JP3132653B2 - Fuel cell power plant with degreasing monitor - Google Patents
Fuel cell power plant with degreasing monitorInfo
- Publication number
- JP3132653B2 JP3132653B2 JP09299799A JP29979997A JP3132653B2 JP 3132653 B2 JP3132653 B2 JP 3132653B2 JP 09299799 A JP09299799 A JP 09299799A JP 29979997 A JP29979997 A JP 29979997A JP 3132653 B2 JP3132653 B2 JP 3132653B2
- Authority
- JP
- Japan
- Prior art keywords
- degreasing
- fuel cell
- odor
- concentration
- gas
- 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.)
- Expired - Fee Related
Links
- 238000005238 degreasing Methods 0.000 title claims description 59
- 239000000446 fuel Substances 0.000 title claims description 47
- 239000007789 gas Substances 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000010248 power generation Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000012806 monitoring device Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Fuel Cell (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、燃料電池発電設備
に係わり、更に詳しくは、燃料電池の最初の昇温時にお
ける脱脂進行状況をモニタすることができる脱脂モニタ
装置を備えた燃料電池発電設備に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell power generation system , and more particularly, to a degreasing monitor capable of monitoring the progress of degreasing when a fuel cell is first heated.
The present invention relates to a fuel cell power generation facility provided with a device .
【０００２】[0002]
【従来の技術】溶融炭酸塩型燃料電池は、図４に模式的
に示すように、薄い平板状の電解質板（タイル）１を燃
料極（アノード）２と空気極（カソード）３の２枚の電
極で挟んで単セル４が構成され、更に複数のセル４と導
電性のバイポーラプレート（セパレータ）５を交互に積
層して高電圧を発生する積層電池（スタック）６が構成
される。以下、単に燃料電池と称する場合には、積層電
池（スタック）を意味する。2. Description of the Related Art As shown schematically in FIG. 4, a molten carbonate fuel cell comprises a thin flat electrolyte plate (tile) 1 composed of a fuel electrode (anode) 2 and an air electrode (cathode) 3. A single cell 4 is formed by sandwiching the above-mentioned electrodes, and a plurality of cells 4 and conductive bipolar plates (separators) 5 are alternately stacked to form a stacked battery (stack) 6 that generates a high voltage. Hereinafter, when simply called a fuel cell, it means a stacked cell (stack).
【０００３】上述したタイル１は、セラミックス粉末板
に電解質（溶融炭酸塩）を浸み込ませたものであり、ア
ノード２及びカソード３は、金属粉末板である。これら
は、小型の燃料電池では、それそれ単体の焼結板として
外部で成形・焼結した後、電池内に組み込んでいたが、
燃料電池の大型化、大出力化につれ、大面積の薄板（例
えば約１ｍ2 以上、厚さ１ｍｍ前後）の製造と組立を容
易にするために電池内含浸法が創案され実施されてい
る。The above-mentioned tile 1 is a ceramic powder plate in which an electrolyte (molten carbonate) is impregnated, and the anode 2 and the cathode 3 are metal powder plates. In small fuel cells, these were molded and sintered externally as individual sintered plates, and then incorporated into the cells.
With the increase in size and output of fuel cells, an in-cell impregnation method has been devised and implemented in order to facilitate the manufacture and assembly of large-area thin plates (for example, about 1 m 2 or more, about 1 mm in thickness).
【０００４】この方法では、タイル１、アノード２、及
びカソード３を、所定の粉末とバインダを混合して可撓
性のある薄板に成形し、これを用いて燃料電池を組み立
てる。この状態で、燃料電池内でタイル、アノード、及
びカソードが互いに積層された状態にあるが、タイル１
はバインダーを含んでおり、そのままでは、燃料電池と
して機能しない。この、タイル１は、電解質及び電解質
保持材の粉末にバインダ等の有機物を加えてシート状に
したものである。In this method, a tile 1, an anode 2, and a cathode 3 are formed into a flexible thin plate by mixing a predetermined powder and a binder, and a fuel cell is assembled using the thin plate. In this state, the tile, the anode, and the cathode are stacked on each other in the fuel cell.
Contains a binder and does not function as a fuel cell as it is. The tile 1 is a sheet formed by adding an organic substance such as a binder to the powder of the electrolyte and the electrolyte holding material.
