JP3813391B2 - Solid polymer fuel cell power generator and method of operating the same - Google Patents

Solid polymer fuel cell power generator and method of operating the same Download PDF

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JP3813391B2
JP3813391B2 JP27319999A JP27319999A JP3813391B2 JP 3813391 B2 JP3813391 B2 JP 3813391B2 JP 27319999 A JP27319999 A JP 27319999A JP 27319999 A JP27319999 A JP 27319999A JP 3813391 B2 JP3813391 B2 JP 3813391B2
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stop valve
temperature
fuel cell
burner
combustion gas
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JP2001093550A (en
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正俊 田中
倫三 三好
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Toshiba Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01B—BOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
    • B01B1/00—Boiling; Boiling apparatus for physical or chemical purposes ; Evaporation in general
    • B01B1/005—Evaporation for physical or chemical purposes; Evaporation apparatus therefor, e.g. evaporation of liquids for gas phase reactions

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Description

【０００１】
【発明の属する技術分野】
本発明は、運転温度が水の沸点以下である固体高分子型燃料電池発電装置に係り、特に、燃料改質に水蒸気と空気などの酸素を含むガスを使用する固体高分子型燃料電池発電装置の構成とその運転方法に関するものである。
【０００２】
【従来の技術】
燃料電池発電装置とは、連続して供給される流体を原料に電気化学反応を行うことにより、化学エネルギーを直接電気エネルギーに変換する発電装置である。その基本的な機器構成を図２６に示す。図に示すように燃料電池発電装置の主要構成機器として、燃料電池１、改質器２、一酸化炭素変成器３、排気ガスバーナー４、水凝縮器５が設けられている。
【０００３】
燃料電池１はイオン伝導性の電解質層とその両面に配置される燃料極１１及び酸化剤極１２を基本構成単位とし、通常はこれを複数単位積層して構成される。燃料極１１に供給されるガスは水素を含有し、燃料電池１にて電力を発生する電気化学反応により水素は水に酸化される。この燃料電池１に供給される水素を含有するガスは改質器２にて製造される。
【０００４】
改質器２は改質触媒層２１を有し、ここで燃料を水蒸気とともに気相での触媒反応により改質し、水素、一酸化炭素、二酸化炭素、水を主成分とする水素リッチガスを提供する。燃料は水素原子及び炭素原子をそれぞれ少なくとも一個は含む分子から構成されている。
【０００５】
