JP2008164305A - Electrochemical sensor, target gas monitor device, and concentration detection method of electrochemical sensor - Google Patents

Electrochemical sensor, target gas monitor device, and concentration detection method of electrochemical sensor Download PDF

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JP2008164305A
JP2008164305A JP2006350707A JP2006350707A JP2008164305A JP 2008164305 A JP2008164305 A JP 2008164305A JP 2006350707 A JP2006350707 A JP 2006350707A JP 2006350707 A JP2006350707 A JP 2006350707A JP 2008164305 A JP2008164305 A JP 2008164305A
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electrochemical sensor
conductor film
proton conductor
generated
target gas
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Masato Kondo
正登 近藤
Kazu Mochizuki
計 望月
Kaoru Ogino
薫 荻野
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Yazaki Corp
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<P>PROBLEM TO BE SOLVED: To use an electrochemical sensor, even in a narrow space that repeats a temperature change, from the normal temperature to a high temperature. <P>SOLUTION: This electrochemical sensor 1, which has a proton conductor film 13 and is provided in an exhaust cylinder for discharging the combustion exhaust gas produced by the combustion of a combustion device, has a supply part for supplying steam in the exhaust cylinder to the proton conductor film 13 and generates a current corresponding to the concentration of the target gas in the exhaust cylinder in between a detection electrode 13a and a counter electrode 13b due to the oxidation reaction of a target gas in the proton conductive film 13 for utilizing the moisture of the steam produced at the detection electrode 13a of the proton conductive film 13 and supplied from a supply part and the reduction reaction of the proton produced at the counter electrode 13b of the proton conductive film 13 by oxidation reaction. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、一酸化炭素等の対象ガスの濃度を検出する電気化学式センサ、対象ガス監視装置、及び、電気化学式センサの濃度検出方法に関するものである。   The present invention relates to an electrochemical sensor that detects the concentration of a target gas such as carbon monoxide, a target gas monitoring device, and a concentration detection method for the electrochemical sensor.

燃焼機器の不完全燃焼等による一酸化炭素（ＣＯ）ガスの発生を監視する燃焼機器用監視装置やＣＯガスを検出し警報するＣＯ警報器は、従来から電気化学式ＣＯセンサを内蔵したものが知られている。   Conventional monitoring devices for combustion equipment that monitor the generation of carbon monoxide (CO) gas due to incomplete combustion of combustion equipment and CO alarms that detect and alarm CO gas have built-in electrochemical CO sensors. It has been.

図６に断面図で示すように、従来の電気化学式ＣＯセンサ１０１は、内部に水１０５が収容された金属製の容器１０２の上部開口１０４にプロトン導電体膜１０３を設置して、その対極１３２を容器１０２内に露出させると共に、反対側の検知極１３１にガス吸着フィルタ１０７ｃを内蔵した金属製のキャップ１０８を重ねて容器１０２の上部開口１０４にかしめ固定して構成されている。   As shown in a cross-sectional view in FIG. 6, the conventional electrochemical CO sensor 101 has a proton conductor film 103 installed in an upper opening 104 of a metal container 102 containing water 105 therein, and a counter electrode 132 thereof. Is exposed to the inside of the container 102, and a metal cap 108 containing a gas adsorption filter 107 c is overlapped on the opposite detection electrode 131 and is caulked and fixed to the upper opening 104 of the container 102.

上述した構成の電気化学式ＣＯセンサ１０１では、周辺雰囲気中のＣＯが、キャップ１０８の導入孔１０８ａから内部に導入されて、活性炭やシリカゲル、ゼオライト等からなるガス吸着フィルタ１０７ｃや導出孔１０８ｂ、そして、キャップ１０８とプロトン導電体膜１０３との間に介設した拡散防止板１０７の拡散制御孔１０７ａを通過して検知極１３１に到達し、ここで、対極１３２側からプロトン導電体膜１０３に供給される容器１０２内の水１０５の水分を利用した酸化反応を起こして、検知極１３１にプロトン（２Ｈ+）と電子（２ｅ-）を発生させる。 In the electrochemical CO sensor 101 configured as described above, CO in the ambient atmosphere is introduced into the inside through the introduction hole 108a of the cap 108, the gas adsorption filter 107c made of activated carbon, silica gel, zeolite, or the like, the outlet hole 108b, and It passes through the diffusion control hole 107a of the diffusion preventing plate 107 interposed between the cap 108 and the proton conductor film 103 and reaches the detection electrode 131, where it is supplied to the proton conductor film 103 from the counter electrode 132 side. Oxidation reaction using the water in the water 105 in the container 102 is caused to generate protons (2H + ) and electrons (2e − ) at the detection electrode 131.

検知極１３１に発生した電子（２ｅ-）はプロトン導電体膜１０３の内部を通過できないので検知極１３１に滞留し、一方、プロトン（２Ｈ+）は、プロトン導電体膜１０３の内部を通過して対極１３２に移動し、ここで、容器２内の酸素と還元反応を起こして、対極１３２に水（Ｈ2Ｏ）を生成する。 The electrons (2e − ) generated in the detection electrode 131 cannot pass through the proton conductor film 103 and thus stay in the detection electrode 131, while the proton (2H + ) passes through the proton conductor film 103. It moves to the counter electrode 132, where it causes a reduction reaction with oxygen in the container 2 to generate water (H 2 O) at the counter electrode 132.