【０００５】電池内含浸法では、燃料電池の組立後、最
初の昇温時にバインダを熱分解等で除去して所定の粉末
のみを残す工程（以下、脱脂工程という）が採用され
る。この工程では、図５に模式的に示すように、燃料電
池を昇温し、その昇温の過程でバインダを完全に熱分解
等により除去し、更に昇温して電解質を溶かしてセラミ
ックス粉末やアノード及びカソードの粒子間の空隙に電
解質（溶融炭酸塩）を溶融・含浸させて、電池として機
能する各セルを完成する。その後は、通常の燃料電池と
して用いられる。[0005] In the in-cell impregnation method, after assembling the fuel cell, a step of removing the binder by thermal decomposition or the like at the first temperature rise to leave only a predetermined powder (hereinafter, referred to as a degreasing step) is employed. In this step, as schematically shown in FIG. 5, the temperature of the fuel cell is raised, the binder is completely removed by thermal decomposition or the like in the process of raising the temperature, and the temperature is further raised to dissolve the electrolyte to make the ceramic powder or the like. An electrolyte (molten carbonate) is melted and impregnated into the gap between the anode and cathode particles to complete each cell functioning as a battery. Thereafter, it is used as a normal fuel cell.
【０００６】[0006]
【発明が解決しようとする課題】上述したように、電池
内含浸法を用いる燃料電池では、最初の昇温過程におい
て、各部材のバインダを除去する脱脂工程がある。この
脱脂工程では、バインダの酸化又は熱分解を促進しかつ
発生したガスをスムースに除去して脱脂反応を円滑に進
めるために窒素／空気混合ガスを供給する必要がある。As described above, in the fuel cell using the in-cell impregnation method, there is a degreasing step for removing the binder of each member in the first heating process. In this degreasing step, it is necessary to supply a nitrogen / air mixed gas in order to promote the oxidation or thermal decomposition of the binder and smoothly remove the generated gas to smoothly advance the degreasing reaction.
【０００７】しかし、脱脂の進行状況を直接モニタする
手段が従来ないため、従来は経験的に電池温度から空気
／窒素比を決めていた。そのため、脱脂反応が激しい
時に酸素含有量が多いとバインダ自体の酸化反応が急激
に進み、異常昇温が生じて電池を激しく損傷させてしま
うことがある。また、逆に脱脂反応が低い時に酸素含
有量が少ないと、バインダの熱分解がほとんど進まず、
バインダがカーボン化して不良箇所ができてしまうこと
がある。更に、脱脂反応自体をモニタできないため、
脱脂工程をいくら長くしても部分的に脱脂が不完全な部
分が生じることがあり、この場合にはカーボン化と同様
に、その後所定の昇温を行っても完全なセルが形成でき
ず、これにより所定の電池性能が発揮できず、燃料電池
を短命化してしまうことがあった。そのため、従来の燃
料電池では、脱脂が完全に行われたかの把握が不可能で
あった。However, since there is no means for directly monitoring the progress of degreasing, the air / nitrogen ratio has conventionally been empirically determined from the battery temperature. Therefore, when the oxygen content is high when the degreasing reaction is intense, the oxidation reaction of the binder itself proceeds rapidly, and an abnormal temperature rise occurs, which may severely damage the battery. Conversely, if the oxygen content is low when the degreasing reaction is low, the thermal decomposition of the binder hardly progresses,
In some cases, the binder is carbonized and defective portions are formed. Furthermore, since the degreasing reaction itself cannot be monitored,
Even if the degreasing step is lengthened, a part where the degreasing is partially incomplete may occur. In this case, as in the case of carbonization, a complete cell cannot be formed even after a predetermined temperature rise, As a result, the predetermined cell performance cannot be exhibited, and the life of the fuel cell may be shortened. For this reason, it was impossible to determine whether or not the degreasing was completely performed in the conventional fuel cell.