燃料には酸素原子は含んでもよいが窒素など水素や水との反応で塩基性化合物を生成し、酸性電解質層を用いた場合にこれを失活させるおそれがある原子、もしくは硫黄やハロゲンなど改質触媒などを被毒する可能性がある原子、金属元素など酸化物が不揮発性である原子を含む化合物は燃料として望ましくない。これらの濃度が低い物質を燃料として選定すると同時に、上記のような望ましくない物質が燃料に含まれている場合には少なくとも被毒などの影響を受けるおそれのある機器に至る前にこれらを除去する必要がある。燃料電池に好適な燃料として都市ガス、ＬＰＧ、メタノール、灯油などが挙げられる。
【０００６】
燃料の改質方法としては、水蒸気のみで行う水蒸気改質と、酸素もしくは空気を水蒸気と併用する部分酸化型水蒸気改質が代表的である。メタンを例にして改質器２での部分酸化型水蒸気改質反応を示す。
【０００７】
【化１】
ＣＨ4 ＋Ｈ2 Ｏ→ＣＯ＋３Ｈ2 …（１）
【化２】
ＣＨ4 ＋Ｏ2 →ＣＯ＋Ｈ2 Ｏ＋Ｈ2 …（２）
【化３】
ＣＯ＋Ｈ2 Ｏ→ＣＯ2 ＋Ｈ2 …（３）
反応（１）は−２０６kJ/molの吸熱反応、標準状態で反応（２）は＋２７８kJ/molの発熱反応で、ＣＯシフト反応と呼ばれる反応（３）は＋４１kJ/molの発熱反応である。水蒸気改質のみの改質器２では（１）及び（３）の反応のみがおこるため、トータルの改質反応は−１６５kJ/molの吸熱反応となり、ＣＨ4 あたり４つのＨ2 が生成する。
【０００８】
しかしながらＯ2 を含むガスのみを酸化剤として用いる狭義の部分酸化改質では、（２）及び（３）の反応からトータルの熱収支は＋３１９kJ/molの発熱反応となるが、ＣＨ4 当たり２つのＨ2 しか生成しない。水とＯ2 の双方を改質に使用する部分酸化型水蒸気改質での熱収支は前記２例の中間となり、Ｏ2 ／ＣＨ4 ＝０．３４で熱的にバランスし、この場合のＣＨ4 当たりのＨ2 生成量は３．３である。Ｏ2 量がこのバランス値より大きい場合には改質反応でのトータル熱収支は発熱となりＣＨ4 当たりのＨ2 生成量は３．３より減少し、効率は低下する。逆にこの値より小さい場合には吸熱となり、ＣＨ4 当たりのＨ2 生成量は３．３より増大し、効率は上昇する。
【０００９】
純然たる水蒸気改質反応では大きな吸熱反応となるので、反応の維持のために外部から大量の熱を供給する必要がある。したがって、改質器２の加熱を目的として複雑な機構が不可欠となり、改質器２は一般に高価となる。一方、部分酸化型水蒸気改質反応では導入するＯ2 量などを調整することで改質器２の機構を簡素化でき安価で済むが、その反面、Ｈ2 の生成効率は水蒸気改質に比較して劣ることになる。
【００１０】
改質触媒層２１に使用する改質触媒としては例えば日産ガードラー社製Ｇ−９０を初めとするニッケル系触媒などが挙げられるが、これ及び後段で挙げるＣｕ−ＺｎＯ系低温一酸化炭素変成触媒はＣｌなどにより被毒する。このため、改質に使用される水蒸気は蒸留水もしくはイオン交換水から発生させることが望ましい。
【００１１】
一酸化炭素は燃料電池１の燃料極１１にて電気化学反応を起こす触媒を被毒するため、可能な限り濃度を低下させることが必要である。改質器２でもＣＯシフト反応は進行するが、改質器２出口でのＣＯ濃度は数パーセントオーダーであり、燃料極１１の触媒被毒を避ける上では充分ではない。そこで、改質器２と燃料電池燃料極１１の中間に一酸化炭素変成器３が設置されている。この一酸化炭素変成器３の働きにより一酸化炭素濃度を望ましいレベルにまで低減することができる。
【００１２】
多くの場合、一酸化炭素変成器３は目標とする一酸化炭素濃度に応じ、複数の一酸化炭素変成器を直列に設置して構成される。一酸化炭素変成器３の例としては、低温一酸化炭素変成器３１と選択酸化式一酸化炭素除去器３２とが挙げられる。低温一酸化炭素変成器３１はＣＯシフト反応を促進する触媒からなる低温一酸化炭素変成触媒層を有しており、ＣＯシフト反応の促進によりＣＯ濃度を低下させるものである。低温一酸化炭素変成器３１ではＣＯのシフトに伴って水素が生成するので水素の生成効率の上では有利であるが、反応が平衡反応であるため、出口の一酸化炭素濃度は出口ガス温度での平衡濃度に制約されることになる。一方、選択酸化式一酸化炭素除去器３２は、充填された触媒上での水素リッチガス中の一酸化炭素と酸素との選択酸化反応により一酸化炭素濃度を低減する機器である。この選択酸化式一酸化炭素除去器３２での反応は不可逆反応であるためシフト反応よりも一酸化炭素濃度を低減することが可能である。但し、一酸化炭素が水素生成に利用されないので、水素の生成効率の上では不利である。加えて一酸化炭素除去量を確保するため一酸化炭素に対して過剰量の酸素が供給され、水素の一部を酸化するので水素の生成効率は更に低くなる。このように一酸化炭素濃度が高い場合に選択酸化式一酸化炭素除去を行うことは水素生成効率の上で不利である。そのため、選択酸化式一酸化炭素除去は通常、数千ｐｐｍの一酸化炭素濃度を数十ｐｐｍ以下に低下させる場合に使用される。