したがって、検知極１３１と対極１３２との間に負荷（図示せず）を接続すると、検知極１３１に滞留した電子（２ｅ-）の対極１３２に向かう流れが負荷に生じ、これにより対極１３２から負荷を経て検知極１３１に向かう短絡電流の流れが生じるので、この負荷に流れる短絡電流を電流−電圧変換することで、周辺雰囲気中のＣＯ濃度に応じた電圧値のＣＯ濃度信号が得られる（例えば特許文献１，２）。 Therefore, when a load (not shown) is connected between the detection electrode 131 and the counter electrode 132, a flow of electrons (2e − ) staying in the detection electrode 131 toward the counter electrode 132 is generated in the load, thereby causing the load from the counter electrode 132 to load. Since a short-circuit current flows toward the detection electrode 131 through the current, a current-voltage conversion is performed on the short-circuit current flowing through the load to obtain a CO concentration signal having a voltage value corresponding to the CO concentration in the ambient atmosphere (for example, Patent Documents 1 and 2).

このような検出原理の構成による電気化学式ＣＯセンサ１０１は、それ自身では、ＣＯ濃度信号の元となる、周辺雰囲気中のＣＯ濃度に応じた大きさの短絡電流を発生させるために、外部からの電力供給を必要としないことから、電池によって長期間駆動する必要のあるＣＯ警報器での利用に適している。
特開２００４−１７０１０１号公報 特開２００４−２７９２９３号公報 The electrochemical CO sensor 101 having such a detection principle configuration itself generates a short-circuit current having a magnitude corresponding to the CO concentration in the ambient atmosphere, which is a source of the CO concentration signal. Since it does not require power supply, it is suitable for use in a CO alarm device that needs to be driven by a battery for a long period of time.
JP 2004-170101 A JP 2004-279293 A

しかしながら、上述した電気化学式ＣＯセンサは、水分を常に供給する必要があるため、センサ部分の数倍にもなる大きさの容器１０２を設ける必要があり、小型化することが困難であった。そのため、燃焼機器の排気筒等の狭い空間に設置することが困難であり、あらゆるサイズ等の排気筒に設けることができず、使用適合範囲の制約が大きかった。また、排気筒内は常温から２５０度程度の高温を繰り返し変化するため、密閉された水タンクである容器１０２からの水漏れ等の問題も懸念されていた。   However, since the above-described electrochemical CO sensor needs to constantly supply moisture, it is necessary to provide a container 102 that is several times larger than the sensor portion, and it is difficult to reduce the size. Therefore, it is difficult to install it in a narrow space such as an exhaust pipe of a combustion device, and it cannot be provided in an exhaust pipe of any size, so that there are large restrictions on the usable compatibility range. Further, since the inside of the exhaust pipe is repeatedly changed from room temperature to a high temperature of about 250 degrees, there has been a concern about problems such as water leakage from the container 102 which is a sealed water tank.

よって本発明は、上述した問題点に鑑み、常温から高温の温度変化を繰り返す狭い空間内でも使用することができる電気化学式センサ、対象ガス監視装置、及び、電気化学式センサの濃度検出方法を提供することを課題としている。   Therefore, in view of the above-described problems, the present invention provides an electrochemical sensor, a target gas monitoring device, and a method for detecting the concentration of an electrochemical sensor that can be used in a narrow space where temperature changes from room temperature to high temperature are repeated. It is an issue.

上記課題を解決するため本発明によりなされた請求項１記載の電気化学式センサは、プロトン導電体膜を有し、燃焼機器の燃焼によって発生した燃焼排ガスを排出する排気筒内に設けられる電気化学式センサであって、前記排気筒内中の水蒸気を前記プロトン導電体膜に供給する供給部を有し、前記プロトン導電体膜の検知極で発生し且つ前記供給部から供給された水蒸気の水分を利用した前記プロトン導電体膜における対象ガスの酸化反応と、前記プロトン導電体膜の対極で発生し且つ前記酸化反応によって発生したプロトンの還元反応とにより、前記排気筒内の対象ガスの濃度に応じた電流を、前記検知極と前記対極との間に発生するようにしたことを特徴とする。   In order to solve the above-mentioned problems, an electrochemical sensor according to claim 1 according to the present invention has a proton conductor film and is provided in an exhaust cylinder for discharging combustion exhaust gas generated by combustion of combustion equipment. And having a supply part for supplying water vapor in the exhaust pipe to the proton conductor film, and utilizing the moisture of the water vapor generated at the detection electrode of the proton conductor film and supplied from the supply part In accordance with the concentration of the target gas in the exhaust pipe, the oxidation reaction of the target gas in the proton conductor film and the reduction reaction of the proton generated at the counter electrode of the proton conductor film and generated by the oxidation reaction An electric current is generated between the detection electrode and the counter electrode.

上記課題を解決するため本発明によりなされた請求項２記載の対象ガス監視装置は、請求項１に記載の電気化学式センサを有し、前記電気化学式センサの前記検知極と前記対極との間に発生する電流を監視して対象ガスの発生を監視することを特徴とする。   The object gas monitoring device according to claim 2, which has been made according to the present invention in order to solve the above problem, has the electrochemical sensor according to claim 1, and is provided between the detection electrode and the counter electrode of the electrochemical sensor. The generation of the target gas is monitored by monitoring the generated current.