【０００８】本発明は、かかる問題点を解決するために
創案されたものである。すなわち、本発明の目的は、燃
料電池の脱脂工程における脱脂の進行状況を直接モニタ
することができ、これにより、熟練者の経験に頼ること
なく、最適条件で脱脂用ガス粗成を変化させ、カーボン
化することなくバインダを確実に除去することができ、
かつ脱脂の完了を客感的に把握することができる、脱脂
モニタ装置を備えた燃料電池発電設備を提供することに
ある。The present invention has been made to solve such a problem. That is, an object of the present invention is to directly monitor the progress of degreasing in a degreasing step of a fuel cell, thereby changing the degreasing gas composition under optimum conditions without relying on the experience of a skilled worker. The binder can be reliably removed without carbonization,
Degreasing, and the completion of degreasing can be grasped in a user-friendly manner.
An object of the present invention is to provide a fuel cell power generation facility provided with a monitor device .
【０００９】[0009]
【課題を解決するための手段】本発明の発明者は、従来
の脱脂工程時に臭い（脱脂臭）を伴うことに着眼した。
この臭いは、バインダの熱分解等により発生し、脱脂の
進行と共にピークを呈し、その後、徐々に減少してい
く。従って、臭気濃度は脱脂状態を示す１つのパラメー
タと考えることができ、この臭気濃度を何らかのセンサ
で検知し、脱脂状態を把握しながらガス組成を変化させ
ていくことにより目的を達成することが可能となる。本
発明はかかる新規の知見と着想に基づき創案されたもの
である。Means for Solving the Problems The inventor of the present invention has noticed that the conventional degreasing process involves an odor (degreasing odor).
This odor is generated due to thermal decomposition of the binder and the like, exhibits a peak as the degreasing progresses, and then gradually decreases. Therefore, the odor concentration can be considered as one parameter indicating the degreased state, and the object can be achieved by detecting the odor concentration with some sensor and changing the gas composition while grasping the degreased state. Becomes The present invention has been made based on such new knowledge and ideas.
【００１０】[0010]
【課題を解決するための手段】すなわち、本発明によれ
ば、電解質板（１）、アノード（２）及びカソード
（３）を、所定の粉末とバインダを混合し、薄板に成形
して燃料電池（１１）を組み立て、この燃料電池（１
１）の組立後、最初の昇温により酸化又は熱分解で前記
バインダを除去して所定の粉末のみを残す脱脂工程の脱
脂進行状況に応じて発生する脱脂臭の臭気濃度をモニタ
する脱脂モニタ装置を備えた燃料電池発電設備におい
て、前記燃料電池（１１）内に、酸素を含む不活性ガス
を供給するガス供給装置（１２）と、前記燃料電池（１
１）の下流に連結した排ガスライン（７）に連通され、
該排ガスライン（７）を流れる排ガスをサンプリング
し、ガス吸着による金属酸化物半導体の抵抗値変化を測
定して、この排ガスの臭気濃度にほぼ比例した出力を出
すことにより、この排ガス中の臭気濃度を検出する臭気
センサ（１４）と、前記不活性ガス中の酸素濃度を制御
する制御装置（１６）と、を備え、これにより燃料電池
（１１）を徐々に昇温し、前記臭気センサ（１４）で検
出された臭気濃度に応じて、該臭気濃度が高いときに不
活性ガス中の酸素濃度を低減し、逆に該臭気濃度が低い
ときに該酸素濃度を高めるように前記制御装置（１６）
で制御する、ことを特徴とする脱脂モニタ装置を備えた
燃料電池発電設備が提供される。That is, according to the present invention, an electrolyte plate (1), an anode (2) and a cathode are provided.
(3) is mixed with a predetermined powder and binder and formed into a thin plate
To assemble the fuel cell (11).
After assembling in 1), the temperature is raised by oxidation or thermal decomposition at the first temperature rise.
Removal of the degreasing process to remove the binder and leave only the specified powder
Monitors the odor concentration of degreasing odor generated according to the progress of fat
Fuel cell power plant equipped with a degreasing monitor
Te, to the fuel cell (11), a gas supply device for supplying an inert gas containing oxygen (12), said fuel cell (1
1) is connected to an exhaust gas line (7) connected downstream of
Exhaust gas flowing through the exhaust gas line (7) is sampled
And measure the change in resistance of the metal oxide semiconductor due to gas adsorption.
And output an output almost proportional to the odor concentration of this exhaust gas.
Thus, the fuel cell comprises an odor sensor (14) for detecting the odor concentration in the exhaust gas and a control device (16) for controlling the oxygen concentration in the inert gas.
