JPH11258199A - Electrochemical odorant sensor - Google Patents
Electrochemical odorant sensorInfo
- Publication number
- JPH11258199A JPH11258199A JP10088168A JP8816898A JPH11258199A JP H11258199 A JPH11258199 A JP H11258199A JP 10088168 A JP10088168 A JP 10088168A JP 8816898 A JP8816898 A JP 8816898A JP H11258199 A JPH11258199 A JP H11258199A
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- JP
- Japan
- Prior art keywords
- dms
- tbm
- working electrode
- odorant
- concentration
- 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.)
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- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、天然ガスやプロパ
ンガスなどの燃料用ガスに付臭剤として添加されるター
シャリーブチルメルカプタン（以下、ＴＢＭと略記す
る）及びジメチルサルファイド（以下、ＤＭＳと略記す
る）の添加量を制御するために、燃料用ガス中の付臭剤
濃度を測定する付臭剤センサに関するものである。The present invention relates to tertiary butyl mercaptan (hereinafter abbreviated as TBM) and dimethyl sulfide (hereinafter abbreviated as DMS) which are added as odorants to fuel gas such as natural gas and propane gas. The present invention relates to an odorant sensor for measuring the odorant concentration in a fuel gas in order to control the amount of odorant added.
【０００２】[0002]
【従来の技術】天然ガスやプロパンガスなどの燃料用ガ
スには、ガス漏れの検知を容易にするために、付臭剤に
より臭い付けが行なわれている。付臭剤としては、ＴＢ
ＭとＤＭＳの等量混合物がよく使用される。一般に、付
臭剤添加後の燃料用ガス中のＴＢＭ濃度及びＤＭＳ濃度
はともに約７ｐｐｍであり、ＴＢＭ濃度とＤＭＳ濃度の
合計は１４〜１５ｐｐｍ程度である。燃料用ガス中のＴ
ＢＭ濃度及びＤＭＳ濃度の測定法として、ガスクロマト
グラフィー法や燃焼−ＮＤＩＲ（非分散赤外分析計）法
などがある。簡便な付臭剤センサとよべるものは存在し
ない。2. Description of the Related Art Fuel gases such as natural gas and propane gas are smelled with an odorant to facilitate detection of gas leaks. As an odorant, TB
An equal mixture of M and DMS is often used. Generally, the TBM concentration and the DMS concentration in the fuel gas after the addition of the odorant are both about 7 ppm, and the total of the TBM concentration and the DMS concentration is about 14 to 15 ppm. T in fuel gas
As a method for measuring the BM concentration and the DMS concentration, there are a gas chromatography method and a combustion-NDIR (non-dispersive infrared spectrometer) method. There is no such thing as a simple odorant sensor.
【０００３】ガスクロマトグラフィー法は、付臭剤を添
加した燃料用ガスをキャリアガスとともに充填物がつめ
られたカラムに送って分離した後、ＴＢＭ濃度及びＤＭ
Ｓ濃度を測定する。燃焼−ＮＤＩＲ法は、付臭剤を添加
した燃料用ガスを燃焼してＴＢＭ及びＤＭＳを二酸化硫
黄に変換し、ＮＤＩＲを用いて二酸化硫黄濃度を測定す
ることにより、ＴＢＭとＤＭＳの合計の濃度を定量す
る。In the gas chromatography method, a fuel gas to which an odorant has been added is sent to a column filled with a carrier together with a carrier gas and separated therefrom.
Measure the S concentration. The combustion-NDIR method converts TBM and DMS to sulfur dioxide by burning a fuel gas to which an odorant has been added, and measures the sulfur dioxide concentration using NDIR to determine the total concentration of TBM and DMS. Quantify.