上記課題を解決するため本発明によりなされた請求項３記載の電気化学式センサの濃度検出方法は、プロトン導電体膜を有する電気化学式センサの濃度検出方法であって、燃焼機器の燃焼によって発生した燃焼排ガスを排出する排気筒内に設けられ、前記排気筒内中の水蒸気を前記プロトン導電体膜に供給し、前記プロトン導電体膜の検知極で発生し且つ前記供給部から供給された水蒸気の水分を利用した前記プロトン導電体膜における対象ガスの酸化反応と、前記プロトン導電体膜の対極で発生し且つ前記酸化反応によって発生したプロトンの還元反応とにより、前記排気筒内の対象ガスの濃度に応じた電流を前記検知極と前記対極との間に発生することを特徴とする。   The method for detecting the concentration of an electrochemical sensor according to claim 3, which has been made in accordance with the present invention to solve the above-mentioned problem, is a method for detecting the concentration of an electrochemical sensor having a proton conductor film, which is a combustion generated by combustion of a combustion device. Moisture of water vapor provided in an exhaust pipe for discharging exhaust gas, supplying water vapor in the exhaust pipe to the proton conductor film, generated at a detection electrode of the proton conductor film, and supplied from the supply unit The concentration of the target gas in the exhaust pipe is reduced by the oxidation reaction of the target gas in the proton conductor film using the oxygen and the reduction reaction of the proton generated at the counter electrode of the proton conductor film and generated by the oxidation reaction. A corresponding current is generated between the detection electrode and the counter electrode.

以上説明したように請求項１，３に記載した本発明によれば、排気筒内の水蒸気をプロトン導電体膜に供給する供給部を設け、その水蒸気の水分を利用して検知極に酸化反応を発生させ且つ対極に還元反応を発生させることで、検知極と対極との間に対象ガスの濃度に応じた電流を発生するようにしたことから、従来の水タンクを不要とすることができる。また、密閉された水タンクを有していないことから、水漏れ等の問題もなくなり、給湯器の排気筒等の常温から高温を繰り返す空間内にも設置することができる。従って、電気化学式センサを小型化でき且つ水漏れ等の問題も解消できるため、給湯器の排気筒等の狭く厳しい空間でも設置することが可能なり、使用適合範囲の制約を低減させることができる。   As described above, according to the first and third aspects of the present invention, the supply portion for supplying the water vapor in the exhaust pipe to the proton conductor film is provided, and the oxidation reaction is performed on the detection electrode using the water content of the water vapor. By generating a reduction reaction at the counter electrode and generating a current according to the concentration of the target gas between the detection electrode and the counter electrode, a conventional water tank can be eliminated. . In addition, since it does not have a sealed water tank, there is no problem of water leakage and the like, and it can be installed in a space that repeats from normal temperature to high temperature such as an exhaust pipe of a water heater. Therefore, since the electrochemical sensor can be reduced in size and problems such as water leakage can be solved, it can be installed in a narrow and severe space such as an exhaust pipe of a water heater, and the restriction on the usable range can be reduced.

以上説明したように請求項２に記載した本発明の対象ガス監視装置によれば、排気筒内の水蒸気の水分を利用することで、使用適合範囲の制約を低減した電気化学式センサの検知極と対極との間に発生する電流を監視して対象ガスの発生を監視するようにしたことから、給湯器の排気筒の常温から高温を繰り返す空間内等における対象ガスの発生を監視することができる。従って、電気化学式センサをより所望の箇所に設置して対象ガスを監視することができるため、監視精度の向上に貢献することができる。   As described above, according to the target gas monitoring device of the present invention described in claim 2, by using the moisture of the water vapor in the exhaust pipe, the detection electrode of the electrochemical sensor that reduces the limitation of the usable compatibility range, Since the generation of the target gas is monitored by monitoring the current generated between the counter electrode, the generation of the target gas can be monitored in a space where the exhaust pipe of the water heater repeats from normal temperature to high temperature. . Accordingly, the target gas can be monitored by installing the electrochemical sensor at a more desired location, which can contribute to improvement in monitoring accuracy.

以下、本発明に係る電気化学式センサの一実施の形態を、図１〜図５の図面を参照して説明する。   Hereinafter, an embodiment of an electrochemical sensor according to the present invention will be described with reference to the drawings of FIGS.

図１に示す電気化学式センサ１は、ハウジングとしての陰極１２と、プロトン導電体膜１３と、取込部材１４と、上述した拡散防止板１７と、を有している。電気化学式センサ１は、図３に示すように、例えば略ボタン電池と同様の形状に形成されている。   The electrochemical sensor 1 shown in FIG. 1 includes a cathode 12 as a housing, a proton conductor film 13, an intake member 14, and the diffusion prevention plate 17 described above. As shown in FIG. 3, the electrochemical sensor 1 is formed, for example, in a shape substantially similar to that of a button battery.

陰極１２は、底部１２ａと、該底部１２の縁部から図１中上方に向かって立設する側壁１２ｂと、側壁１２ｂの端部から底部１２ａに対して平行且つ底部１２ａの周縁の一部を覆うように連接する連接部１２ｃと、を有し、導電性部材で形成している。該連接部１２ｃは、底部１２ａと対向する開口１２ｄを形成している。即ち、陰極１２が、プロトン導電体膜１３、取込部材１４等の他の部材を収容する収容部材（ハウジング）として機能している。   The cathode 12 includes a bottom portion 12a, a side wall 12b erected upward from the edge of the bottom portion 12 in FIG. 1, and a part of the periphery of the bottom portion 12a parallel to the bottom portion 12a from the end of the side wall 12b. And a connecting portion 12c that is connected so as to be covered, and is formed of a conductive member. The connecting portion 12c forms an opening 12d that faces the bottom portion 12a. That is, the cathode 12 functions as a housing member (housing) that houses other members such as the proton conductor film 13 and the capturing member 14.