【００１３】
ところで、前記低温一酸化炭素変成器３１におけるＣＯシフト反応は低温で平衡上有利であるため、反応温度は３００℃以下、さらに言えば２００℃程度が望ましい。これに対して改質器２の運転温度は最低４００℃、通常６００℃以上の高温なので、改質器２から出た水素リッチガスを低温一酸化炭素変成器３１に供給する際、水素リッチガスの温度を低下させなくてはならない。そのため、改質器２と低温一酸化炭素変成器３１の間には水素リッチガス冷却器２２が設置されている。
【００１４】
また、前記都市ガス、ＬＰＧ、灯油などの燃料には、有機化合物の形で微量の硫黄分が含まれており、上記の反応器に使用される各種触媒を、特に低温で被毒することがある。このような触媒の一例としてＣｕ−ＺｎＯ系低温一酸化炭素変成触媒が挙げられる。そのため、低温一酸化炭素変成器３１の前段において、硫黄分を除去する脱硫器３３が設けられている。一酸化炭素と異なり、硫黄分を化学反応によって非被毒性の気体に転換することはできないので、通常、脱硫器３３の前段で含硫黄有機化合物をＨ2 Ｓガス、ＳＯ2 ガスなどに変化させた上で脱硫器３３にて吸収材層による吸収除去を行うようになっている。このような脱硫器３３吸収材層の例としてはＺｎＯなどが知られている。
【００１５】
脱硫器３３は改質器２の前段に置かれる場合と、改質器２の後段に置かれる場合とがある。脱硫器３３が改質器２の前段に置かれる場合、燃料中の含硫黄有機化合物をＨ2 Ｓなどに変化させるための反応器を更にその前段に設置する必要があり、機器が煩雑で小型化が困難になるが、改質触媒層２１の硫黄被毒を避ける上ではより確実である。これに対して脱硫器３３が改質器２の後段に置かれる場合、含硫黄有機化合物は特段の前処理無しで改質器２にてＨ2 Ｓに変化するため、機器の簡素化・低コスト化を図ることができる。Ｎｉ系などの改質触媒も高温では硫黄被毒の影響は小さく、このような形態は可能だが、脱硫器３３の代表的な吸収材であるＺｎＯは高温で揮発性であるため、脱硫器３３は水素リッチガス冷却器２２と低温一酸化炭素変成器３１の間に設置されることが望ましい。図２６では脱硫器３３は水素リッチガス冷却器２２と低温一酸化炭素変成器３１の間に設置されているが、上記のように改質器２の上流でもよい。
【００１６】
上記のような手段により有害な不純物を除去された水素リッチガスは燃料電池１に入り、燃料電池燃料極１１を通過する間に燃料電池酸化剤極１２を流動する空気中に含まれる酸素との間に下記の電気化学反応が発生し、電力と熱が生成すると共に、その含有する水素が消費される。生成した電力は直流であるが、通常イナバーターを介して交流に変換され、需要端に供給される。また、生成熱は燃料電池冷却媒体径路１３を流通する冷却媒体により燃料電池の外に排出される。
【００１７】
【化４】
燃料極：２Ｈ2 → ４Ｈ+ ＋４ｅ- …（４）
【化５】
酸化剤極：Ｏ2 ＋４ＨＨ+ ＋４ｅ- → ２Ｈ2 Ｏ…（５）
効率の面では電気化学反応による水素リッチガス中の水素の利用率が高いほうが良いが、利用率が高くなり過ぎると水素リッチガス流量の変動や燃料電池１内での水素リッチガス配流の不均一などの要因により燃料欠乏に陥る危険がある。そのため、水素利用率は８０％以下にすることが望ましい。
【００１８】
燃料電池燃料極１１に供給された可燃ガスの一部は未反応のまま燃料電池燃料極１１から排出される。かかる未反応可燃ガスには、電気化学反応に利用されなかった水素のほか、改質器２で改質されなかった燃料や改質器２もしくは一酸化炭素変成器３１で副生した炭化水素がありうる。これらをそのまま環境に排出することは安全上問題が有る。そこで、これらを燃焼するために排気ガスバーナー４が設けられている。排気ガスバーナー４の酸化剤としては燃料電池酸化剤極１２排出ガスの一部もしくは大気を使用することが一般的である。排気ガスバーナー４の燃焼ガスは高温であるため、機器の加熱源として使用することができる。
