EP2856146A1 - Appareil de mesure et procédé pour appréhender la proportion d'hydrocarbures dans des gaz et tenant compte de la sensibilité aux influences parasites - Google Patents

Appareil de mesure et procédé pour appréhender la proportion d'hydrocarbures dans des gaz et tenant compte de la sensibilité aux influences parasites

Info

Publication number
EP2856146A1
EP2856146A1 EP13729277.7A EP13729277A EP2856146A1 EP 2856146 A1 EP2856146 A1 EP 2856146A1 EP 13729277 A EP13729277 A EP 13729277A EP 2856146 A1 EP2856146 A1 EP 2856146A1
Authority
EP
European Patent Office
Prior art keywords
content
measuring
gas
gas stream
gas flow
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Withdrawn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
EP13729277.7A
Other languages
German (de)
English (en)
Inventor
Martin Friedrich
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.)
Beko Technologies GmbH
Original Assignee
Beko Technologies 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 Beko Technologies GmbH filed Critical Beko Technologies GmbH
Publication of EP2856146A1 publication Critical patent/EP2856146A1/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Withdrawn legal-status Critical Current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
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
    • G01N27/4045—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors for gases other than oxygen
    • 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
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0042—SO2 or SO3
    • 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
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0059—Avoiding interference of a gas with the gas to be measured
    • 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
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
    • G01N33/4975—Physical analysis of biological material of gaseous biological material, e.g. breath other than oxygen, carbon dioxide or alcohol, e.g. organic vapours
    • 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
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0037—NOx
    • 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
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/004—CO or CO2
    • 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
    • G01N33/0062—General constructional details of gas analysers, e.g. portable test equipment concerning the measuring method or the display, e.g. intermittent measurement or digital display
    • G01N33/0063—General constructional details of gas analysers, e.g. portable test equipment concerning the measuring method or the display, e.g. intermittent measurement or digital display using a threshold to release an alarm or displaying means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to a measuring device and a method for determining a measured value in a gas stream taking into account cross-sensitivities of the measuring device due to at least one further constituent in the gas stream which disturbs the measured gas.
  • the cross-sensitivity represents the sensitivity of a measuring device to variables other than the measured variable or the measured value, ie the quantity to be measured.
  • a variable that is not a measurable variable but influences the information about the measured value supplied by the measuring device is called influencing variable. It causes the measured value to change simply because the influencing variable changes.
  • Important factors include temperature, humidity, air pressure, electric field or magnetic field.
  • the object of the invention is to provide a measuring device and a method for determining a measured value in a gas stream which at least substantially largely eliminates interfering cross-sensitivities of the measuring device due to at least one further ingredient influencing the measured gas value.
  • the meter should be simple and have a low susceptibility to errors.
  • the object is achieved by a measuring device for determining a measured value in a gas stream taking into account cross-sensitivities of the measuring device due to at least one further constituent disturbing the measured value of the measuring gas in the gas stream which has
  • a device for dividing a source gas stream to be measured into a first sample gas stream and a second sample gas stream
  • a sensor element with a sensor for determining the measured value
  • the sensor element is alternately supplied with the first sample gas stream or the modified second sample gas stream for determining a first intermediate measured value in the first sample gas stream and for determining an intermediate measured value in the second sample gas stream
  • the evaluation unit calculates the final measured value on the basis of the two intermediate measurement results.
  • the object is achieved by a method for determining a content of a measurement gas in a gas stream taking into account cross-sensitivities of the measuring device due to at least one further content of the measurement gas disturbing further ingredient in the gas stream, which is characterized by the method steps,
  • the original gas stream to be measured is divided into a first sample gas stream and a second sample gas stream.
  • the splitting of the original gas stream can be done by an actual physical splitting, for example by means of a separator, alternatively, the source gas stream, for example by means of valves alternately supplied to the sensor element.
  • the invention is based on the assumption that there are two gases in the original gas stream which influence the final measured value via their cross-sensitivity. If, for example, the content of the first gas in the original gas stream is to be determined, the presence of the second gas influences the final measured value, this represents the interfering further ingredient.
  • the invention is based on the idea of first dividing the source gas stream into two sample gas streams and influencing one of the sample gas streams by changing an influencing variable influencing the content of the sample gas.
  • two measurements can be performed with only one sensor element, which leads to different results.