プロトン導電体膜１３は、検知極１３ａと、対極１３ｂと、を有している。プロトン導電体膜１３は、拡散防止板１７よりも小さな略円盤状に形成している。プロトン導電体膜１３は、対極１３ｂと陰極１２の底部１２ａの内面が接した状態で底部１２ａ上に設けられることで、対極１３ｂと陰極１２と電気的に接続している。そして、プロトン導電体膜１３の検知極１３ａ上には、拡散防止板１７を積層している。   The proton conductor film 13 has a detection electrode 13a and a counter electrode 13b. The proton conductor film 13 is formed in a substantially disk shape smaller than the diffusion preventing plate 17. The proton conductor film 13 is electrically connected to the counter electrode 13b and the cathode 12 by being provided on the bottom 12a in a state where the counter electrode 13b and the inner surface of the bottom 12a of the cathode 12 are in contact with each other. A diffusion prevention plate 17 is laminated on the detection electrode 13 a of the proton conductor film 13.

取込部材１４は、活性炭フィルタ１４ａと、該活性炭フィルタ１４ａを収容する収容部１４ｂと、複数の取込孔１４ｃと、供給部としての供給孔１４ｄと、を有している。活性炭フィルタ１４ａは、検知対象ガスである一酸化炭素と水蒸気を通過するものであれば、シリカゲル、ゼオライト等の他の部材を用いることもできる。   The intake member 14 includes an activated carbon filter 14a, a housing portion 14b that accommodates the activated carbon filter 14a, a plurality of intake holes 14c, and a supply hole 14d as a supply portion. As the activated carbon filter 14a, other members such as silica gel and zeolite can be used as long as they pass carbon monoxide and water vapor which are detection target gases.

収容部１４ｂは、導電性部材によって形成しており、上ケース１４ｂ１と下ケース１４ｂ２とを有している。そして、上ケース１４ｂ１と下ケース１４ｂ２とは、内部に活性炭フィルタ１４ａを収容して覆った状態でかしめ固定している。収容部１４ｂは、陰極１２内に収容され且つ拡散防止板１７を介して検知極１３ａに積層されることで、検知極１３ａと電気的に接続している。   The accommodating portion 14b is formed of a conductive member and has an upper case 14b1 and a lower case 14b2. The upper case 14b1 and the lower case 14b2 are caulked and fixed in a state in which the activated carbon filter 14a is accommodated and covered. The accommodating portion 14 b is accommodated in the cathode 12 and is stacked on the detection electrode 13 a via the diffusion prevention plate 17 so as to be electrically connected to the detection electrode 13 a.

収容部材１４は、絶縁性のガスケット１５によって対極１３ｂ内に固定することで、陰極１２（対極１３ｂ）とは絶縁している。収容部材１４は、陰極１２に収容固定されると、開口１２ｄから外部に上ケース１４ｂ１の一部が若干突出する構造となっており、その突出量は任意に設定することができる。そして、上ケース１４ｂ１が電気化学式センサ１の陽極となっている。   The housing member 14 is insulated from the cathode 12 (counter electrode 13b) by being fixed in the counter electrode 13b by an insulating gasket 15. When the accommodating member 14 is accommodated and fixed in the cathode 12, a part of the upper case 14b1 protrudes slightly from the opening 12d to the outside, and the protruding amount can be arbitrarily set. The upper case 14b1 serves as the anode of the electrochemical sensor 1.

複数の取込孔１４ｃは、上ケース１４ｂ１に設けられて外部から水蒸気、ＣＯガス等を取込部材１４内に取り込んでいる。供給孔１４ｄは、取込部材１４内に取り込んだ水蒸気、ＣＯガス等を拡散防止板１７の供給部１７ａを介してプロトン導電体膜１３に供給する。即ち、電気化学式センサ１の周囲の水蒸気、ＣＯガス等は、取込部材１４の取込孔１４ｃから取込部材１４内に取り込まれ、活性炭フィルタ１４ａ、供給孔１４ｄ、拡散防止板１７の供給部１７ａを通過してプロトン導電体膜１３に到達する。   The plurality of intake holes 14c are provided in the upper case 14b1 and take in water vapor, CO gas, and the like from the outside into the intake member 14. The supply hole 14 d supplies water vapor, CO gas, or the like taken into the take-in member 14 to the proton conductor film 13 through the supply part 17 a of the diffusion prevention plate 17. That is, water vapor, CO gas, etc. around the electrochemical sensor 1 are taken into the take-in member 14 from the take-in hole 14c of the take-in member 14, and are supplied to the activated carbon filter 14a, the supply hole 14d, and the diffusion prevention plate 17 It passes through 17a and reaches the proton conductor film 13.

プロトン導電体膜１３に供給される水蒸気の水分を利用した酸化反応を起こして、検知極１３ａにプロトン（２Ｈ+）と電子（２ｅ-）を発生させる。検知極１３ａに発生した電子（２ｅ-）はプロトン導電体膜１３の内部を通過できないので検知極１３ａに滞留し、一方、プロトン（２Ｈ+）は、プロトン導電体膜１３の内部を通過して対極１３ｂに移動し、ここで、酸素と還元反応を起こして対極１３ｂに水（Ｈ2Ｏ）を生成する。 Oxidation reaction using the moisture of water vapor supplied to the proton conductor film 13 is caused to generate protons (2H + ) and electrons (2e − ) at the detection electrode 13a. The electrons (2e − ) generated in the detection electrode 13a cannot pass through the proton conductor film 13 and thus stay in the detection electrode 13a, while the proton (2H + ) passes through the proton conductor film 13 and passes through the proton conductor film 13. It moves to the counter electrode 13b where it undergoes a reduction reaction with oxygen to produce water (H 2 O) at the counter electrode 13b.

