JP2004020377A - Catalytic combustion type gas sensor - Google Patents

Catalytic combustion type gas sensor Download PDF

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Publication number
JP2004020377A
JP2004020377A JP2002175622A JP2002175622A JP2004020377A JP 2004020377 A JP2004020377 A JP 2004020377A JP 2002175622 A JP2002175622 A JP 2002175622A JP 2002175622 A JP2002175622 A JP 2002175622A JP 2004020377 A JP2004020377 A JP 2004020377A
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Prior art keywords
gas
catalyst
silicon
combustion type
gas sensor
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JP2002175622A
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Japanese (ja)
Inventor
Takashi Sasaki
佐々木 孝
Tsutomu Eguchi
江口 強
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Honda Motor Co Ltd
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Honda Motor Co Ltd
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Priority to JP2002175622A priority Critical patent/JP2004020377A/en
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Abstract

<P>PROBLEM TO BE SOLVED: To prevent a catalyst from being poisoned by a silicon compound, so as to maintain detection sensitivity for a flammable gas favorably. <P>SOLUTION: This catalytic combustion type gas sensor comprises a gas detecting element deposited with a metal oxide sintered body for carrying the catalyst on a temperature measuring resistor, a compensating element deposited with a metal oxide for carrying no catalyst on the temperature measuring resistor, an electric power source for impressing a fixed voltage to the gas detecting element and the compensating element, and a container for storing the gas detecting element and the compensating element and provided with an inlet of the flammable gas. In the gas sensor, a silicon trap filter containing a material poisoned by silicon or the silicon compound is provided in the inlet of the flammable gas. <P>COPYRIGHT: (C)2004,JPO