  • the change of the second measuring gas flow is known, for example the measuring gas is reduced or completely removed, the real measured value can be calculated from the two intermediate measured values.
  • the invention is particularly suitable for a measuring device for the determination of sulfur dioxide (SO 2 ) in a measuring gas in which nitrogen dioxide (NO 2 ) is also contained.
  • a sulfur dioxide sensor has a strong cross-sensitivity to nitrogen dioxide. It is particularly difficult that the sensor for both gases in about the same amount of sensitivity, but the output at Nitrogen dioxide is negative. If the same proportion of sulfur dioxide and nitrogen dioxide is present in the sample gas, the output signal is approximately 0.
  • Sulfur dioxide dissolves almost completely in water and is practically completely removed after passing through a moistening element, preferably in conjunction with a membrane, for example a hollow fiber bundle (membrane moistener), which is lapped with water.
  • a moistening element preferably in conjunction with a membrane, for example a hollow fiber bundle (membrane moistener), which is lapped with water.
  • Nitrogen dioxide on the other hand, does not dissolve in water, so it is still completely present at the outlet of the humidifying element.
  • the first sample gas stream is fed directly to the sensor element, the second sample gas stream only after passing through the moistening element.
  • One important advantage of the invention is, inter alia, that assuming that, apart from nitrogen dioxide, no further gases are present in the measurement gas, to which the sulfur dioxide sensor has a cross-sensitivity, the sulfur dioxide sensor can also be used as a nitrogen dioxide sensor or measuring cell can. This results in a significant reduction in costs and maintenance over the life of the meter.
  • the gas humidification by means of the membrane humidifier with hollow fiber membranes is particularly advantageous for the field of respiratory gas measurement.
  • One Such membrane humidifier is inexpensive to produce and works very reliably over long lifetimes. Added to this is its low specific weight.
  • the hollow fiber bundle is advantageously lapped with water that softens, for example, via a mixed-bed cartridge before it enters the membrane humidifier in order to avoid lime deposits in the membrane humidifier.
  • the water supply can be cyclically released, for example, every hour for about 10 seconds.
  • the wastewater is discharged into the sewage system.
  • the moistening takes place according to the invention at about 2 bar overpressure.
  • the moisture at the outlet is almost 100% relative humidity at 2 bar overpressure.
  • a relative humidity of approx. 40% relative humidity is established.
  • the measuring device can be calibrated by means of at least one, preferably two reference gases, which are provided via external compressed gas cylinders. It is both a slope correction, an offset correction, as well as a combined slope and offset correction possible.
  • the sample gas is switched off via valves and simultaneously switched over to one of the reference gases, which act as calibration gases.
  • the others During the calibration process it is thus possible to switch between humidified and dry reference gas.
  • the sensor element has further sensors with which, for example, in addition to the content of nitrogen dioxide and sulfur dioxide, the content of carbon monoxide, nitrogen monoxide, carbon dioxide and oxygen can be determined. Also for these sensors, the possibility can be provided to calibrate them with reference gas.
  • the carbon dioxide sensor has a low moisture dependency. Therefore, this sensor is operated according to the invention only with dry sample gas. In contrast, the electrochemical gas sensors must not only be operated with dry air, otherwise the electrolyte will dry out. The carbon monoxide, the Nitrogen dioxide and oxygen sensors are therefore always operated with humidified air. Since these gases do not dissolve in water, the measured value is not distorted by the humidification.
  • Sulfur dioxide dissolves in water and is therefore almost completely absorbed by the gas as it passes through the humidifying element. Therefore, valves are cyclically switched between dry and humidified sample gas. On average, in this embodiment, the sensor element reaches a measured value of about 20% relative humidity, which is sufficient to prevent the cells from drying out over the operating period.
  • an oxygen volume calculation takes place, the partial pressure dependence being corrected by the measured ambient pressure. This additionally improves the measuring accuracy, since the output signal of the measuring cell (current signal) is a function of the 02 partial pressure.
  • the moisture dependency of the oxygen volume calculation (vol%) is compensated by the measured ambient humidity. This also improves the measurement accuracy, since the output signal of the oxygen measuring cell (current signal) has a relatively significant dependence on the relative gas humidity.
  • the meter has an amperiometric, lead-free oxygen measuring cell, which has a very long life expectancy.
  • the commonly used sensor element is, in principle, a lead-air galvanic cell in which the lead electrode is consumed by the measurement of the oxygen.
  • the life expectancy of the lead cell is strongly dependent on the partial pressure of oxygen and the temperature, as well as on the storage time and the storage conditions (storage under exclusion of air).
  • the amperiometric measuring cell does not have these disadvantages, the cell is not consumed because the electrolyte is restored by the reaction at the counter electrode.
  • a carbon dioxide volume calculation takes place in which the partial pressure dependence is corrected by the measured ambient pressure.
  • the operating principle of the carbon dioxide sensor is an optical one NDIR measuring method.
  • the absorption of the I R light depends on the density of the gas (ie the partial pressure).
  • the TCO Temporal Compensation Offset
  • the TCO Temporal Compensation Offset of the amperiometric measuring cells (except for the oxygen measurement) is corrected by a fourth electrode. Only by optimizing the measuring cell and measuring the zero level in the electrolyte can it be possible to achieve the required measuring accuracy.