【０００４】[0004]
【発明が解決しようとする課題】ガスクロマトグラフィ
ー法は、カラムでの分離に時間がかかり、分析結果が得
られるまでに７分程度の時間が必要なので、燃料用ガス
製造時の付臭剤モニタとして用いるには応答時間がかか
りすぎるという欠点があった。燃焼−ＮＤＩＲ法は、燃
料用ガス燃焼時に多量の水が発生するので、二酸化硫黄
を正確に測定するために十分な除湿を行なう必要があ
る。さらに、燃料用ガス燃焼のために酸素を必要とす
る。これらの従来の方法では、燃焼や分離などの前処理
が必要である。そのため、装置が複雑であり、応答時間
もかかる。さらに装置のコストも高いという問題もあっ
た。In the gas chromatography method, it takes a long time to perform separation on a column, and it takes about 7 minutes to obtain an analysis result. Therefore, an odorant monitor during fuel gas production is required. There was a disadvantage that the response time was too long to use. In the combustion-NDIR method, a large amount of water is generated at the time of combustion of a fuel gas. Therefore, it is necessary to perform sufficient dehumidification in order to accurately measure sulfur dioxide. In addition, oxygen is required for fuel gas combustion. These conventional methods require pretreatment such as combustion and separation. Therefore, the device is complicated and the response time is long. There was also a problem that the cost of the apparatus was high.
【０００５】そこで本発明は、従来法に比較して、簡
便、迅速に付臭剤をモニタリングでき、かつ安価な付臭
剤センサを提供することを目的とするものである。Accordingly, an object of the present invention is to provide an inexpensive odorant sensor which can monitor an odorant easily and quickly as compared with a conventional method.
【０００６】[0006]
【課題を解決するための手段】本発明による電気化学式
付臭剤センサは、電解液が充填されたセンサボディで、
電解液と被検ガスとの接触面にガス透過性隔膜が設けら
れ、その隔膜の電解液側には作用極が形成され、作用極
に対し電解液を介して対極と比較極が配置され、ＴＢＭ
とＤＭＳに等感度で応答するように作用極の電位が−
０．１Ｖ〜０．４Ｖの範囲で一定に保たれ、対極と作用
極間の電流により被検ガス中のＴＢＭとＤＭＳの合計の
濃度を測定するものである。An electrochemical odorant sensor according to the present invention is a sensor body filled with an electrolyte,
A gas-permeable diaphragm is provided on the contact surface between the electrolyte and the test gas, a working electrode is formed on the electrolyte side of the diaphragm, and a counter electrode and a comparison electrode are arranged with respect to the working electrode via the electrolyte. TBM
And the potential of the working electrode is-
It is kept constant in the range of 0.1 V to 0.4 V, and measures the total concentration of TBM and DMS in the test gas by the current between the counter electrode and the working electrode.
【０００７】このような電気化学式付臭剤センサでは、
作用極と対極との電位差を一定に保ちながら電解を行な
うと、測定成分の酸化還元反応が選択的に進行する。そ
のときに出力される酸化還元電流を測定することによっ
て測定成分の濃度を知ることができる。本発明では、比
較極の電位を基準として、対極に対する作用極の電位
（以下、設定電位という）をターシャリーブチルメルカ
プタンとジメチルサルファイドに等感度で応答するよう
に一定に保ち、対極と作用極間の酸化電流により燃料用
ガス中のターシャリーブチルメルカプタンとジメチルサ
ルファイドの合計の濃度を測定する。この設定電位は、
対極と比較極が白金ブラックでコーティングされた白金
電極で、電解液が６Ｍ硫酸の場合、−０．１Ｖ〜０．４
Ｖの範囲、例えば−６０ｍＶ〜０Ｖの範囲に設定され
る。In such an electrochemical odorant sensor,
When electrolysis is performed while keeping the potential difference between the working electrode and the counter electrode constant, the oxidation-reduction reaction of the measurement component proceeds selectively. By measuring the oxidation-reduction current output at that time, the concentration of the measurement component can be known. In the present invention, the potential of the working electrode with respect to the counter electrode (hereinafter referred to as a set potential) is maintained constant with respect to the tertiary butyl mercaptan and dimethyl sulfide with equal sensitivity based on the potential of the reference electrode, and the potential between the counter electrode and the working electrode is maintained. The total concentration of tertiary butyl mercaptan and dimethyl sulfide in the fuel gas is measured by the oxidation current of. This set potential is
When the counter electrode and the reference electrode are platinum electrodes coated with platinum black and the electrolyte is 6 M sulfuric acid, -0.1 V to 0.4
V, for example, -60 mV to 0 V.
