infrarouge pour gaz
WO2000047990A2 (fr) * 1999-02-13 2000-08-17 Genzyme Virotech Gmbh Analyseur de gaz et son utilisation pour etablir des diagnostics medicaux
US6202408B1 (en) * 1998-03-13 2001-03-20 Fev Motorentechnik Gmbh & Co., Kg Method and apparatus for a zero-point stabilization of an exaust gas sensor

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3316371A1 (de) * 1983-05-05 1984-11-08 Heinz Till Verfahren und vorrichtung zur kontrolle von kegs
DE4038993C2 (de) * 1990-12-06 1995-07-06 Lehmann Martin Verfahren zum Selektionieren von Behältnissen und Meßanordnung zur Durchführungs des Verfahrens
US5352611A (en) * 1992-06-01 1994-10-04 The Coca-Cola Company Method and system for sampling and determining the presence of compounds in containers
DE4302657C1 (de) * 1993-01-30 1994-03-03 Holstein & Kappert Maschf Verfahren zur Bestimmung von Kontaminaten in Behältern
DE4306833C2 (de) * 1993-02-05 1995-04-27 Khs Masch & Anlagenbau Ag Verfahren zur Bestimmung von durch Reststoffe kontaminierten Mehrwegflaschen oder Behältern
EP0647847A1 (fr) * 1993-09-14 1995-04-12 Elpatronic Ag Utilisation d'un spectromètre de masse à ionisation de récipients
FR2710153B1 (fr) * 1993-09-17 1995-12-01 Alpha Mos Sa Procédés et appareils de détection des substances odorantes et applications.
DE4427314C2 (de) * 1994-08-02 1997-02-20 Graessle Walter Gmbh Vorrichtung zur Untersuchung von Behältern auf Fremdgase
DE19505474C2 (de) * 1995-02-17 1998-04-02 Kronseder Maschf Krones Verfahren und Vorrichtung zum Prüfen von Flaschen aus Kunststoff auf Kontaminationen
DE19807658C1 (de) * 1998-02-24 2001-05-23 Wma Airsense Analysentechnik G Verfahren und Einrichtung zur Bestimmung von gasförmigen Verbindungen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3126647A1 (de) * 1981-07-07 1983-01-20 Hans Dr. 2000 Hamburg Fuhrmann "verfahren zur kalibrierung von gas-halbleitern fuer messzwecke, die vermittels kalibriereinrichtungen automatisch in bestimmten zeitabstaenden geprueft bzw. nachjustiert werden"
US4723436A (en) * 1985-06-15 1988-02-09 Dragerwerk Aktiengesellschaft Process for calibrating a gas metering instrument
EP0571783A2 (fr) * 1992-05-29 1993-12-01 Msi Elektronik Gmbh Méthode et appareil pour la calibration de détecteurs de gaz dans des appareils de mesure pour l'analyse de gaz, l'analyse de gaz de fumée et/ou la détermination de l'efficacité des installations de combustion et appareil de mesure pour la réalisation de cette méthode
WO1996006345A1 (fr) * 1994-08-18 1996-02-29 Msa (Britain) Limited Detecteur a infrarouge pour gaz
US6202408B1 (en) * 1998-03-13 2001-03-20 Fev Motorentechnik Gmbh & Co., Kg Method and apparatus for a zero-point stabilization of an exaust gas sensor
WO2000047990A2 (fr) * 1999-02-13 2000-08-17 Genzyme Virotech Gmbh Analyseur de gaz et son utilisation pour etablir des diagnostics medicaux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ENDRES H-E ET AL: "A thin-film SnO2 sensor system for simultaneous detection of CO and NO2 with neural signal evaluation", SENSORS AND ACTUATORS B, ELSEVIER SEQUOIA S.A., LAUSANNE, CH, vol. 36, no. 1, 1 October 1996 (1996-10-01), pages 353 - 357, XP004061094, ISSN: 0925-4005 *

Also Published As

Publication number Publication date
DE10146434B4 (de) 2004-08-19
EP1428020A1 (fr) 2004-06-16
DE10146434A1 (de) 2003-04-10

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