WO2007096203A1 - Détecteur de gaz - Google Patents
Détecteur de gaz Download PDFInfo
- Publication number
- WO2007096203A1 WO2007096203A1 PCT/EP2007/050129 EP2007050129W WO2007096203A1 WO 2007096203 A1 WO2007096203 A1 WO 2007096203A1 EP 2007050129 W EP2007050129 W EP 2007050129W WO 2007096203 A1 WO2007096203 A1 WO 2007096203A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- gas
- gas sensor
- sensor according
- electrode
- Prior art date
Links
- 239000007789 gas Substances 0.000 claims abstract description 93
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005259 measurement Methods 0.000 claims abstract description 26
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004020 conductor Substances 0.000 claims abstract description 14
- 230000004888 barrier function Effects 0.000 claims abstract description 10
- 238000009792 diffusion process Methods 0.000 claims abstract description 10
- 238000005086 pumping Methods 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
- 239000010931 gold Substances 0.000 claims description 12
- -1 hydrogen ions Chemical class 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 6
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 108010083687 Ion Pumps Proteins 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
- G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
-
- 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
- G01N27/416—Systems
- G01N27/417—Systems using cells, i.e. more than one cell and probes with solid electrolytes
- G01N27/419—Measuring voltages or currents with a combination of oxygen pumping cells and oxygen concentration cells
-
- 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
- G01N33/0054—Ammonia
-
- 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 gas sensor for determining a hydrogen-containing gas component and / or its concentration in a measuring gas, according to the preamble of claim 1.
- EP 0 693 180 B1 discloses an ammonia sensor which operates on an amperometric basis, wherein a membrane permeable to ammonia seals off the sensor to form a sample gas sample.
- the electrolyte contains a metal ion which is not oxidizable by atmospheric oxygen in aqueous solution and which forms a complex, oxygen-oxidizable metal ion with ammonia.
- This sensor is designed for room temperature and / or aqueous solutions. Its field of application is accordingly limited.
- WO 01/48466 A2 discloses a sensor element of a gas sensor for determining the concentration of hydrogen present in a gas mixture or of hydrogen-containing gas components such as ammonia or hydrocarbons.
- an emf caused by different hydrogen or proton concentration at two measuring or reference electrodes is determined by measuring the applied electrical voltage in the so-called "Nernst cell” operating mode.
- the present invention is based on the object to improve a gas sensor for the determination of hydrogen-containing gas components in a sample gas, in particular NH3 shares, according to the manner outlined in the introduction.
- the invention relates to a gas sensor for determining a hydrogen-containing gas component and / or its concentration in a measurement gas, in particular for the determination of NH 3 , comprising two protons conductively connected by a proton conductor electrodes, wherein between a measurement gas ausiqueden sensor area and a first, with respect to a Splitting the hydrogen-containing gas component catalytically active electrode is disposed a diffusion barrier.
- the gas sensor is characterized in that the proton conductor is connected to the two electrodes as a hydrogen ion pumping cell.
- a pump cell is understood as meaning an amperometrically operated electrolyte contacted via two electrodes. That is, at the two electrodes is a potential difference, and caused by the ion migration through the electrolyte electric current is z. B. detected as a measure of the concentration of hydrogen in the sample gas. The same applies of course to a proton conductor.
- the hydrogen proton conductor formed as a solid may be composed of barium zirconate, in particular of doped barium zirconate.
- the construction of such a gas sensor can be carried out, for example, in the form of a planar sensor element.
- a basic ceramic for example, an yttrium-stabilized zirconia
- the diffusion barrier serves as a gas resistance between the sample gas to be tested for specific proportions and / or concentrations and a sample gas sample chamber. It delimits the sample gas sample chamber from the sensor area to be exposed to the sample gas. In this sensor area, it may be z. B. may be an opening on one side of the sensor.
- the so-called “hydrogen pump” formed from the two electrodes and the hydrogen proton conductor pumps out the hydrogen (H) formed in the splitting of ammonia (NH 3 ) in ionized form (H + ) from the sample gas sample chamber For example, back to the room in which the sample gas to be tested is located, but it would also be conceivable to pump it off in an area which is separate from this room.
- this first electrode may be made of a suitably suitable material, for example of platinum, in particular of pure platinum.
- H total hydrogen content
- a first possible source of error for determining the concentration of the hydrogen fraction in a sensor constructed in this way can be eliminated by providing a first oxygen ion pumping cell, preferably arranged close to the diffusion barrier in the sample gas sample chamber. This ensures the removal of existing in the sample gas, free oxygen molecules, which could otherwise enter into a measurement falsifying binding with hydrogen or would usually.