【００１９】
排気ガスバーナー４の燃焼ガス及びバーナー４で使用されなかった燃料電池酸化剤極１２の排出ガスは、水素リッチガス製造のため添加された水及び燃料電池１及び排気ガスバーナー４で消費された燃料から発生した水を含んでいる。この水を回収するために排気ガス出口に水凝縮器５が設置されている。
【００２０】
以上のような構成を有する燃料電池発電装置は、燃料電池の電解質層によっていくつかのタイプに分かれている。すなわち、燐酸を使用する燐酸型燃料電池、アルカリ水溶液を使用するアルカリ型燃料電池、溶融炭酸塩を使用する溶融炭酸塩型燃料電池、固体セラミックス電解質を用いる固体電解質型燃料電池、固体高分子電解質を使用する固体高分子電解質型燃料電池などが挙げられる。これらのうちで固体高分子電解質型燃料電池は、水の沸点以下の比較的低温で運転されるために比較的短時間で起動可能であり、かつ高出力密度が期待され、更には燐酸型に見られるような電解質の減損がないことから、近年特に注目を集めている。
【００２１】
【発明が解決しようとする課題】
しかしながら、固体高分子電解質型燃料電池においては発電装置としての効率を上昇させるにあたり、次のような解決すべき課題がある。発電効率は燃料からのＨ2 の生成効率に依存するが、これを高めるためには改質器２での反応を水蒸気改質に近づけなくてはならない。しかしそれは改質反応が吸熱側に傾くことを意味し、外部からの熱供給が必要となる。発電装置内で最大の発熱量を示す機器は燃料電池１であるが、運転温度が通常水の沸点以下の低温であるため、通常６００℃以上の高温で運転される改質器２への熱供給には利用できない。従って改質器２への熱供給には、他の加熱源を用いる必要がある。そこで従来より、排気ガスバーナー４の使用が検討されている。
【００２２】
また、発電装置内には改質器２に供給する水蒸気を発生させる水蒸発器が設置されるが、この水蒸発器の加熱源としても排気ガスバーナー４が期待されている。これは燃料電池１の運転温度が水の沸点以下であるため、燃料電池１の発熱が水蒸気の発生にも使用できないからである。
【００２３】
このように排気ガスバーナー４に対する熱源としての需要は大きいが、その発熱は燃料電池１の発熱の高々５０〜６０％程度しかない。通常、燃料電池１は、その燃料極１１入口におけるＨ2 量を１００とすると８０を発電に消費し、その５０〜６０％程度を電気エネルギーに、残余の４０〜５０％程度を熱に変換する。従って燃料電池１の発熱は燃料極１１入口におけるＨ2 量に換算して３２〜４０程度である。しかし、排気ガスバーナー４で燃焼されるＨ2 量は発電で消費されなかった２０のみであり、燃料電池１の発熱に比較して少ない。このため、排気ガスバーナー４から発生する熱量の効率的な運用が要請されていた。
【００２４】
また、燃料電池発電装置が起動するためには各機器が機能を発揮する温度にまで昇温させる必要がある。燃料極１１の触媒は前述したように一酸化炭素により被毒するが、これは触媒表面に一酸化炭素が吸着し触媒活性サイトを被覆することが原因である。従って、運転前に燃料極１１に流通するガス中に一酸化炭素が含まれているとこれにより触媒活性サイトが被覆され、運転開始時には燃料極１１の触媒が重被毒状態に陥る可能性がある。運転中の水素リッチガス中に含まれる一酸化炭素を低減させることは勿論であるが、起動前に燃料極１１に流通するガスについても一酸化炭素を低減させなくてはならない。そのため、改質器２への原料ガス導入及び発電開始に先立ち、低温一酸化炭素変成器３１及び選択酸化式一酸化炭素除去器３２を充分運転可能な温度に昇温させる必要がある。
【００２５】
さらに、改質反応を開始するためにも改質触媒層２１はある程度の温度まで昇温する必要がある。ニッケル系改質触媒を例に取ると、運転温度範囲は４００℃〜１３００℃とされているので、４００℃程度までの昇温は必要と考えられる。改質触媒が燃焼触媒として作用し、原料ガスの燃焼による昇温が期待できるとしても、発火条件が整う温度まで改質触媒層２１を昇温する必要があるので、改質器２への原料ガス導入に先立って改質器２を充分運転可能な温度にまで昇温する必要がある。
【００２６】