即ち、検知極１３ａでは、供給孔１４ｄから供給された水蒸気の水分を利用したプロトン導電体膜１３におけるＣＯガス（対象ガス）の酸化反応が発生する。対極１３ｂでは、その酸化反応によって発生したプロトンの還元反応が発生する。よって、検知極１３ａと対極１３ｂとの間には、取り込んだＣＯガスの濃度に応じた電流を発生する。   That is, in the detection electrode 13a, an oxidation reaction of the CO gas (target gas) occurs in the proton conductor film 13 using the moisture of the water vapor supplied from the supply hole 14d. At the counter electrode 13b, a reduction reaction of protons generated by the oxidation reaction occurs. Therefore, a current corresponding to the concentration of the captured CO gas is generated between the detection electrode 13a and the counter electrode 13b.

したがって、陽極である上ケース１４ｂ１と陰極１２を介して検知極１３ａと対極１３ｂとの間に負荷を接続すると、検知極１３ａに滞留した電子（２ｅ-）の対極１３ｂに向かう流れが負荷に生じ、これにより対極１３ｂから負荷を経て検知極１３ａに向かう短絡電流の流れが生じるので、この負荷に流れる短絡電流を電流−電圧変換することで、周辺雰囲気中のＣＯガスの濃度に応じた電圧値のＣＯ濃度信号が得られる。 Therefore, when a load is connected between the detection electrode 13a and the counter electrode 13b via the upper case 14b1 which is an anode and the cathode 12, a flow of electrons (2e − ) staying in the detection electrode 13a toward the counter electrode 13b is generated in the load. As a result, a short-circuit current flows from the counter electrode 13b through the load to the detection electrode 13a, so that the voltage value corresponding to the concentration of CO gas in the ambient atmosphere is obtained by performing current-voltage conversion on the short-circuit current flowing through the load. The CO concentration signal is obtained.

上述した構造の電気化学式センサ１は、図２及び図３に示すように、燃焼機器である給湯器２に接続された排気筒３内に設けられる。該排気筒３は、給湯器２の燃焼室２ａにおける燃焼により発生した燃焼排ガスと水蒸気を屋外へ導いて屋外に排出する。そして、本最良の形態では、電気化学式センサ１の天井部分、つまり、陰極１２の開口１２ｄが排気筒３内の流れ方向Ｘに向かうように、排気筒３内に配置した場合について説明するが、電気化学式センサ１は流れ方向Ｘに対して任意の向きで配置することができる。   As shown in FIGS. 2 and 3, the electrochemical sensor 1 having the above-described structure is provided in an exhaust pipe 3 connected to a water heater 2 that is a combustion device. The exhaust tube 3 guides the combustion exhaust gas and water vapor generated by the combustion in the combustion chamber 2a of the water heater 2 to the outdoors and discharges them to the outdoors. And in this best mode, although the ceiling part of the electrochemical sensor 1, that is, the case where the opening 12d of the cathode 12 is arranged in the exhaust pipe 3 so as to face the flow direction X in the exhaust pipe 3, will be described. The electrochemical sensor 1 can be arranged in an arbitrary direction with respect to the flow direction X.

電気化学式センサ１は、排気筒３を貫通した一対の端子６の各々が、陽極である上ケース１４ｂ１と陰極１２を介して検知極１３ａと対極１３ｂとに電気的に接続されている。一対の端子６は、排気筒３内に設けられることから、常温から高温の変化に対応することが可能な部材で形成しており、排気筒３の外側に取り付けられた台座４を貫通している。台座４は、耐熱性の部材によって形成しており、一対の端子６が貫通する部分から排気筒３内の各種ガスが外部に漏れないように一対の端子６に密着している。   In the electrochemical sensor 1, each of a pair of terminals 6 penetrating the exhaust tube 3 is electrically connected to a detection electrode 13a and a counter electrode 13b via an upper case 14b1 that is an anode and a cathode 12. Since the pair of terminals 6 are provided in the exhaust tube 3, the pair of terminals 6 is formed of a member that can cope with a change from normal temperature to high temperature, and penetrates the pedestal 4 attached to the outside of the exhaust tube 3. Yes. The pedestal 4 is formed of a heat-resistant member, and is in close contact with the pair of terminals 6 so that various gases in the exhaust tube 3 do not leak outside from the portion through which the pair of terminals 6 penetrate.

対象ガス監視装置５は、排気筒３内に配置した電気化学式センサ１を有している。対象ガス監視装置５は、一対の端子６を介して電気化学式センサ１に電気的に接続すると共に、給湯器２にケーブル等を介して電気的に接続している。対象ガス監視装置５は、電気化学式センサ１の検知極１３ａと対極１３ｂとの間に発生する電流を監視して対象ガスの発生を監視し、その濃度に応じたガス濃度信号（濃度レベル、異常の有無などの信号）を給湯器２に出力する。そして、給湯器２は、入力されたガス濃度信号に基づいて、遮断弁の遮断、ＣＯガス漏れ警報等の各種処理を行う。   The target gas monitoring device 5 has an electrochemical sensor 1 disposed in the exhaust tube 3. The target gas monitoring device 5 is electrically connected to the electrochemical sensor 1 via a pair of terminals 6 and is electrically connected to the water heater 2 via a cable or the like. The target gas monitoring device 5 monitors the current generated between the detection electrode 13a and the counter electrode 13b of the electrochemical sensor 1 to monitor the generation of the target gas, and a gas concentration signal (concentration level, abnormal) according to the concentration. A signal such as the presence or absence of) is output to the water heater 2. Then, the water heater 2 performs various processes such as shut-off of the shut-off valve and CO gas leak alarm based on the input gas concentration signal.