Description

【0001】
【発明の属する技術分野】
本発明は、水素ガス等の可燃性ガスを検知する接触燃焼式ガスセンサに関するものである。
【0002】
【従来の技術】
一般的な接触燃焼式ガスセンサとしては、例えば、図2に示すような構成のものが知られている。筒状容器11の各端部には、ベース部12と焼結フィルタ13がそれぞれに配置されている。そして、このベース部12には、筒状容器11の内部に向かって、可燃性ガスを検知する素子等から構成されたブリッジ回路部14が固定され、電源15にこのブリッジ回路部14が接続されている。このブリッジ回路部14には、可燃性ガスに対して活性な触媒を担持した金属酸化物焼結体により白金コイル等の測温抵抗体を覆った構造のガス検知素子と、可燃性ガスに対して活性な触媒を含まない以外はガス検知素子と同様の構造の補償素子とが用いられており、図3に示すように、ガス検知素子21、補償素子22および2つの固定抵抗23,24が各枝辺に組み込まれ、さらに検出部25に接続されたブリッジ回路を構成している。
【0003】
この接触燃焼式ガスセンサには、電源15により一定の電圧が印加されており、可燃性ガスの非存在下においては、ブリッジ回路は平衡が保たれるように設計されているので、検出部25では電流が検出されない。そして、可燃性ガスが焼結フィルタ13から接触燃焼式ガスセンサ内に入り込み、ガス検知素子21に接触すると、可燃性ガスの燃焼が起こり、その燃焼熱により測温抵抗体の電気抵抗値が増加する。これに対し、補償素子22においては、可燃性ガスが接触しても燃焼が起こらず温度変化が生じない。その結果、ブリッジ回路の平衡がくずれて、可燃性ガスの濃度に比例した不平衡電流が検出部25に流れるため、この電流の測定により可燃性ガス濃度を検出することができる。
【0004】
このような接触燃焼式ガスセンサは、環境温度および湿度の影響をほとんど受けることが無く、広い濃度範囲でほぼ直線的に検出でき、可燃性ガス検出の精度および再現性が優れており、さらに、消費電力が小さく、機器を小型化することができるため、各分野に広く利用されている。
【0005】
【発明が解決しようとする課題】
しかしながら、上記の接触燃焼式ガスセンサは、雰囲気中のシリコン化合物、特に、車両に用いた場合には、車両内の様々な部品から飛散してくるシリコン化合物によって検知素子の触媒が被毒され、可燃性ガスの検出感度が低下してしまうという問題を有していた。また、上記のシリコン化合物による被毒は、接触燃焼式ガスセンサへの通電により、触媒で選択的に生じるという問題もあった。
【0006】
したがって、本発明は、シリコン化合物による触媒の被毒を防止し、可燃性ガスの検出感度を良好に維持することが可能な接触燃焼式ガスセンサを提供することを目的としている。
【0007】
【課題を解決するための手段】
本発明の接触燃焼式ガスセンサは、触媒を担持する金属酸化物焼結体を測温抵抗体に付着させてなるガス検知素子と、触媒を担持しない金属酸化物を測温抵抗体に付着させてなる補償素子と、ガス検知素子および補償素子とに一定の電圧を印加する電源と、ガス検知素子および補償素子が収められ、かつ可燃性ガスの入口が設けられた容器と、可燃性ガスの入口に設けられた、シリコンまたはシリコン化合物に被毒される材料を含んだシリコントラップフィルタとからなることを特徴としている。
【0008】
また、本発明の接触燃焼式ガスセンサにおいては、シリコントラップフィルタ中に抵抗体が設けられており、この抵抗体が、ガス検知素子および補償素子と並列に、電源に接続されていることが好ましい。
【0009】
本発明によれば、シリコンまたはシリコン化合物に被毒される材料を含んだシリコントラップフィルタを、可燃性ガスの入口に設けることによって、雰囲気中のシリコン化合物がシリコントラップフィルタにおける触媒の被毒に消費されるため、ガス検知素子における触媒が被毒されることがなく、可燃性ガスの検出感度を良好に維持することができるという効果を奏する。
【0010】
【発明の実施の形態】
以下、本発明の接触燃焼式ガスセンサについてさらに詳細に説明する。
本発明の接触燃焼式ガスセンサにおいては、触媒を担持する金属酸化物焼結体の担体を測温抵抗体に付着させてなるガス検知素子と、触媒を担持しない金属酸化物を測温抵抗体に付着させてなる補償素子とが用いられている。これらの素子に用いられる金属酸化物としては、アルミナまたはゼオライトから選ばれた少なくとも1種類が挙げられるが、同じ金属酸化物である必要はない。また、ガス検知素子に用いられる触媒としては、検出する可燃性ガスの種類によって、白金、ルテニウム、およびロジウムの群から適宜選択することが好ましい。
【0011】
上記のガス検知素子および補償素子を作製する方法としては、例えば、まず、直径60μmの白金線を、外径0.6mmに10回巻いて長さ1.5mmのコイルを作製する。次いで、この白金コイルに、アルミナのペーストを付着させ、800℃で焼成して白金コイルにアルミナ担体を固着させることにより、補償素子が作製される。次に、このアルミナ焼結担体を塩化白金酸水溶液に浸漬し、引き上げた後、600℃で加熱分解して白金触媒をアルミナ焼結担体に担持させることにより、ガス検知素子が作製される。
【0012】
上記のようにして得られたガス検知素子および補償素子は、前述したように、2つの固定抵抗とともに、電源により一定の電圧が印加された状態で平衡が保たれたブリッジ回路を構成し、本発明の接触燃焼式ガスセンサが形成される。この接触燃焼式ガスセンサにおいては、焼結フィルタからセンサ内部に可燃性ガスが入り込み、ガス検知素子に接触すると、触媒の存在により燃焼され、その燃焼熱により測温抵抗体の電気抵抗値を増加させる。一方、補償素子には触媒が含まれていないため、可燃性ガスが接触しても燃焼が起こらない。その結果、ブリッジ回路における平衡がくずれ、この時可燃性ガスの濃度に比例して生じる不平衡電流によって、可燃性ガス濃度が検出される。
【0013】
ここで、本発明の接触燃焼式ガスセンサは、図1に示すように、ガス検知素子および補償素子等からなるブリッジ回路14が収められ、かつ可燃性ガスの入口部に焼結フィルタ13を設けた筒状容器11からなり、この焼結フィルタ上に、シリコントラップフィルタ16が設けられている。このシリコントラップフィルタ16は、シリコンまたはシリコン化合物に被毒される材料を含んで形成され、ポーラス状に構成されている。そして、本発明の接触燃焼式ガスセンサ内に入り込む全てのガスは、このトラップフィルタ16を通過するため、ガス検知素子における触媒を被毒し得るシリコン化合物がこのシリコントラップフィルタ16における触媒の被毒に消費される。そのため、本発明の接触燃焼式ガスセンサ内にシリコン化合物17が入り込むことを防止することができ、ガス検知素子における触媒が被毒されることがなく、可燃性ガスの検出感度を良好に維持することができる。
【0014】
また、本発明の接触燃焼式ガスセンサにおけるシリコントラップフィルタ16には、導電線18等の通電機能を備えることが好ましい。このようにして、シリコントラップフィルタ16を通電させ、温度を上げることにより、シリコントラップフィルタ16における触媒を通電状態のガス検知素子における触媒とほぼ同等の環境条件とし、トラップフィルタ16における触媒の被毒をさらに促進することができ、ガス検知素子における触媒を被毒し得るシリコン化合物を確実に捉えることができる。
【0015】
本発明の接触燃焼式ガスセンサは、このような特徴を有するものであれば、図1に示した構成に限定されるものではなく、一般公知の接触燃焼式ガスセンサの構成に適用することも可能である。
【0016】
【発明の効果】
以上説明したように、本発明の接触燃焼式ガスセンサによれば、シリコンまたはシリコン化合物に被毒される材料を含んだシリコントラップフィルタを可燃性ガスの入口に設けることによって、雰囲気中のシリコン化合物がシリコントラップフィルタにおける触媒の被毒に消費されるため、ガス検知素子における触媒が被毒されることがなく、可燃性ガスの検出感度を良好に維持することができる。
【図面の簡単な説明】
【図1】本発明の接触燃焼式ガスセンサの一例の構成を模式的に示した図である。
【図2】従来の接触燃焼式ガスセンサの一例を模式的に示した図である。
【図3】接触燃焼式ガスセンサのブリッジ回路を示した図である。
【符号の説明】
11…筒状容器、12…ベース、13…焼結フィルタ、14…ブリッジ回路部、15…電源、16…シリコントラップフィルタ、
17…トラップされたシリコン化合物、18…導電線、21…ガス検知素子、
22…補償素子、23,24…固定抵抗、25…検出部。
[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a catalytic combustion type gas sensor for detecting a flammable gas such as hydrogen gas.
[0002]
[Prior art]
As a general contact combustion type gas sensor, for example, one having a configuration as shown in FIG. 2 is known. At each end of the cylindrical container 11, a base portion 12 and a sintered filter 13 are respectively arranged. A bridge circuit section 14 composed of an element for detecting a flammable gas or the like is fixed to the base section 12 toward the inside of the cylindrical container 11. The bridge circuit section 14 is connected to a power supply 15. ing. The bridge circuit section 14 includes a gas detection element having a structure in which a temperature measuring resistor such as a platinum coil is covered with a metal oxide sintered body carrying a catalyst active for combustible gas, and a gas detection element for combustible gas. A compensating element having the same structure as that of the gas detecting element except that it does not contain an active catalyst is used. As shown in FIG. 3, a gas detecting element 21, a compensating element 22, and two fixed resistors 23 and 24 are used. A bridge circuit is incorporated in each branch and further connected to the detection unit 25.