【０００８】電気化学式ガスセンサは、原理的に酸化成
分の干渉を受けるが、燃料用ガスは炭化水素が主な成分
であり、干渉を受ける成分が少ないので、燃料用ガス中
の付臭剤の測定を行なうことができる。[0008] In principle, the electrochemical gas sensor is subject to interference of oxidizing components. However, since the fuel gas is mainly composed of hydrocarbons and the amount of interference is small, the measurement of the odorant in the fuel gas is performed. Can be performed.
【０００９】[0009]
【実施例】図１に一実施例としての電気化学式付臭剤セ
ンサを示す。この実施例は電気化学式（定電位電解式）
ガスセンサに属するものである。絶縁性材料で形成され
たセンサボディ２０は、その底部に開口２２をもち、そ
の開口２２が疎水性多孔質膜の隔膜２４で閉じられてい
る。センサボディ内には電解液２６として６Ｍの硫酸が
入れられており、隔膜２４上には電解液側に作用極２８
が形成されている。作用極２８は隔膜２４上に蒸着やス
パッタリング法により形成された金薄膜である。電解液
２６中には対極３０と比較極３２が完全に浸漬されて固
定されている。対極３０及び比較極３２は白金ブラック
でコーティングされている。FIG. 1 shows an electrochemical odorant sensor as one embodiment. This example is of the electrochemical type (potential electrolysis type)
It belongs to a gas sensor. The sensor body 20 formed of an insulating material has an opening 22 at the bottom, and the opening 22 is closed by a hydrophobic porous membrane 24. 6 M sulfuric acid is contained in the sensor body as an electrolyte 26, and a working electrode 28 is provided on the diaphragm 24 on the electrolyte side.
Are formed. The working electrode 28 is a gold thin film formed on the diaphragm 24 by vapor deposition or sputtering. The counter electrode 30 and the comparison electrode 32 are completely immersed and fixed in the electrolytic solution 26. The counter electrode 30 and the comparison electrode 32 are coated with platinum black.
【００１０】センサボディ２０内には電解液２６上に空
気層３４が設けられており、空気層３４は内圧調整口３
６の疎水性薄膜を介して大気とつながっている。その結
果、温度が変化してもセンサボディ２０内の圧力は変化
しない。センサボディの中心部には作用極２８を固定す
るために中ジャケット３８が配置され、中ジャケット３
８の中心部を通って作用極のリード線４０が外部から作
用極２８へと導かれている。リード線４０の先端はカー
ボンのシート状集電体４２により作用極２８に押しつけ
られ、電気的接触が保たれている。中ジャケット３８の
中心部にはサーミスタ８２が設けられており、そのサー
ミスタ８２、作用極２８、対極３０及び比較極３２のそ
れぞれのリード線が電解液２６と隔離された位置に設け
られたプリアンプ８４に接続されている。In the sensor body 20, an air layer 34 is provided on the electrolyte 26, and the air layer 34
6, and is connected to the atmosphere via a hydrophobic thin film. As a result, even if the temperature changes, the pressure in the sensor body 20 does not change. A middle jacket 38 is disposed at the center of the sensor body to fix the working electrode 28,
A working electrode lead wire 40 is guided from the outside to the working electrode 28 through the central portion of the working electrode 8. The distal end of the lead wire 40 is pressed against the working electrode 28 by a carbon sheet-like current collector 42 to maintain electrical contact. A thermistor 82 is provided at the center of the middle jacket 38, and a preamplifier 84 is provided at a position where the leads of the thermistor 82, the working electrode 28, the counter electrode 30, and the comparison electrode 32 are separated from the electrolyte 26. It is connected to the.
【００１１】リード線４０を介して作用極２８に電圧を
印加し、比較極３２の電位を基準として作用極２８の電
位を一定に保つ。開口２２から隔膜２４を介して作用極
２８にＴＢＭ及びＤＭＳを接触させると、ＴＢＭ及びＤ
ＭＳの酸化還元反応が選択的に進行する。そのときに出
力される酸化還元電流をプリアンプ８４により増幅して
測定することによってＴＢＭ及びＤＭＳの濃度を定量す
る。A voltage is applied to the working electrode 28 via the lead wire 40, and the potential of the working electrode 28 is kept constant with reference to the potential of the comparison electrode 32. When TBM and DMS are brought into contact with the working electrode 28 from the opening 22 through the diaphragm 24, the TBM and DMS
The redox reaction of MS proceeds selectively. The concentration of TBM and DMS is quantified by amplifying and measuring the redox current output at that time by the preamplifier 84.