（試験結果）
次に、上述した電気化学式センサ１のプロトン導電体膜１３とその環境の水分量を比較する試験結果を、以下に説明する。なお、窒素（Ｎ2）＝１００％、ＣＯ＝５００ｐｐｍのＮ2ドライガスを排気筒３内に流した結果、図４，５に示すＮ2ドライガスの特性を得ることができた。なお、図４において、縦軸は電気化学式センサ１のセンサ出力（Ｖ）、横軸は時間（秒）をそれぞれ示している。また、図５において、縦軸は電気化学式センサ１のセンサ出力（Ｖ）、横軸は時間（分）をそれぞれ示している。 (Test results)
Next, test results comparing the proton conductor film 13 of the electrochemical sensor 1 and the amount of water in the environment will be described below. As a result of flowing N 2 dry gas of nitrogen (N 2 ) = 100% and CO = 500 ppm into the exhaust tube 3, the characteristics of the N 2 dry gas shown in FIGS. 4 and 5 were obtained. In FIG. 4, the vertical axis indicates the sensor output (V) of the electrochemical sensor 1, and the horizontal axis indicates time (seconds). In FIG. 5, the vertical axis indicates the sensor output (V) of the electrochemical sensor 1, and the horizontal axis indicates time (minutes).

図４，５の各グラフから、プロトン導電体膜１３中の水分を計算する。このとき、図４中の領域１は遷移領域と考え、領域２においてプロトン導電体膜１３の水分が消費されたものと考えた。そして、電気化学式センサ１の濃度出力は、１．１０〜３．７５（ｎＡ／ｐｐｍ）であり、平均値を３（ｎＡ／ｐｐｍ）とすると、５００（ｐｐｍ）では１５００（ｎＡ）であり、リニアに出力が低下すると仮定すると、平均をとって７５０（ｎＡ）となる。   The moisture in the proton conductor film 13 is calculated from the graphs of FIGS. At this time, the region 1 in FIG. 4 was considered as a transition region, and the water in the proton conductor film 13 was considered to be consumed in the region 2. The concentration output of the electrochemical sensor 1 is 1.10 to 3.75 (nA / ppm). If the average value is 3 (nA / ppm), 500 (ppm) is 1500 (nA). Assuming that the output decreases linearly, the average is 750 (nA).

図４における領域２の時間を約８時間とすると、電気量は７５０＊１０-9＊８＊３６００＝９．０２１６（Ｃ）と算出することができる。そして、電子は、０．０２１６／９６５００＝２．２４＊１０-7（ｍｏｌ）を消費する。Ｈ2Ｏの単位物質量当たりの質量を１８（ｇ／ｍｏｌ）とし、電子２個でＨ2Ｏ１個とすると、水分は１８＊０．５＊２．２４＊１０-7＝２．０１６（μｇ）と求められる。つまり、８時間で２．０１６（μｇ）の水分が消費されたことになる。 If the time of region 2 in FIG. 4 is about 8 hours, the amount of electricity can be calculated as 750 * 10 −9 * 8 * 3600 = 9.0216 (C). And an electron consumes 0.0216 / 96500 = 2.24 * 10 < -7 > (mol). When the mass per unit amount of H 2 O is 18 (g / mol) and two electrons are H 2 O, the moisture content is 18 * 0.5 * 2.24 * 10 −7 = 2.016 ( μg). That is, 2.016 (μg) of water was consumed in 8 hours.

一方、図４中の領域２に対応した図５のグラフを示す式ｙ＝−０．００１ｘ＋２．６５５９より、水分が完全になくなり、出力＝０になる時間を算出すると、ｘ＝２６５５．９（分）となる。即ち、８時間で２．０１６（μｇ）が消費されたので、２６５５．９（分）では、１１．１５（μｇ）が消費され、これがプロトン導電体膜１３中の全水分と考えられる。   On the other hand, from the equation y = −0.001x + 2.6559 showing the graph of FIG. 5 corresponding to the region 2 in FIG. 4, when the time when the water is completely removed and the output = 0 is calculated, x = 2655.9 ( Min). That is, since 2.016 (μg) was consumed in 8 hours, 11.65 (μg) was consumed at 2655.9 (minutes), which is considered to be the total moisture in the proton conductor film 13.

ここで、使用されるプロトン導電体膜１３をＮａｆｉｏｎ１１７とすると、３６０（ｇ／ｍ2）となる。膜の直径をφ８（ｍｍ）とすると、膜の質量は３６０＊π／４（８＊１０-3）2＝０．０１８（ｇ）となり、水分量は０．１（ｗｔ％）となる。 Here, when the proton conductor film 13 to be used is Nafion 117, 360 (g / m 2 ) is obtained. When the diameter of the film is φ8 (mm), the mass of the film is 360 * π / 4 (8 * 10 −3 ) 2 = 0.018 (g), and the water content is 0.1 (wt%).

次に、環境の水分量は、５度における水蒸気量が６．８（ｇ／ｍ3）であり、２０度の空気密度は１．２０５（ｋｇｆ／ｍ3）なので、６．８／１２０５＊１００＝０．５６（ｗｔ％）となる。この値は、上述したプロトン導電体膜１３中の水分量０．１（ｗｔ％）よりも高くなっている。従って、プロトン導電体膜１３中の水分は冬季を想定した湿度よりも低いため、従来の水タンクがなくても電気化学式センサ１の性能を維持できることを確認することができた。 Next, the amount of water in the environment is 6.8 (g / m 3 ) at 5 degrees, and the air density at 20 degrees is 1.205 (kgf / m 3 ), so 6.8 / 1205 * 100 = 0.56 (wt%). This value is higher than the water content 0.1 (wt%) in the proton conductor film 13 described above. Therefore, since the moisture in the proton conductor film 13 is lower than the humidity assumed in winter, it has been confirmed that the performance of the electrochemical sensor 1 can be maintained without a conventional water tank.