The temperature of (11) is gradually increased, and when the odor concentration is high, an error is detected according to the odor concentration detected by the odor sensor (14).
Oxygen concentration in active gas is reduced, and the odor concentration is low.
The control device (16) may sometimes increase the oxygen concentration.
With a degreasing monitor device, characterized in that
A fuel cell power plant is provided.
【００１１】上記本発明の構成によれば、臭気センサ
（１４）として、ガス吸着による金属酸化物半導体の抵
抗値変化を測定するガスセンサを用いることにより、人
間が感じる臭いとほぼ同一の特性で臭気濃度を検出する
ことができる。従って、かかる臭気センサ（１４）によ
り、燃料電池の脱脂工程における脱脂の進行状況を直接
モニタすることができ、かつ脱脂の完了を臭気センサ
（１４）による臭気濃度から客観的に把握することがで
きる。According to the configuration of the present invention, the odor sensor is provided.
As (14) , by using a gas sensor that measures a change in the resistance value of the metal oxide semiconductor due to gas adsorption, the odor concentration can be detected with almost the same characteristics as the odor felt by humans. Therefore, the progress of the degreasing in the degreasing step of the fuel cell can be directly monitored by the odor sensor (14) , and the completion of the degreasing is determined by the odor sensor.
(14) due to be able to objectivity grasp from the odor concentration.
【００１２】なお、実際の運転では、臭気センサ（１
４）により臭気が検出できない時点で脱脂の完了と判断
することができるが、更に、臭気濃度は脱脂されたバイ
ンダの量に比例するので、脱脂時の臭気濃度のピーク値
や特性曲線における時間積分値と（電池の解体試験でわ
かる）脱脂状態との関係を予め把握しておけば、より確
実に脱脂の完全性の判断基準とすることができる。In actual operation, the odor sensor (1)
According to 4), it can be determined that degreasing is completed when no odor can be detected. However, since the odor concentration is proportional to the amount of the degreased binder, the peak value of the odor concentration at the time of degreasing and the time integration in the characteristic curve are determined. If the relationship between the value and the degreasing state (determined by a battery disassembly test) is grasped in advance, it can be more reliably used as a criterion for determining the completeness of degreasing.
【００１３】また、本発明によれば、臭気センサ（１
４）で検出された臭気濃度に応じて不活性ガス中の酸素
濃度を制御することにより、熟練者の経験に頼ることな
く、最適条件で脱脂用ガス粗成を変化させ、カーボン化
することなくバインダを確実に除去することができる。
この場合、本発明の好ましい実施形態によれば、前記制
御装置（１６）により、臭気濃度の高いときに酸素濃度
を低減するのがよい。この制御により、脱脂反応が激し
い時には酸素濃度を下げてバインダ自体の酸化反応を抑
制して、異常昇温等を防止することができ、逆に脱脂反
応が低い時には酸素濃度を高めて、バインダの酸化及び
熱分解を促進し、バインダのカーボン化を防止すること
ができる。Further, according to the present invention, the odor sensor (1)
By controlling the oxygen concentration in the inert gas according to the odor concentration detected in 4) , without changing the degreasing gas composition under optimum conditions without relying on the experience of a skilled person, without carbonizing The binder can be reliably removed.
In this case, according to a preferred embodiment of the present invention, the control device (16) preferably reduces the oxygen concentration when the odor concentration is high. By this control, when the degreasing reaction is intense, the oxygen concentration is reduced to suppress the oxidation reaction of the binder itself, and abnormal temperature rise can be prevented. Conversely, when the degreasing reaction is low, the oxygen concentration is increased to increase the binder concentration. Oxidation and thermal decomposition can be promoted, and carbonization of the binder can be prevented.