また、水蒸発器に関して言えば、これを昇温させなければ水蒸気が発生しない。部分酸化型水蒸気改質反応では原料ガスに水蒸気を使用しなくとも水素生成が可能であるが、通常運転時の水蒸気導入を前提とした場合より投入燃料に対する発熱量が著しく増大するため、改質触媒層２１が高熱で損傷する可能性がある。ニッケル系改質触媒を例に取ると耐用温度は１３００℃であり、一時的にせよ局所的にせよこれ以上高温にすることは避ける必要がある。そのため、改質器２への原料ガス導入に先立ち、水蒸発器６１を昇温して水蒸気が発生可能な状態にしなくてはならない。
【００２７】
固体高分子型燃料電池以外のタイプ、例えば燐酸型燃料電池では各機器に流通する燃料電池冷却媒体を用いての昇温が可能であった。すなわち、低温一酸化炭素変成器３１においてＣｕ−ＺｎＯ系の低温一酸化炭素変成触媒を使用した場合、運転温度は約２００℃である。しかし、これは水の沸点以下である固体高分子型燃料電池の運転温度よりも高く、燃料電池冷却媒体を使ってこの温度まで昇温させることはできない。このように、固体高分子型燃料電池発電装置を起動するためには燃料電池冷却媒体を使用できず、新たな方法が求められている。さらには、発電装置全体の小型化と高効率化を図るために、各機器のコンパクト化や放熱損失の低減が要求されていた。
【００２８】
本発明は、以上のような従来技術の持つ課題を解消するために提案されたものであり、その主たる目的は、コンパクトで機器構成が簡素でありながら、停止状態から短時間で起動でき、かつ排熱を有効に回収する高効率の固体高分子型燃料電池発電装置及びその運転方法を提供することにある。
【００２９】
また、本発明の他の目的は、各機器のコンパクト化及び放熱損失の低減を実現し、装置全体の小型化とさらなる高効率化を図った固体高分子型燃料電池発電装置を提案することにある。
【００３０】
【課題を解決するための手段】
本発明は、上記の目的を達成するために提案されたものであり、水素を含むガスを燃料とし固体高分子を電解質として酸化剤極と燃料極を有する燃料電池と、燃料電池を経由して冷却媒体を循環させる燃料電池冷却媒体径路と、燃料電池冷却媒体径路の燃料電池上流から燃料電池冷却媒体を分岐しこれを燃料電池冷却媒体径路に燃料電池下流にて合流させる燃料処理系冷却媒体径路と、燃料電池冷却媒体径路で冷却媒体を循環させる冷却媒体循環ポンプと、これら冷却媒体から熱量を除去し冷却媒体の温度を調整する燃料電池冷却媒体冷却器と、燃料電池燃料極上流に設置され改質触媒層を有しこの改質触媒層において炭素原子と水素原子を分子中に少なくとも各々一個以上含む燃料及び酸素を含む気体及び水蒸気の混合気を水素リッチガスに改質する改質器と、水素リッチガス流路の改質器下流に設置され水素リッチガスと燃料処理系冷却媒体径路を流通する燃料電池冷却媒体との熱交換を行う水素リッチガス冷却器と、水素リッチガス冷却器下流に設置され低温一酸化炭素変成触媒層を有する低温一酸化炭素変成器と、低温一酸化炭素変成器上流に設置され吸収材層を有しこの吸収材層により燃料もしくは水素リッチガス中の硫黄分を吸収する脱硫器と、低温一酸化炭素変成器下流に設置され選択酸化式一酸化炭素除去触媒層を有する単数もしくは複数の選択酸化式一酸化炭素除去器と、燃料電池の燃料極からの排気ガスの全量と酸化剤極からの排気ガスの全量もしくは一部を混合して燃焼する排気ガスバーナーと、排気ガスバーナーの燃焼ガス及び酸化剤極の排気ガスの混合ガスから水を凝縮させる水凝縮器とが備えられた固体高分子型燃料電池発電装置において、次のような特徴を有している。
【００３１】
請求項１の発明は、改質器に供給する水蒸気を発生させる水蒸発器と、水蒸発器で発生した水蒸気を過熱する水蒸気過熱器と、改質器に供給する燃料を酸素を含むガスと混合した状態で加熱する燃料混合ガス予熱器とが設けられ、排気ガスバーナーからの燃焼ガスが、水蒸気過熱器、燃料混合ガス予熱器、水蒸発器、水凝縮器の順に通過するように燃焼ガス流路が形成されたことを特徴とする。
【００３２】