[0003]
Since a constant voltage is applied to this contact combustion type gas sensor by the power supply 15 and the bridge circuit is designed so that the equilibrium is maintained in the absence of combustible gas, the detection unit 25 No current is detected. When the combustible gas enters the contact combustion type gas sensor from the sintering filter 13 and comes into contact with the gas detection element 21, combustion of the combustible gas occurs, and the heat of combustion increases the electric resistance value of the temperature measuring resistor. . On the other hand, in the compensating element 22, even if the combustible gas comes into contact, combustion does not occur and no temperature change occurs. As a result, the equilibrium of the bridge circuit is lost, and an unbalanced current proportional to the concentration of the combustible gas flows to the detection unit 25, so that the concentration of the combustible gas can be detected by measuring this current.
[0004]
Such a contact combustion type gas sensor is almost unaffected by the environmental temperature and humidity, can detect almost linearly in a wide concentration range, has excellent accuracy and reproducibility of combustible gas detection, and further has a high consumption efficiency. Since the power is small and the device can be miniaturized, it is widely used in various fields.
[0005]
[Problems to be solved by the invention]
However, in the above-mentioned catalytic combustion type gas sensor, the catalyst of the sensing element is poisoned by the silicon compound in the atmosphere, particularly when used in a vehicle, the silicon compound scattered from various parts in the vehicle, and the flammable gas is burned. There is a problem that the detection sensitivity of the reactive gas is reduced. Further, there is also a problem that the poisoning by the silicon compound is selectively generated by the catalyst when the catalytic combustion type gas sensor is energized.
[0006]
Accordingly, an object of the present invention is to provide a catalytic combustion type gas sensor capable of preventing poisoning of a catalyst by a silicon compound and maintaining good detection sensitivity of combustible gas.
[0007]
[Means for Solving the Problems]
The catalytic combustion type gas sensor of the present invention comprises a gas sensing element formed by attaching a catalyst-carrying metal oxide sintered body to a resistance temperature detector, and a metal oxide not carrying a catalyst attached to a resistance temperature detector. A compensating element, a power supply for applying a constant voltage to the gas detecting element and the compensating element, a container in which the gas detecting element and the compensating element are housed and provided with a combustible gas inlet, and a combustible gas inlet And a silicon trap filter containing a material poisoned by silicon or a silicon compound.
[0008]
In the contact combustion type gas sensor of the present invention, it is preferable that a resistor is provided in the silicon trap filter, and the resistor is connected to a power supply in parallel with the gas detection element and the compensation element.
[0009]
According to the present invention, the silicon compound in the atmosphere is consumed for poisoning of the catalyst in the silicon trap filter by providing the silicon trap filter containing the material poisoned by silicon or the silicon compound at the inlet of the flammable gas. Therefore, there is an effect that the catalyst in the gas detection element is not poisoned, and the detection sensitivity of the combustible gas can be favorably maintained.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the catalytic combustion type gas sensor of the present invention will be described in more detail.
In the catalytic combustion type gas sensor of the present invention, a gas detection element in which a metal oxide sintered body supporting a catalyst is attached to a resistance temperature detector, and a metal oxide not supporting a catalyst is connected to the resistance temperature detector. A compensating element attached is used. Examples of the metal oxide used for these devices include at least one selected from alumina and zeolite, but they need not be the same metal oxide. Further, it is preferable that the catalyst used in the gas detecting element is appropriately selected from the group consisting of platinum, ruthenium, and rhodium depending on the type of the combustible gas to be detected.
[0011]