【００１４】[0014]
【発明の実施の形態】以下、本発明の好ましい実施形態
を図面を参照して説明する。なお、各図において共通す
る部分には同一の符号を付し、重複した説明を省略す
る。図１は、本発明の燃料電池の脱脂モニタ装置の全体
構成図である。この図において、本発明の脱脂モニタ装
置１０は、燃料電池１１内に酸素を含む不活性ガスを供
給するガス供給装置１２と、燃料電池１１を通過したガ
ス中の臭気濃度を検出する臭気センサ１４と、不活性ガ
ス中の酸素濃度を制御する制御装置１６とを備える。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below with reference to the drawings. In addition, the same reference numerals are given to the common parts in the respective drawings, and the duplicate description will be omitted. FIG. 1 is an overall configuration diagram of a degreasing monitoring device for a fuel cell according to the present invention. 1, a degreasing monitor 10 of the present invention includes a gas supply device 12 for supplying an inert gas containing oxygen into a fuel cell 11 and an odor sensor 14 for detecting an odor concentration in the gas passing through the fuel cell 11. And a control device 16 for controlling the oxygen concentration in the inert gas.
【００１５】図１において、ガス供給装置１２は、燃料
電池１１に窒素ガスを供給する流量調節弁１２ａと空気
を供給する流量調節弁１２ｂからなり、流量調節弁１２
ａ，１２ｂの開度調節により不活性ガス中の酸素濃度を
調節できるようになっている。また、燃料電池１１の排
ガスライン７は、脱脂中には図示しないフレアスタック
に導かれ、燃焼処理される。In FIG. 1, a gas supply device 12 comprises a flow control valve 12a for supplying nitrogen gas to the fuel cell 11 and a flow control valve 12b for supplying air.
The oxygen concentration in the inert gas can be adjusted by adjusting the opening degrees of a and 12b. Further, the exhaust gas line 7 of the fuel cell 11 is guided to a flare stack (not shown) during degreasing, and is subjected to combustion processing.
【００１６】臭気センサ１４は、排ガスライン７に連通
し、このラインを流れる排ガスをサンプリングし、その
臭気を感知するようになっている。この臭気センサ１４
は、後述するように、好ましくはガス吸着による金属酸
化物半導体の抵抗値変化を測定して臭気濃度にほぼ比例
した出力を出すガスセンサである。また図１において、
１７は解析装置であり、解析装置１７と制御装置１６に
より、臭気センサ１４で検出された臭気濃度に応じて不
活性ガス中の酸素濃度を制御するようになっている。こ
の制御装置１６は、臭気濃度の高いときに酸素濃度を低
減し、即ち脱脂反応が激しい時には酸素濃度を下げてバ
インダ自体の酸化反応を抑制して、異常昇温等を防止す
ることができ、逆に臭気濃度の低いとき、即ち脱脂反応
が低い時には酸素濃度を高めて、バインダの酸化及び熱
分解を促進し、バインダのカーボン化を防止する。 The odor sensor 14 communicates with the exhaust gas line 7, sampling the exhaust gas flowing through the line, the
It is designed to sense odor . This odor sensor 14
Is a gas sensor that preferably measures a change in resistance value of a metal oxide semiconductor due to gas adsorption and outputs an output substantially proportional to the odor concentration, as described later. In FIG. 1,
Reference numeral 17 denotes an analyzer, which controls the oxygen concentration in the inert gas in accordance with the odor concentration detected by the odor sensor 14 by the analyzer 17 and the controller 16. This
Control device 16 lowers the oxygen concentration when the odor concentration is high.
If the degreasing reaction is severe, reduce the oxygen concentration
Suppresses the oxidation reaction of the inductor itself to prevent abnormal temperature rise, etc.
On the contrary, when the odor concentration is low,
When the temperature is low, increase the oxygen concentration to
Promotes decomposition and prevents carbonization of the binder.
【００１７】図２は、臭気センサの原理図である。この
図において、（Ａ）はガス検知素子の拡大図であり、
（Ｂ）は基本回路、（Ｃ）は出力特性図である。（Ａ）
に示すようにガス検知素子は、金属酸化物半導体と白金
線コイルからなる。白金線コイルに流れる電流によって
約３００〜４５０℃に保たれた金属酸化物半導体が可燃
性ガスのような電子供与性ガスを吸着すると、その電子
濃度が増し半導体の熱伝導度が向上し、その結果、放熱
量が増し、半導体の温度が下がって白金線の抵抗が低下
する。この抵抗変化を（Ｂ）のブリッジ回路で検出し
て、（Ｃ）のように臭気濃度にほぼ比例した出力を得る
ようになっている。FIG. 2 shows the principle of the odor sensor. In this figure, (A) is an enlarged view of the gas detection element,
(B) is a basic circuit, and (C) is an output characteristic diagram. (A)
As shown in (1), the gas detection element includes a metal oxide semiconductor and a platinum wire coil. When a metal oxide semiconductor maintained at about 300 to 450 ° C. by an electric current flowing through a platinum wire coil adsorbs an electron-donating gas such as a flammable gas, the electron concentration increases, and the thermal conductivity of the semiconductor improves. As a result, the heat radiation increases, the temperature of the semiconductor decreases, and the resistance of the platinum wire decreases. This change in resistance is detected by the bridge circuit (B), and an output substantially proportional to the odor concentration is obtained as shown in (C).