- a first oxygen ion pumping cell preferably arranged close to the diffusion barrier in the sample gas sample chamber. This ensures the removal of existing in the sample gas, free oxygen molecules, which could otherwise enter into a measurement falsifying binding with hydrogen or would usually.
- ceramic solid electrolyte is provided with two electrodes and acted upon by a corresponding electrical voltage.
- a voltage source can be provided by means of which a pumping voltage (Up) can be applied at least during the measurement process between the two electrodes of the hydrogen ion pump.
- This pumping voltage is preferably designed so that it is selectively parameterized for the splitting of the hydrogen-containing gas component, in particular NH 3 , into hydrogen (H) + one or more complementary components, such as nitrogen (N), at the first electrode.
- the sample gas sample may preferably be parameterized so that it does not cause splitting of water (H 2 O) also present in the sample gas sample in the form of water vapor into oxygen (O) and hydrogen (H 2 ).
- H 2 O water
- O oxygen
- H 2 hydrogen
- Solid electrolyte of yttrium stabilized zirconia by means of the two associated with him two electrodes, inner and outer, are quantified by the resulting ion current or the corresponding electrode current exactly. But this again is an exact quantification of the complementary hydrogen ion current or the associated electron flow to the hydrogen ion pump possible.
- the attached figure shows a schematic cross section through a gas sensor for determining a hydrogen-containing gas component and / or their concentration in a measurement gas, in particular for the determination of NH 3 .
- the attached figure shows a schematic cross section through a gas sensor 1.
- a proton conductor 2 which can be connected via two electrodes 3, 4 to a voltage source 5.
- a diffusion barrier 8 is provided in order to separate a sample gas sample chamber 6 from a sensor region 7 to be exposed to the sample gas.
- this diffusion barrier may have a selective filtering effect, so that only certain gas fractions can pass through it.
- the electrode 3 arranged in the interior of the sample gas sample chamber 6 is preferably catalytically active with respect to a splitting of a hydrogen-containing gas component.
- the proton conductor 2 is connected to the two electrodes 3, 4 as a hydrogen ion pumping cell 9.
- Ceramic bodies (10, 11, 12), preferably yttrium-stabilized zirconia, are provided as carrier bodies for the sensor 1.
- a heating element 13 is inside an insulation 14 embedded. By means of this heating element, the sensor can be adjusted to a specific operating temperature.
- the hydrogen ion pumping cell 9 is arranged in the plane of the layer 11 together with the sample gas sample chamber 6 and the diffusion barrier 8.
- the sensor region 7 to be exposed to the measurement gas is in this case designed, for example, in the end region of the sensor 1. Through it, the test gas to be tested can diffuse across the diffusion barrier 8 into the sample gas sample chamber 6.
- an electric current flowing through the two electrodes 3, 4 is detected as a measure of the concentration of hydrogen ions of the gas component to be detected by the ammeter 15 shown here by way of example.
- a first oxygen-ion pump cell for eliminating such measurement errors. It comprises the ceramic solid-state electrolyte 17 formed as a carrier element as well as the two electrodes 18, 19. The outer electrode 18 is additionally coated with a protective layer 20. For operation of the oxygen-ion pumping cell 16, a current or voltage source 21 is further provided.
- the present invention therefore additionally proposes a second oxygen pumping cell 23 spatially or functionally associated with the sample gas sampling chamber. This is how the Oxygen Ionenpumpzelle 21, an inner electrode 23 and an outer electrode 24, which are conductively connected to each other by an electrolyte oxygen ions.
- this oxygen-ion conducting electrolyte is again produced by the ceramic body in the form of a yttrium-stabilized zirconia, which is designed as a carrier body.
- a protective layer 26 is also shown here by way of example.
- the inner electrode 23 of the second oxygen-ion pumping cell 22 in the vicinity of the inner Electrode 3 of the hydrogen ion pumping cell 9 is arranged.
- these two electrodes face each other in the sample gas sample chamber 6.
- all the oxygen atoms released by the splitting of the water (H 2 O) into (2H) plus (O) can be quantified. This is done by means of the electrons of the corresponding electric current flowing through the amperometer 28 shown here by way of example.
- the measurement error resulting from the splitting of water is known and can be reliably corrected by a corresponding subtraction on the measurement result of the hydrogen ion pump cell. What remains is only the hydrogen ion current, which results from the splitting of the measurement gas component to be detected, such as NH 3 .
- the present invention further provides that the two inner electrodes 19, 23 of the two oxygen-ion pumping cells 16, 22 are constructed from materials which as far as possible do not split the water into Support or cause hydrogen and oxygen fractions. You can do this, for example, from a Blend of platinum (Pt) with about 0.5% gold (Au) or consist of a mixture of palladium (Pd) with about 5, 0% gold (Au).