  • the TCG (Temperature Compensation Gain) of the amperiometric measuring cells is calibrated in the application temperature range. This is done by measuring or calibrating the gas concentration in the range of the limit values at several different temperatures and mathematical correction.
  • a correction value can be determined in relation to the factory calibration. About the amount of the correction value can make a statement about the aging of the measuring cell and initiate a service request. By this method, it is possible to detect the aging state of the cell. Despite the aging and the reduced sensitivity, correct values are measured again after calibration of the slope. Thus, it is possible to optimize the maintenance intervals.
  • a self-test of the device is carried out.
  • the self-test checks all gas paths and volume flows. This is an important feature to increase the reliability of the device. In the case of a sealed gas path, the measuring cells would not give an alarm when the limit values were exceeded and the error would not be detected.
  • the humidification is permanently monitored. If the humidification fails, the gas paths are shut off to protect the measuring cells, which otherwise would dry out after a few hours of dry operation. Also by this measure, the reliability of the device is increased because a dried measuring cell provides a zero signal and thus the safe alarm would not be guaranteed. In addition, dry operation would cause considerable damage.
  • operation via a water tank is possible in order to be independent of an external water supply. The water level in the tank is ideally monitored and a low level service request is made. This possibility of water supply, the customer has lower installation costs, if there is no water supply in the vicinity of the device.
  • the service intervals are also monitored according to the invention and a service request is signaled to the outside. For reasons of operational safety, regular maintenance is indispensable.
  • the automatic monitoring of the service interval prevents failure of the device due to forgotten maintenance.
  • the measuring range up to -60C td, f is guaranteed.
  • the polymer sensor can only guarantee reliable measurement results up to about -40 C td, f. Especially at high operating temperatures, the measurement accuracy of a polymer sensor is not sufficient.
  • the meter has an internal data logger for recording the measurement data.
  • an internal event logger for recording events is installed. This feature enables analysis of hidden errors or occurred errors between service intervals.
  • FIG. 1 shows a first simplified functional representation of a measuring device according to the invention
  • FIG. 1 shows a schematic representation of the essential elements of a measuring device 20 according to the invention.
  • This device has a sensor element 22 with various sensors.
  • a source gas stream 26 is divided by gas lines and by means of valves 27 into a first sample gas stream 38 and a second sample gas stream 39. In the embodiment shown, the distribution of the original gas stream takes place
  • the first sample gas stream 38 is fed directly to the sensor element 22, the second sample gas stream 39, however, first a humidification, preferably a membrane humidifier 28.
  • the membrane humidifier 28 has a water connection 30 and a water outlet 32. Subsequently, the humidified second gas stream 39 also reaches the sensor element 22 via a valve
  • the water supply can be cyclically released, for example, every hour for about 10 seconds.
  • the amount of water is about 100 ml.
  • the annual consumption is therefore only about 876 liters.
  • a not shown mixed bed cartridge is designed for this amount of water and relatively small with about 200 ml volume.
  • the sensor element comprises various sensors, including a sulfur dioxide sensor 34 (S02 sensor), a nitrogen monoxide sensor 36 (NO sensor), a nitrogen dioxide sensor 42 (N0 2 sensor), a carbon monoxide sensor 44 (CO sensor), an oxygen sensor (0 2 sensor) 46, a temperature sensor 48 and a carbon dioxide sensor 50 (C0 2 sensor).
  • a sulfur dioxide sensor 34 S02 sensor
  • NO sensor nitrogen monoxide sensor
  • N0 2 sensor nitrogen dioxide sensor 42
  • CO sensor carbon monoxide sensor 44
  • oxygen sensor (0 2 sensor) 46 a temperature sensor 48
  • C0 2 sensor 50 carbon dioxide sensor 50
  • the sulfur dioxide sensor 34 in contrast to the embodiment shown on the assumption that except nitrogen dioxide in the sample gas no other gases available are the, to which the sulfur dioxide sensor 34 has a cross sensitivity, the sulfur dioxide sensor 34 also determine the content of nitrogen, the nitrogen dioxide sensor 42 can then be omitted.
  • the nitrogen dioxide sensor 42 is more selective than the sulfur dioxide sensor 34 and has advantages in principle.
  • the selectivity is not absolutely necessary, so that the measured value of the sulfur dioxide sensor 34 humidified gas flow both for the nitrogen dioxide compensation of Sulfur dioxide measured value, as well as for the nitrogen dioxide measurement can be used.
  • the condition in this case is that the humidifying element removes all of the sulfur dioxide, otherwise the nitrogen dioxide reading would be falsified by the amount of residual sulfur dioxide. According to experimental results, this is the case.
  • the first sample gas stream 38 is fed to the sulfur dioxide sensor 34, the nitrogen monoxide sensor 36 and the carbon dioxide sensor 50.
  • the second sample gas stream 39 is supplied to the sulfur dioxide sensor 34, the nitrogen monoxide sensor 36, and the other sensors except for the carbon dioxide sensor 50.
  • the measuring device 20 can be calibrated by means of two reference gas streams 52, 54, which are provided via external compressed gas cylinders.
  • the measuring device 20 has a plurality of throttles 56.
  • FIG. 2 shows a second variant of the invention. This differs from the variant of FIG. 1 in that the sulfur dioxide sensor 34 and the nitrogen monoxide sensor 36 are operated in a dry / damp-timed manner,
  • the carbon dioxide measurement is performed separated.