【００１８】図３は、脱脂時における臭気濃度の実際の
計測例である。この図において、横軸は時間、縦軸は温
度と臭気濃度であり、図中の上の曲線は電池部材温度
（電池温度に相当する）、下の曲線は臭気センサの出力
カーブ（臭気トレンド）である。この図から、図２に示
した臭気センサ１４を用いて、燃料電池の脱脂工程で発
生する臭気をこのセンサで検知し、脱脂状態を把握でき
ることがわかる。FIG. 3 is an example of actual measurement of the odor concentration at the time of degreasing. In this figure, the horizontal axis is time, the vertical axis is temperature and odor concentration, the upper curve in the figure is the battery member temperature (corresponding to the battery temperature), and the lower curve is the output curve of the odor sensor (odor trend). It is. From this figure, it can be understood that the odor sensor 14 shown in FIG. 2 can be used to detect the odor generated in the degreasing step of the fuel cell and to grasp the degreasing state.
【００１９】上述したように、本発明の構成によれば、
臭気センサ１４として、ガス吸着による金属酸化物半導
体の抵抗値変化を測定するガスセンサを用いることによ
り、人間が感じる臭いとほぼ同一の特性で臭気濃度を検
出することができる。従って、かかる臭気センサ１４に
より、燃料電池の脱脂工程における脱脂の進行状況を直
接モニタすることができ、かつ脱脂の完了を臭気センサ
による臭気濃度から客感的に把握することができる。As described above, according to the configuration of the present invention,
By using, as the odor sensor 14, a gas sensor that measures a change in the resistance value of the metal oxide semiconductor due to gas adsorption, the odor concentration can be detected with almost the same characteristics as the odor felt by humans. Therefore, the progress of the degreasing in the degreasing step of the fuel cell can be directly monitored by the odor sensor 14, and the completion of the degreasing can be grasped from the odor concentration by the odor sensor.
【００２０】なお、本発明は上述した実施形態に限定さ
れず、本発明の要旨を逸脱しない範囲で種々変更できる
ことは勿論である。It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that various changes can be made without departing from the spirit of the present invention.
【００２１】[0021]
【発明の効果】上述したように、本発明の燃料電池の脱
脂モニタ装置は、燃料電池の脱脂工程における脱脂の進
行状況を直接モニタすることができ、これにより、熟練
者の経験に頼ることなく、最適条件で脱脂用ガス粗成を
変化させ、カーボン化することなくバインダを確実に除
去することができ、かつ脱脂の完了を客感的に把握する
ことができる、等の優れた効果を有する。As described above, the fuel cell degreasing monitoring apparatus of the present invention can directly monitor the progress of degreasing in the fuel cell degreasing step, and thus can rely on the experience of a skilled person. It has excellent effects such as changing the degreasing gas composition under optimal conditions, reliably removing the binder without carbonization, and being able to objectively grasp the completion of degreasing. .
【図１】本発明の燃料電池の脱脂モニタ装置の全体構成
図である。FIG. 1 is an overall configuration diagram of a fuel cell degreasing monitoring device of the present invention.
【図２】臭気センサの原理図である。FIG. 2 is a principle diagram of an odor sensor.
【図３】脱脂時における臭気濃度の計測例である。FIG. 3 is a measurement example of an odor concentration at the time of degreasing.
【図４】燃料電池の模式的構成図である。FIG. 4 is a schematic configuration diagram of a fuel cell.
【図５】従来の燃料電池の昇温例である。FIG. 5 is an example of a temperature rise of a conventional fuel cell.