以上のような請求項１の発明では、燃料電池で消費されなかった可燃性物質を排気ガスバーナーで燃焼し、この燃焼ガスを水蒸気過熱器、燃料混合ガス予熱器、水蒸発器、水凝縮器と高温の機器から順に通過させることにより、排気ガスバーナーの燃焼熱を効率よく回収することができる。これらの機器の運転温度は、その出口温度が改質器に供給する反応ガス温度である、水蒸気過熱器が最も高く、次いで燃料混合ガス予熱器、熱交換後の排気ガス温度が水の沸点程度である水蒸発器、熱交換後の排気ガス温度が燃料電池排出ガスの露点を下回る水凝縮器の順で低下する。一方、効率の面では、部分酸化型改質器での発熱を抑制することが望ましく、そのためには原料ガスの温度を可能な限り上昇させることが望ましい。従って、熱回収のための高温ガスもこの順番に従って流通させることが効率の面で最も望ましい。
【００３３】
また、空気などの酸素を含んだガスと燃料との混合ガスを加熱する燃料混合ガス予熱器の運転温度は、水蒸気過熱器のそれより低く抑える必要があるが、これは水蒸気と共存しない状態で空気など酸素を含んだガスと燃料の混合ガスを加熱した場合には、水蒸気と共存した場合に比較してより低い温度で発火する可能性があるためである。
【００３４】
ところで、水蒸発器で必要な温度は水蒸気の過熱や燃料混合ガスの予熱に必要な温度より低いにもかかわらず熱量としては多いので、仮に燃料混合ガス予熱に先立って水蒸発を行うと、加熱源である排気ガスバーナーの燃焼ガス温度が下がり、燃料混合ガスの温度が上がらなくなって効率の面で不利である。本発明では水蒸発器と水蒸気過熱器とを分離しているため、このような効率面での不利を回避することができ、しかも流量制御が容易である。
【００３５】
請求項２の発明は、請求項１記載の固体高分子型燃料電池発電装置において、改質器の外筒部に水素リッチガス冷却器が設置され、改質器及び水素リッチガス冷却器が複合一体化されたことを特徴とする。
【００３６】
以上のような請求項２の発明では、改質器及び水素リッチガス冷却器を複合一体化させることで発電装置の体積を減少させることができる。また、フロー上連続している改質器と水素リッチガス冷却器の間の接続流路を極小化することができる。さらに、より高温で運転される改質器を、より低温で運転される水素リッチガス冷却器で包囲するため、改質器表面から大気への放熱損失を抑制する機能もある。
【００３７】
請求項３の発明は、請求項１または２記載の固体高分子型燃料電池発電装置において、排気ガスバーナーの外筒部に水蒸気過熱器が設置され、排気ガスバーナー及び水蒸気過熱器が複合一体化されたことを特徴とする。
【００３８】
請求項４の発明は、請求項３記載の固体高分子型燃料電池発電装置において、排気ガスバーナー及び水蒸気過熱器が複合一体化された機器の外筒部に混合ガス予熱器が設置され、排気ガスバーナーと水蒸気過熱器と混合ガス予熱器とが複合一体化されたことを特徴とする。
【００３９】
以上の請求項３または４の発明では、水蒸気過熱器もしくは燃料混合ガス予熱器を排気ガスバーナーと複合一体化させることで発電装置体積の減少が可能である。また、フローシークエンス上連続した排気ガスバーナーと水蒸気過熱器もしくは燃料混合ガス予熱器との間の接続流路を極小化できる。さらに、より高温で運転される排気ガスバーナーを、より低温で運転される水蒸気過熱器もしくは燃料混合ガス予熱器で囲むので、排気ガスバーナー表面から大気への放熱損失を抑えることができる。
【００４０】
請求項５の発明は、請求項２、３または４記載の固体高分子型燃料電池発電装置において、改質器外筒部に水素リッチガス冷却器と共に水蒸発器が設置され、改質器と水素リッチガス冷却器と水蒸発器とが複合一体化されたことを特徴とする。
【００４１】
上記の請求項５の発明では、改質器に水素リッチガス冷却器及び水蒸発器を複合一体化させることで、前記請求項２の発明の持つ作用効果に加えて、装置のコンパクト化をいっそう進めることができる。
【００４２】
請求項６の発明は、請求項１、２、３、４または５記載の固体高分子型燃料電池発電装置において、脱硫器が水素リッチガス流路の水素リッチガス冷却器と低温一酸化炭素変成器の中間に設置され、低温一酸化炭素変成器及び脱硫器が複合一体化されたことを特徴とする。
【００４３】
以上の請求項６の発明では、低温一酸化炭素変成器及び脱硫器を複合一体化させることにより、装置体積の減少、並びに低温一酸化炭素変成器における放熱損失の抑制を実現することができる。
【００４４】