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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)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Molecular Biology (AREA)
  • Biomedical Technology (AREA)
  • Hematology (AREA)
  • Urology & Nephrology (AREA)
  • Biophysics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Investigating Or Analyzing Materials By The Use Of Magnetic Means (AREA)
  • Measuring Volume Flow (AREA)

Abstract

L'invention concerne un appareil de mesure (20) pour la détermination d'une valeur de mesure dans un courant de gaz tenant compte de la sensibilité du dispositif de mesure aux influences parasites par suite d'au moins un autre constituant perturbant dans le courant de gaz la valeur de mesure du gaz à mesurer. L'appareil de mesure comporte : - un dispositif pour répartir un courant du gaz d'origine (26) à mesurer en un premier courant de gaz à mesurer (38) et en un deuxième courant de gaz à mesurer (39); - un dispositif pour modifier la teneur en gaz à mesurer dans le deuxième courant de gaz à mesurer (39) par variation d'une grandeur d'influence influençant la teneur du gaz à mesurer; - un élément capteur (22) doté d'un capteur pour la détermination de la valeur de mesure; - une unité d'évaluation pour évaluer les valeurs de mesure, sachant que - l'élément capteur (22) reçoit alternativement le premier courant de gaz (38) ou le deuxième courant de gaz (39) modifié pour la détermination d'une première valeur de mesure intermédiaire dans le premier courant de gaz (38) et pour la détermination d'une valeur de mesure intermédiaire dans le deuxième courant de gaz (39), l'unité d'évaluation calculant la valeur de mesure définitive sur la base des deux résultats de mesure intermédiaires. En outre, l'invention concerne un procédé correspondant pour la détermination d'une valeur de mesure dans un courant de gaz.
EP13729277.7A 2012-05-30 2013-05-29 Appareil de mesure et procédé pour appréhender la proportion d'hydrocarbures dans des gaz et tenant compte de la sensibilité aux influences parasites Withdrawn EP2856146A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012010613 2012-05-30
PCT/EP2013/061130 WO2013178714A1 (fr) 2012-05-30 2013-05-29 Appareil de mesure et procédé pour appréhender la proportion d'hydrocarbures dans des gaz et tenant compte de la sensibilité aux influences parasites

Publications (1)

Publication Number Publication Date
EP2856146A1 true EP2856146A1 (fr) 2015-04-08

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EP13729277.7A Withdrawn EP2856146A1 (fr) 2012-05-30 2013-05-29 Appareil de mesure et procédé pour appréhender la proportion d'hydrocarbures dans des gaz et tenant compte de la sensibilité aux influences parasites

Country Status (8)

Country Link
US (1) US20150136616A1 (fr)
EP (1) EP2856146A1 (fr)
JP (1) JP2015518155A (fr)
KR (1) KR20150022929A (fr)
CN (1) CN104350382A (fr)
BR (1) BR112014029268A2 (fr)
IN (1) IN2014MN02226A (fr)
WO (1) WO2013178714A1 (fr)

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KR20150022929A (ko) 2015-03-04
IN2014MN02226A (fr) 2015-07-17
CN104350382A (zh) 2015-02-11
US20150136616A1 (en) 2015-05-21
JP2015518155A (ja) 2015-06-25
WO2013178714A1 (fr) 2013-12-05
BR112014029268A2 (pt) 2017-06-27

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