As a method for manufacturing the above gas detection element and the compensation element, for example, first, a platinum wire having a diameter of 60 μm is wound 10 times around an outer diameter of 0.6 mm to manufacture a coil having a length of 1.5 mm. Next, an alumina paste is adhered to the platinum coil, baked at 800 ° C., and an alumina carrier is fixed to the platinum coil, whereby a compensating element is manufactured. Next, this alumina sintered carrier is immersed in an aqueous chloroplatinic acid solution, pulled up, and then thermally decomposed at 600 ° C. to carry a platinum catalyst on the alumina sintered carrier, thereby producing a gas detection element.
[0012]
As described above, the gas sensing element and the compensating element obtained as described above, together with the two fixed resistors, constitute a balanced bridge circuit in a state where a constant voltage is applied by the power supply, and An inventive catalytic combustion gas sensor is formed. In this contact combustion type gas sensor, a combustible gas enters the inside of the sensor from the sintered filter, and when it comes into contact with the gas detection element, it is burned by the presence of a catalyst, and the heat of combustion increases the electric resistance value of the temperature measuring resistor. . On the other hand, since the compensating element does not include a catalyst, combustion does not occur even if the combustible gas comes into contact. As a result, the equilibrium in the bridge circuit is disrupted, and the concentration of the combustible gas is detected by an unbalanced current generated in proportion to the concentration of the combustible gas.
[0013]
Here, in the catalytic combustion type gas sensor of the present invention, as shown in FIG. 1, a bridge circuit 14 including a gas detecting element and a compensating element is housed, and a sintered filter 13 is provided at an inlet of a combustible gas. It consists of a cylindrical container 11, and a silicon trap filter 16 is provided on this sintered filter. The silicon trap filter 16 is formed to contain a material poisoned by silicon or a silicon compound, and is configured in a porous shape. Since all the gas entering the catalytic combustion type gas sensor of the present invention passes through the trap filter 16, the silicon compound which can poison the catalyst in the gas detection element is not affected by the poisoning of the catalyst in the silicon trap filter 16. Consumed. Therefore, the silicon compound 17 can be prevented from entering the catalytic combustion type gas sensor of the present invention, the catalyst in the gas detection element is not poisoned, and the detection sensitivity of the combustible gas can be maintained well. Can be.
[0014]
In addition, it is preferable that the silicon trap filter 16 in the contact combustion type gas sensor of the present invention has a function of energizing the conductive wire 18 and the like. In this way, by energizing the silicon trap filter 16 and raising the temperature, the catalyst in the silicon trap filter 16 is made to have almost the same environmental conditions as the catalyst in the energized gas detection element, and the catalyst in the trap filter 16 is poisoned. Can be further promoted, and a silicon compound that can poison the catalyst in the gas detection element can be reliably captured.
[0015]
The contact combustion type gas sensor of the present invention is not limited to the configuration shown in FIG. 1 as long as it has such features, and can be applied to the configuration of a generally known contact combustion type gas sensor. is there.
[0016]
【The invention's effect】
As described above, according to the catalytic combustion type gas sensor of the present invention, the silicon compound in the atmosphere is provided by providing the silicon trap filter containing the material poisoned by silicon or the silicon compound at the inlet of the flammable gas. Since the catalyst is consumed by the poisoning of the catalyst in the silicon trap filter, the catalyst in the gas detecting element is not poisoned, and the detection sensitivity of the flammable gas can be favorably maintained.
[Brief description of the drawings]
FIG. 1 is a diagram schematically showing a configuration of an example of a contact combustion type gas sensor of the present invention.
FIG. 2 is a diagram schematically showing an example of a conventional catalytic combustion type gas sensor.
FIG. 3 is a diagram showing a bridge circuit of the catalytic combustion type gas sensor.
[Explanation of symbols]
11 ... cylindrical container, 12 ... base, 13 ... sintered filter, 14 ... bridge circuit part, 15 ... power supply, 16 ... silicon trap filter,
17: trapped silicon compound, 18: conductive wire, 21: gas detection element,
22: compensating element, 23, 24: fixed resistance, 25: detecting section.