また、ドライガス→水蒸気を含んだガス→ドライガスの順で各ガスを流し、電気化学式センサ１のセンサ出力（検知極１３ａと対極１３ｂとの間の電位差）の過渡特性を測定した結果、ドライガスと水蒸気を含んだガスとの過渡特性に同一であることが確認できた。さらに、ドライガスを１０時間連続で流しながらセンサ出力の過渡特性を測定した結果、大きな変化がないことを確認できた。   Further, as a result of measuring the transient characteristics of the sensor output of the electrochemical sensor 1 (potential difference between the detection electrode 13a and the counter electrode 13b) by flowing each gas in the order of dry gas → gas containing water vapor → dry gas, It was confirmed that the transient characteristics of the gas and the gas containing water vapor were the same. Furthermore, as a result of measuring the transient characteristics of the sensor output while flowing dry gas continuously for 10 hours, it was confirmed that there was no significant change.

このような試験結果から、本発明のように電気化学式センサ１の構成から従来の水タンクを削除しても、排気筒３内の水蒸気をプロトン導電体膜１３に供給する構成とすることで、図６に示すような従来の水タンクを有する電気化学式センサと同様のセンサ出力を得ることができることを確認できた。   From such a test result, even if the conventional water tank is deleted from the configuration of the electrochemical sensor 1 as in the present invention, the configuration in which the water vapor in the exhaust tube 3 is supplied to the proton conductor film 13 is as follows. It was confirmed that a sensor output similar to that of an electrochemical sensor having a conventional water tank as shown in FIG. 6 can be obtained.

以上説明した電気化学式センサ１によれば、排気筒３内の水蒸気をプロトン導電体膜１３に供給する供給孔（供給部）１６を設け、その水蒸気の水分を利用して検知極１３ａに酸化反応を発生させ且つ対極１３ｂに還元反応を発生させることで、検知極１３ａと対極１３ｂとの間に対象ガスの濃度に応じた電流を発生するようにしたことから、従来の水タンクを不要とすることができる。また、密閉された水タンクを有していないことから、水漏れ等の問題もなくなり、給湯器２の排気筒３等の常温から高温を繰り返す空間内にも設置することができる。従って、電気化学式センサ１を小型化でき且つ水漏れ等の問題も解消できるため、給湯器２の排気筒等の狭く厳しい空間でも設置することが可能なり、使用適合範囲の制約を低減させることができる。   According to the electrochemical sensor 1 described above, the supply hole (supply part) 16 for supplying water vapor in the exhaust tube 3 to the proton conductor film 13 is provided, and the detection electrode 13a is oxidized using the water content of the water vapor. And generating a reduction reaction at the counter electrode 13b, a current corresponding to the concentration of the target gas is generated between the detection electrode 13a and the counter electrode 13b, so that a conventional water tank is not required. be able to. Moreover, since it does not have a sealed water tank, there is no problem of water leakage and the like, and it can be installed in a space where the exhaust pipe 3 of the water heater 2 repeats from normal temperature to high temperature. Therefore, since the electrochemical sensor 1 can be reduced in size and problems such as water leakage can be solved, it can be installed even in a narrow and severe space such as the exhaust pipe of the water heater 2, and the restriction of the usable range can be reduced. it can.

また、排気筒３内の水蒸気の水分を利用することで、使用適合範囲の制約を低減した電気化学式センサ１の検知極１３ａと対極１３ｂとの間に発生する電流を監視して対象ガスの発生を監視するようにしたことから、給湯器２の排気筒３の常温から高温を繰り返す空間内等における対象ガスの発生を監視することができる。従って、電気化学式センサ１をより所望の箇所に設置して対象ガスを監視することができるため、監視精度の向上に貢献することができる。   In addition, by using the moisture of the water vapor in the exhaust tube 3, the current generated between the detection electrode 13a and the counter electrode 13b of the electrochemical sensor 1 with reduced restrictions on the applicable range of use is monitored to generate the target gas. Therefore, it is possible to monitor the generation of the target gas in a space where the exhaust tube 3 of the water heater 2 repeats from normal temperature to high temperature. Therefore, since the target gas can be monitored by installing the electrochemical sensor 1 at a more desired location, it is possible to contribute to improvement of monitoring accuracy.

なお、上述した実施形態では、本発明の電気化学式センサ１を燃焼機器である給湯器２に取り付けられた排気筒３内に設ける場合について説明したが、本発明はこれに限定するものではなく、例えば給湯器２内に組み込まれた排気筒内に設けるなど種々異なる実施形態とすることができる。   In the above-described embodiment, the case where the electrochemical sensor 1 of the present invention is provided in the exhaust pipe 3 attached to the water heater 2 that is a combustion device has been described, but the present invention is not limited thereto. For example, it can be set as various different embodiments, such as providing in the exhaust pipe integrated in the water heater 2. FIG.

また、上述した実施形態では、請求項中の供給部を拡散防止板１７の供給部１７ａとした場合について説明したが、本発明はこれに限定するものではなく、例えば陰極１２に孔として設けて排気筒３内から直接水蒸気を供給するなど種々異なる実施形態とすることができる。   Further, in the above-described embodiment, the case where the supply portion in the claims is the supply portion 17a of the diffusion prevention plate 17 has been described. However, the present invention is not limited to this, and for example, the cathode 12 is provided as a hole. Various embodiments such as supplying water vapor directly from the inside of the exhaust tube 3 can be adopted.

さらに、上述した本最良の形態では、対象ガス監視装置５を給湯器２の外部に設ける場合について説明するが、本発明はこれに限定するものではなく、対象ガス監視装置５内に内蔵したり、ＣＯガス警報装置に内蔵又は接続するなど種々異なる実施形態とすることができる。   Further, in the above-described best mode, the case where the target gas monitoring device 5 is provided outside the water heater 2 will be described. However, the present invention is not limited to this, and the target gas monitoring device 5 may be built in the target gas monitoring device 5. Various embodiments may be employed such as being built in or connected to a CO gas alarm device.