請求項７の発明は、請求項１、２、３、４、５または６記載の固体高分子型燃料電池発電装置において、燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する第１の合流点が形成され、燃料混合ガス予熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、分岐点の下流に燃焼ガスが合流する第２の合流点が形成され、装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器、水凝縮器の順に通過するように構成され、かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置されたことを特徴とする。
【００４５】
以上の構成を有する請求項７の発明においては、装置起動時に起動バーナーからの燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器、水凝縮器の順に通過する。このことにより、改質器に原料となるガスが供給される前に予め各機器を充分高温に昇温することができ、しかも起動時に生成した一酸化炭素の吸着による燃料極触媒被毒を防止することができる。と同時に、燃料電池冷却媒体を昇温する。
【００４６】
また、改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層、すなわち燃料電池燃料極の上流に位置する機器については、水素リッチガスが流通する経路とは独立して起動バーナー燃焼ガスの流通経路を設置したので、燃料処理系の触媒層において高温・還元性雰囲気での使用が想定されていても、燃焼ガスの流通による酸化及び結露の心配がなく、活性低下が起こらず、起動前の還元操作も不要である。
【００４７】
請求項８の発明は、請求項７記載の固体高分子型燃料電池発電装置において、起動バーナーと第１の合流点の間に第１止め弁が設けられ、分岐点と燃料電池冷却媒体加熱器の間に第２止め弁が設けられ、選択酸化式一酸化炭素除去触媒層と第２の合流点の間に第３止め弁が設けられたことを特徴とする。
【００４８】
このような請求項８の発明では、流路の切替えを止め弁の開閉で行うので、起動バーナーの燃焼ガス流路と排気バーナーの燃焼ガス流路を共通化でき、機器を簡素化することができる。
【００４９】
請求項９の発明は、請求項８の発明にかかる固体高分子型燃料電池発電装置の運転方法であり、装置起動時でかつ水蒸発器温度、燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁、第２止め弁及び第３止め弁が開き、装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかの温度が予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第１止め弁が開いて第２止め弁及び第３止め弁が閉じ、第２止め弁及び第３止め弁が開いた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、第２止め弁及び第３止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて運転状態に移行し、運転時には第１止め弁、第２止め弁及び第３止め弁が閉じ、停止時には第１止め弁が閉じて第２止め弁及び第３止め弁が開くことを特徴とする。
【００５０】
請求項９の発明においては、以上のような運転方法を実施することにより、各機器をほぼ同調して所定の温度にまで昇温することができ、さらには過剰な昇温を防止することができる。
【００５１】
請求項１０の発明は、請求項８記載の固体高分子型燃料電池発電装置において、第２止め弁と第３止め弁の間の流路のいずれかの箇所に第２の分岐点が形成され、第２の分岐点には外気に開放される配管が接続され、この配管に第４止め弁が設けられたことを特徴とする。
【００５２】