【００１２】この実施例を用いてＴＢＭ及びＤＭＳの電
気化学的特性を調べた結果を図２に示す。図２は、作用
極２８の設定電位を−０．２Ｖ〜０．４Ｖの範囲で変化
させて、窒素中に等濃度のＴＢＭとＤＭＳをそれぞれ含
む試料を測定したときの、作用極２８と対極３０間の電
流値を表す図であり、（Ａ）中の破線はＴＢＭを測定し
たもの、（Ｂ）中の破線はＤＭＳを測定したものであ
る。それぞれの実線は窒素のみを測定したものである。
横軸は設定電位（Ｖ）を表し、縦軸は電流値（μＡ）を
表す。窒素測定時の電流値とＴＢＭ又はＤＭＳ測定時の
電流値の差が出力値となる。図２（Ａ），（Ｂ）から、
ＴＢＭ、ＤＭＳともに設定電位が−０．１Ｖ〜０．４Ｖ
の範囲で酸化還元反応を生ずることがわかる。FIG. 2 shows the result of examining the electrochemical characteristics of TBM and DMS using this example. FIG. 2 shows the working electrode 28 and the counter electrode when changing the set potential of the working electrode 28 in the range of -0.2 V to 0.4 V and measuring a sample containing TBM and DMS at the same concentration in nitrogen. It is a figure showing the electric current value between 30. The broken line in (A) measured TBM, and the broken line in (B) measured DMS. Each solid line is obtained by measuring only nitrogen.
The horizontal axis represents the set potential (V), and the vertical axis represents the current value (μA). The difference between the current value when measuring nitrogen and the current value when measuring TBM or DMS is the output value. From FIGS. 2A and 2B,
Set potential of -0.1V to 0.4V for both TBM and DMS
It can be seen that an oxidation-reduction reaction occurs within the range.
【００１３】図３は、設定電位を−０．１Ｖ〜０．４Ｖ
の範囲でＴＢＭ又はＤＭＳを測定したときの、濃度換算
した測定値（濃度）と既知の試料ガス濃度の相関（直線
性）を表す図である。横軸は試料ガス濃度（ｐｐｍ）、
縦軸は測定値（ｐｐｍ）である。図３において、ＴＢ
Ｍ、ＤＭＳともに高い直線性をもつので、この実施例を
ＴＢＭ、ＤＭＳの定量に用いることができる。FIG. 3 shows that the set potential is between -0.1 V and 0.4 V.
FIG. 6 is a diagram showing a correlation (linearity) between a measured value (concentration) converted into a concentration and a known sample gas concentration when TBM or DMS is measured in the range of FIG. The horizontal axis is the sample gas concentration (ppm),
The vertical axis is the measured value (ppm). In FIG. 3, TB
Since both M and DMS have high linearity, this example can be used for the quantification of TBM and DMS.
【００１４】また、図２から、設定電位が−６０ｍＶ〜
０Ｖのときに、ＴＢＭの出力値とＤＭＳの出力値がほぼ
等しいことがわかる。図４は、設定電位を−６０ｍＶと
して、濃度がほぼ同じＴＢＭ及びＤＭＳを測定したとき
のＴＢＭの出力値ピークとＤＭＳの出力値ピークを表す
図である。測定したＤＭＳの濃度は８．９３ｐｐｍ、Ｔ
ＢＭの濃度は８．９７ｐｐｍであった。この設定電位
で、ＴＢＭの感度とＤＭＳの感度がほぼ等しいことがわ
かる。ＴＢＭの感度とＤＭＳの感度を等しくすることに
より、燃料用ガス中に含まれるＴＢＭとＤＭＳの合計の
濃度を測定することができる。FIG. 2 shows that the set potential is -60 mV or more.
It can be seen that at 0 V, the output value of the TBM is almost equal to the output value of the DMS. FIG. 4 is a diagram showing the TBM output value peak and the DMS output value peak when measuring the TBM and DMS having substantially the same concentration with the set potential being −60 mV. The measured DMS concentration was 8.93 ppm, T
The concentration of BM was 8.97 ppm. It can be seen that the TBM sensitivity and the DMS sensitivity are almost equal at this set potential. By making the sensitivity of TBM equal to that of DMS, the total concentration of TBM and DMS contained in the fuel gas can be measured.