Claims (2)

触媒を担持する金属酸化物焼結体を測温抵抗体に付着させてなるガス検知素子と、
触媒を担持しない金属酸化物を測温抵抗体に付着させてなる補償素子と、
前記ガス検知素子および前記補償素子とに一定の電圧を印加する電源と、
前記ガス検知素子および前記補償素子が収められ、かつ可燃性ガスの入口が設けられた容器と、
前記可燃性ガスの入口に設けられた、シリコンまたはシリコン化合物に被毒される材料を含んだシリコントラップフィルタとからなることを特徴とする接触燃焼式ガスセンサ。
A gas detection element formed by attaching a metal oxide sintered body carrying a catalyst to a resistance temperature detector,
A compensating element formed by attaching a metal oxide that does not carry a catalyst to the resistance temperature detector,
A power supply for applying a constant voltage to the gas detection element and the compensation element;
A container in which the gas detection element and the compensation element are housed, and in which a combustible gas inlet is provided;
A contact combustion type gas sensor, comprising: a silicon trap filter provided at an inlet of the combustible gas and containing a material poisoned by silicon or a silicon compound.
前記シリコントラップフィルタ中には、抵抗体が設けられており、この抵抗体は、前記ガス検知素子および前記補償素子と並列に、電源に接続されていることを特徴とする請求項1に記載の接触燃焼式ガスセンサ。2. The silicon trap filter according to claim 1, wherein a resistor is provided in the silicon trap filter, and the resistor is connected to a power supply in parallel with the gas detection element and the compensation element. Contact combustion type gas sensor.
JP2002175622A 2002-06-17 2002-06-17 Catalytic combustion type gas sensor Pending JP2004020377A (en)

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WO2006090433A1 (en) * 2005-02-22 2006-08-31 Fis Inc. Hydrogen gas sensor and process for producing the same
WO2007097025A1 (en) * 2006-02-27 2007-08-30 Fis Inc. Hydrogen gas sensor
JP2008249494A (en) * 2007-03-30 2008-10-16 Fis Inc Hydrogen gas sensor
DE102007054340A1 (en) 2007-11-14 2009-05-28 Rational Ag Cooking device for cooking food, has mesoporous filter made of material consisting of silicon oxide and/or silicate for selectively filtering gaseous silicon connections from sample gas of space atmosphere using filter
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JP5044540B2 (en) * 2006-02-27 2012-10-10 エフアイエス株式会社 Hydrogen gas sensor
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WO2011145492A1 (en) * 2010-05-17 2011-11-24 本田技研工業株式会社 Catalytic combustion type gas sensor
JPWO2011145492A1 (en) * 2010-05-17 2013-07-22 本田技研工業株式会社 Contact combustion type gas sensor
CN102914562A (en) * 2011-08-02 2013-02-06 日立汽车系统株式会社 Hydrogen sensing device
CN110865100A (en) * 2019-12-18 2020-03-06 中国电子科技集团公司第四十九研究所 Sheet-type structure integrated catalytic combustion type combustible gas sensor and preparation method thereof

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