１ 電解質板（タイル） ２ 燃料極（アノード） ３ 空気極（カソード） ４ 単セル ５ バイポーラプレート（セパレータ） ６ 積層電池（スタック） ７ 排ガスライン １０ 脱脂モニタ装置 １１ 燃料電池 １２ ガス供給装置 １２ａ，１２ｂ 流量調節弁 １４ 臭気センサ １６ 制御装置 １７ 解析装置 Reference Signs List 1 electrolyte plate (tile) 2 fuel electrode (anode) 3 air electrode (cathode) 4 single cell 5 bipolar plate (separator) 6 laminated battery (stack) 7 exhaust gas line 10 degreasing monitor device 11 fuel cell 12 gas supply device 12a, 12b Flow control valve 14 Odor sensor 16 Control device 17 Analysis device
Claims (1)
ソード（３）を、所定の粉末とバインダを混合し、薄板
に成形して燃料電池（１１）を組み立て、この燃料電池
（１１）の組立後、最初の昇温により酸化又は熱分解で
前記バインダを除去して所定の粉末のみを残す脱脂工程
の脱脂進行状況に応じて発生する脱脂臭の臭気濃度をモ
ニタする脱脂モニタ装置を備えた燃料電池発電設備にお
いて、 前記 燃料電池（１１）内に、酸素を含む不活性ガスを供
給するガス供給装置（１２）と、前記 燃料電池（１１）の下流に連結した排ガスライン
（７）に連通され、該排ガスライン（７）を流れる排ガ
スをサンプリングし、ガス吸着による金属酸化物半導体
の抵抗値変化を測定して、この排ガスの臭気濃度にほぼ
比例した出力を出すことにより、この排ガス中の臭気濃
度を検出する臭気センサ（１４）と、前記 不活性ガス中の酸素濃度を制御する制御装置（１
６）と、を備え、 これにより燃料電池（１１）を徐々に昇温し、前記臭気
センサ（１４）で検出された臭気濃度に応じて、該臭気
濃度が高いときに不活性ガス中の酸素濃度を低減し、逆
に該臭気濃度が低いときに該酸素濃度を高めるように前
記制御装置（１６）で制御する、ことを特徴とする脱脂
モニタ装置を備えた燃料電池発電設備。1. An electrolyte plate (1), an anode (2) and a capacitor.
Sword (3) is prepared by mixing the powder and binder
And the fuel cell (11) is assembled.
After assembling (11), the first temperature rise causes oxidation or thermal decomposition
Degreasing step of removing the binder and leaving only a predetermined powder
The odor concentration of the degreasing odor generated according to the progress of degreasing
Fuel cell power generation equipment equipped with a degreasing monitor
There are, to the fuel cell (11), a gas supply device for supplying an inert gas containing oxygen (12), the exhaust gas line which is connected downstream of the fuel cell (11)
(7), the exhaust gas flowing through the exhaust gas line (7).
Metal oxide semiconductor by gas sampling
Of the odor concentration of this exhaust gas
By issuing a proportional output, the odor sensor (14) for detecting the odor concentration of the exhaust gas, a control device for controlling the oxygen concentration of the inert gas (1
6), comprising a, thereby the fuel cell (11) the temperature was gradually raised, depending on the odor concentration detected by the odor sensor (14),該臭gas
When the concentration is high, reduce the oxygen concentration in the inert gas,
Before increasing the oxygen concentration when the odor concentration is low
Degreasing controlled by the controller (16).
Fuel cell power generation equipment equipped with a monitoring device .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09299799A JP3132653B2 (en) | 1997-10-31 | 1997-10-31 | Fuel cell power plant with degreasing monitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09299799A JP3132653B2 (en) | 1997-10-31 | 1997-10-31 | Fuel cell power plant with degreasing monitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11135141A JPH11135141A (en) | 1999-05-21 |
| JP3132653B2 true JP3132653B2 (en) | 2001-02-05 |
Family
ID=17877083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09299799A Expired - Fee Related JP3132653B2 (en) | 1997-10-31 | 1997-10-31 | Fuel cell power plant with degreasing monitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3132653B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101893413B1 (en) * | 2016-12-21 | 2018-08-31 | (주)센코 | Odor measurement device |
-
1997
- 1997-10-31 JP JP09299799A patent/JP3132653B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11135141A (en) | 1999-05-21 |
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