【００１５】この実施例では、燃焼や分離などの前処理
を行なわずに、燃料用ガス中のＴＢＭ及びＤＭＳを直接
測定できるので、簡便かつ迅速に測定することができ、
燃料用ガス製造時のモニタリングに好都合である。電気
化学式ガスセンサを用いた付臭剤センサは、この実施例
に限られるものではなく、他の形式の電気化学ガスセン
サも利用することができる。In this embodiment, the TBM and DMS in the fuel gas can be directly measured without performing pretreatment such as combustion and separation, so that the measurement can be performed simply and quickly.
This is convenient for monitoring during fuel gas production. The odorant sensor using the electrochemical gas sensor is not limited to this embodiment, and other types of electrochemical gas sensors can be used.
【００１６】また、従来の燃焼式ガス漏れセンサは、ガ
ス漏れ以外の炭化水素や炭素化合物に反応して誤作動す
ることがある。ガス漏れセンサにはｐｐｂ程度の低濃度
検知が求められるので、ＴＢＭ及びＤＭＳに対する電気
化学式ガスセンサの感度を向上させると、ＴＢＭやＤＭ
Ｓを検知するガス漏れセンサとして応用することができ
る。Further, the conventional combustion type gas leak sensor sometimes malfunctions in response to hydrocarbons or carbon compounds other than the gas leak. Since the gas leak sensor is required to detect a low concentration of about ppb, if the sensitivity of the electrochemical gas sensor to TBM and DMS is improved, TBM or DM
It can be applied as a gas leak sensor for detecting S.
【００１７】[0017]
【発明の効果】本発明の電気化学式付臭剤センサでは、
ＴＢＭとＤＭＳに等感度で応答するように作用極の電位
が一定に保たれ、対極と作用極間の電流により被検ガス
中のＴＢＭとＤＭＳの合計の濃度を測定するので、燃焼
や分離などの前処理を行なわずに、燃料用ガス中のＴＢ
Ｍ及びＤＭＳを直接測定できるので、簡便かつ迅速に測
定することができる。さらに、電気化学式ガスセンサ
は、ガスクロマトグラフィー装置や燃焼−ＮＤＩＲ装置
に比べて安価なので、低コストにて付臭剤センサを提供
することができる。According to the electrochemical odorant sensor of the present invention,
The potential of the working electrode is kept constant so that it responds to TBM and DMS with equal sensitivity, and the total concentration of TBM and DMS in the test gas is measured by the current between the counter electrode and working electrode. Of TB in fuel gas without pretreatment
Since M and DMS can be measured directly, they can be measured simply and quickly. Further, since the electrochemical gas sensor is inexpensive as compared with a gas chromatography device or a combustion-NDIR device, an odorant sensor can be provided at low cost.
【図１】 一実施例を表す断面図である。FIG. 1 is a cross-sectional view illustrating one embodiment.
【図２】 作用極の設定電位を−０．２Ｖ〜０．４Ｖの
範囲で変化させて、ＴＢＭ又はＤＭＳを測定したとき
の、作用極と対極間の電流値を表す図であり、（Ａ）は
ＴＢＭを測定したもの、（Ｂ）はＤＭＳを測定したもの
である。FIG. 2 is a diagram showing a current value between a working electrode and a counter electrode when a TBM or DMS is measured by changing a set potential of a working electrode in a range of −0.2 V to 0.4 V; ) Shows the result of measuring TBM, and (B) shows the result of measuring DMS.
【図３】 設定電位を−０．１Ｖ〜０．４Ｖの範囲でＴ
ＢＭ又はＤＭＳを測定したときの、濃度換算した測定値
（濃度）と試料ガス濃度の相関（直線性）を表す図であ
る。FIG. 3 shows that the set potential is T in a range of -0.1V to 0.4V.
FIG. 7 is a diagram illustrating a correlation (linearity) between a measured value (concentration) converted into a concentration and a sample gas concentration when BM or DMS is measured.