このように上述した実施例は本発明の代表的な形態を示したに過ぎず、本発明は、実施形態に限定されるものではない。即ち、本発明の骨子を逸脱しない範囲で種々変形して実施することができる。   As described above, the above-described embodiments are merely representative forms of the present invention, and the present invention is not limited to the embodiments. That is, various modifications can be made without departing from the scope of the present invention.

本発明の電気化学式センサの断面を示す断面図である。It is sectional drawing which shows the cross section of the electrochemical type sensor of this invention. 図１中の電気化学式センサの配置と対象ガス監視装置の関係を説明するための図である。It is a figure for demonstrating the relationship between arrangement | positioning of the electrochemical type sensor in FIG. 1, and a target gas monitoring apparatus. 図１中の電気化学式センサの排気筒に対する取付例を説明するための部分断面図である。It is a fragmentary sectional view for demonstrating the example of attachment with respect to the exhaust pipe of the electrochemical sensor in FIG. 図１中の電気化学式センサのセンサ出力と時間との関係を示すグラフである。It is a graph which shows the relationship between the sensor output of the electrochemical sensor in FIG. 1, and time. 図１中のプロトン導電膜の水分の消費に対応したセンサ出力と時間との関係を示すグラフである。It is a graph which shows the relationship between the sensor output corresponding to the consumption of the water | moisture content of the proton conductive film in FIG. 1, and time. 一般的な従来の電気化学式ＣＯセンサの構成を示す断面図である。It is sectional drawing which shows the structure of a general conventional electrochemical CO sensor.

符号の説明Explanation of symbols

１ 電気化学式センサ
２ 燃焼機器（給湯器）
３ 排気筒
５ 対象ガス監視装置
１２ 陰極
１３ プロトン導電体膜
１３ａ 検知極
１３ｂ 対極
１４ 収容部材
１７ 拡散防止板
１７ａ 供給部（孔） 1 Electrochemical sensor 2 Combustion equipment (water heater)
3 Exhaust cylinder 5 Target gas monitoring device 12 Cathode 13 Proton conductor membrane 13a Detection electrode 13b Counter electrode 14 Housing member 17 Diffusion prevention plate 17a Supply section (hole)

Claims (3)

プロトン導電体膜を有し、燃焼機器の燃焼によって発生した燃焼排ガスを排出する排気筒内に設けられる電気化学式センサであって、
前記排気筒内中の水蒸気を前記プロトン導電体膜に供給する供給部を有し、
前記プロトン導電体膜の検知極で発生し且つ前記供給部から供給された水蒸気の水分を利用した前記プロトン導電体膜における対象ガスの酸化反応と、前記プロトン導電体膜の対極で発生し且つ前記酸化反応によって発生したプロトンの還元反応とにより、前記排気筒内の対象ガスの濃度に応じた電流を、前記検知極と前記対極との間に発生するようにしたことを特徴とする電気化学式センサ。 An electrochemical sensor that has a proton conductor film and is provided in an exhaust cylinder that discharges combustion exhaust gas generated by combustion of combustion equipment,
A supply unit for supplying water vapor in the exhaust pipe to the proton conductor film;
Oxidation reaction of the target gas in the proton conductor film generated at the detection electrode of the proton conductor film and using the moisture of water vapor supplied from the supply unit, and generated at the counter electrode of the proton conductor film and the An electrochemical sensor characterized in that a current corresponding to the concentration of the target gas in the exhaust pipe is generated between the detection electrode and the counter electrode by a reduction reaction of protons generated by the oxidation reaction. . 請求項１に記載の電気化学式センサを有し、前記電気化学式センサの前記検知極と前記対極との間に発生する電流を監視して対象ガスの発生を監視することを特徴とする対象ガス監視装置。   A target gas monitor comprising the electrochemical sensor according to claim 1, wherein current generated between the detection electrode and the counter electrode of the electrochemical sensor is monitored to monitor generation of the target gas. apparatus. プロトン導電体膜を有する電気化学式センサの濃度検出方法であって、
燃焼機器の燃焼によって発生した燃焼排ガスを排出する排気筒内に設けられ、前記排気筒内中の水蒸気を前記プロトン導電体膜に供給し、前記プロトン導電体膜の検知極で発生し且つ前記供給部から供給された水蒸気の水分を利用した前記プロトン導電体膜における対象ガスの酸化反応と、前記プロトン導電体膜の対極で発生し且つ前記酸化反応によって発生したプロトンの還元反応とにより、前記排気筒内の対象ガスの濃度に応じた電流を前記検知極と前記対極との間に発生することを特徴とする電気化学式センサの濃度検出方法。 A method for detecting the concentration of an electrochemical sensor having a proton conductor film,
Provided in an exhaust cylinder for discharging combustion exhaust gas generated by combustion of combustion equipment, supplying water vapor in the exhaust cylinder to the proton conductor film, generated at the detection electrode of the proton conductor film and the supply The oxidation reaction of the target gas in the proton conductor film using the moisture of the water vapor supplied from the unit, and the reduction reaction of the proton generated at the counter electrode of the proton conductor film and generated by the oxidation reaction, A method for detecting a concentration of an electrochemical sensor, wherein a current corresponding to a concentration of a target gas in a cylinder is generated between the detection electrode and the counter electrode.
JP2006350707A 2006-12-26 2006-12-26 Electrochemical sensor, target gas monitor device, and concentration detection method of electrochemical sensor Abandoned JP2008164305A (en)

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