- the inner electrode 3 of the hydrogen ion pump cell can consist, for example, of pure platinum (Pt), which, as is known, has very good catalytic properties with regard to a splitting of hydrogen-containing gas components.
- the proton conductor 2 may itself be composed of proportions of barium zirconate, in particular of doped barium zirconate. In the present example, this barium zirconate is embedded in an insulation 29 in the form of aluminum oxide (Al 2 O 3).
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
La présente invention concerne un détecteur (1) de gaz destiné à déterminer une composante gazeuse contenant de l'hydrogène et/ou sa concentration dans un gaz de mesure, notamment pour déterminer la présence de NH3, comprenant deux électrodes (3, 4) reliées par un conducteur (2) de protons de manière à conduire les protons, une barrière (8) de diffusion étant disposée entre une zone (7) du détecteur à exposer au gaz de mesure et une première électrode (3) ayant une action catalytique du point de vue de la décomposition de la composante gazeuse contenant de l'hydrogène. Le détecteur de gaz se caractérise en ce que le conducteur (2) de protons est connecté avec les deux électrodes (3, 4) en tant que cellule (5, 15) de pompage d'ions d'hydrogène.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07703682A EP1989539A1 (fr) | 2006-02-22 | 2007-01-08 | Detecteur de gaz |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006008227.3 | 2006-02-22 | ||
| DE102006008227A DE102006008227A1 (de) | 2006-02-22 | 2006-02-22 | Gassensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007096203A1 true WO2007096203A1 (fr) | 2007-08-30 |
Family
ID=37834152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2007/050129 WO2007096203A1 (fr) | 2006-02-22 | 2007-01-08 | Détecteur de gaz |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1989539A1 (fr) |
| DE (1) | DE102006008227A1 (fr) |
| WO (1) | WO2007096203A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018132368A (ja) * | 2017-02-14 | 2018-08-23 | 株式会社Ｓｏｋｅｎ | アンモニアセンサ素子 |
| JP2018146346A (ja) * | 2017-03-03 | 2018-09-20 | 株式会社Ｓｏｋｅｎ | アンモニアセンサ素子 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008056791A1 (de) | 2008-11-11 | 2010-05-12 | Volkswagen Ag | Sensorvorrichtung zum Messen einer Ammoniakkonzentration |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0678740A1 (fr) * | 1994-04-21 | 1995-10-25 | Ngk Insulators, Ltd. | Méthode et dispositif pour mesurer un composant de gaz |
| EP1306666A2 (fr) * | 1995-03-09 | 2003-05-02 | Ngk Insulators, Ltd. | Méthode et appareil pour mesurer un composant de gaz combustible en brûlant le composant |
| US20030221975A1 (en) * | 2002-05-29 | 2003-12-04 | Denso Corporation | Hydrogen-containing gas measurement sensor element and measuring method using same |
| DE10226207A1 (de) * | 2002-06-13 | 2003-12-24 | Volkswagen Ag | Verfahren und Vorrichtung zur Konzentrationsbestimmung einer Methankomponente |
-
2006
- 2006-02-22 DE DE102006008227A patent/DE102006008227A1/de not_active Ceased
-
2007
- 2007-01-08 WO PCT/EP2007/050129 patent/WO2007096203A1/fr active Application Filing
- 2007-01-08 EP EP07703682A patent/EP1989539A1/fr not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0678740A1 (fr) * | 1994-04-21 | 1995-10-25 | Ngk Insulators, Ltd. | Méthode et dispositif pour mesurer un composant de gaz |
| EP1306666A2 (fr) * | 1995-03-09 | 2003-05-02 | Ngk Insulators, Ltd. | Méthode et appareil pour mesurer un composant de gaz combustible en brûlant le composant |
| US20030221975A1 (en) * | 2002-05-29 | 2003-12-04 | Denso Corporation | Hydrogen-containing gas measurement sensor element and measuring method using same |
| DE10226207A1 (de) * | 2002-06-13 | 2003-12-24 | Volkswagen Ag | Verfahren und Vorrichtung zur Konzentrationsbestimmung einer Methankomponente |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018132368A (ja) * | 2017-02-14 | 2018-08-23 | 株式会社Ｓｏｋｅｎ | アンモニアセンサ素子 |
| JP2018146346A (ja) * | 2017-03-03 | 2018-09-20 | 株式会社Ｓｏｋｅｎ | アンモニアセンサ素子 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1989539A1 (fr) | 2008-11-12 |
| DE102006008227A1 (de) | 2007-08-23 |
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| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
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