【図４】 設定電位を−６０ｍＶとして、濃度がほぼ等
しいＴＢＭ及びＤＭＳを測定したときのＴＢＭの出力値
ピークとＤＭＳの出力値ピークを表す図である。FIG. 4 is a diagram showing a TBM output value peak and a DMS output value peak when measuring a TBM and a DMS having substantially the same concentration with a set potential of −60 mV.
２０ センサボディ ２２ 底部の開口 ２４ 疎水性多孔質膜の隔膜 ２６ 電解液 ２８ 作用極 ３０ 対極 ３２ 比較極 ３４ 空気層 ３６ 内圧調整口 ３８ 中ジャケット ４０ 作用極のリード線 ４２ カーボンシート DESCRIPTION OF SYMBOLS 20 Sensor body 22 Bottom opening 24 Hydrophobic porous membrane diaphragm 26 Electrolyte 28 Working electrode 30 Counter electrode 32 Comparative electrode 34 Air layer 36 Internal pressure adjusting port 38 Middle jacket 40 Working electrode lead wire 42 Carbon sheet
Claims (1)
ターシャリーブチルメルカプタン及びジメチルサルファ
イドの濃度を測定する付臭剤センサであって、 電解液が充填されたセンサボディで、前記電解液と被検
ガスとの接触面にガス透過性隔膜が設けられ、前記隔膜
の前記電解液側には作用極が形成され、前記作用極に対
し前記電解液を介して対極と比較極が配置され、ターシ
ャリーブチルメルカプタンとジメチルサルファイドに等
感度で応答するように前記作用極の電位が−０．１Ｖ〜
０．４Ｖの範囲で一定に保たれ、前記対極と前記作用極
間の電流により被検ガス中のターシャリーブチルメルカ
プタンとジメチルサルファイドの合計の濃度を測定する
ことを特徴とする電気化学式付臭剤センサ。1. An odorant sensor for measuring the concentration of tertiary butyl mercaptan and dimethyl sulfide added as an odorant to a fuel gas, wherein the sensor body is filled with an electrolyte. A gas permeable diaphragm is provided on the contact surface between the sample and the test gas, a working electrode is formed on the electrolyte side of the diaphragm, and a counter electrode and a comparison electrode are disposed with respect to the working electrode via the electrolyte. , The potential of the working electrode is -0.1 V to respond to tertiary butyl mercaptan and dimethyl sulfide with equal sensitivity.
An electrochemical odorant which is kept constant within a range of 0.4 V and measures the total concentration of tertiary butyl mercaptan and dimethyl sulfide in the test gas by the current between the counter electrode and the working electrode. Sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10088168A JPH11258199A (en) | 1998-03-16 | 1998-03-16 | Electrochemical odorant sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10088168A JPH11258199A (en) | 1998-03-16 | 1998-03-16 | Electrochemical odorant sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11258199A true JPH11258199A (en) | 1999-09-24 |
Family
ID=13935398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10088168A Pending JPH11258199A (en) | 1998-03-16 | 1998-03-16 | Electrochemical odorant sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11258199A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007004350A1 (en) * | 2005-07-05 | 2007-01-11 | Gs Yuasa Corporation | Electrochemical gas sensor and process for producing the same |
| WO2018207879A1 (en) * | 2017-05-10 | 2018-11-15 | 株式会社ユーグレナ | Method for evaluating sulfur compound-containing substance, and method for quantifying volatile low molecular weight sulfur compound |
-
1998
- 1998-03-16 JP JP10088168A patent/JPH11258199A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007004350A1 (en) * | 2005-07-05 | 2007-01-11 | Gs Yuasa Corporation | Electrochemical gas sensor and process for producing the same |
| JP4835436B2 (en) * | 2005-07-05 | 2011-12-14 | 株式会社Ｇｓユアサ | Electrochemical gas sensor and manufacturing method thereof |
| WO2018207879A1 (en) * | 2017-05-10 | 2018-11-15 | 株式会社ユーグレナ | Method for evaluating sulfur compound-containing substance, and method for quantifying volatile low molecular weight sulfur compound |
| JP6426329B1 (en) * | 2017-05-10 | 2018-11-21 | 株式会社ユーグレナ | Method of evaluating sulfur compound-containing substance and method of determining volatile low molecular weight sulfur compound |
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