請求項１１の発明は、請求項１０の発明にかかる固体高分子型燃料電池発電装置の運転方法であり、装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁、第２止め弁及び第３止め弁が開いて第４止め弁が閉じ、装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかが予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第２止め弁及び第３止め弁が閉じて第１止め弁及び第４止め弁が開き、第２止め弁及び第３止め弁が開いて第４止め弁が閉じた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、第２止め弁及び第３止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて第４止め弁が開いて運転状態に移行し、運転時には第１止め弁、第２止め弁及び第３止め弁が閉じて第４止め弁が開き、装置停止時には第２止め弁または第３止め弁の少なくとも一方と第４止め弁が開くことを特徴とする。
【００５３】
上記請求項１０及び１１の発明によれば、各機器をほぼ同調して所定の温度にまで昇温でき、過剰昇温を防ぐと共に、第４止め弁の働きにより起動バーナー燃焼ガス流路の減圧を防止することができる。
【００５４】
請求項１２の発明は、請求項１、２、３、４、５または６記載の固体高分子型燃料電池発電装置において、燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、燃料混合ガス予熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、大気中に出て、一方、分岐点にて分岐された残余の起動バーナーからの燃焼ガスは更に水蒸発器、水凝縮器の順に通過するように構成され、かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置されたことを特徴とする。
【００５５】
上記請求項１２の発明においては、装置起動時に起動バーナーからの燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過するまでは、前記請求項７の発明と同じであるが、それ以降熱交換に使用されることなく大気中に放出される点が異なっている。このような請求項１２の発明によれば、各機器を充分高温に昇温することができると同時に、簡易な装置を構築することができる。
【００５６】
請求項１３の発明は、請求項１２記載の固体高分子型燃料電池発電装置において、起動バーナーと合流点の間に第１止め弁が、分岐点と脱硫器吸収材層の間に第２止め弁が設けられたことを特徴とする。
【００５７】
請求項１４の発明は、請求項１３の発明にかかる固体高分子型燃料電池発電装置の運転方法であり、装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁及び第２止め弁が開き、装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかが予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第１止め弁が開いて第２止め弁が閉じ、第２止め弁が開いた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、第２止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて運転状態に移行し、運転時には第１止め弁及び第２止め弁が閉じることを特徴とする。
【００５８】
上記の請求項１３及び１４の発明では、請求項１２記載の固体高分子型燃料電池発電装置において、各機器をほぼ同調して所定の温度にまで昇温でき、過剰昇温を防ぎながら、装置の簡略化を図ることができる。
【００５９】
請求項１５の発明は、請求項１、２、３、４、５または６記載の固体高分子型燃料電池発電装置において、燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器、水蒸発器、燃料電池冷却媒体加熱器、水凝縮器の順に通過するように構成されたことを特徴とする。
【００６０】
以上の請求項１５の発明では、高温が必要な改質器の昇温及び昇温に多くの熱量を必要とする燃料電池冷却媒体加熱器や水蒸発器の加熱にのみ起動バーナー燃焼ガスを利用している。つまり、起動バーナー燃焼ガスによる昇温を選択的に実施することにより燃焼ガス流路をシンプルにし、装置の簡易化を進めることができる。
【００６１】
請求項１６の発明は、請求項１５記載の固体高分子型燃料電池発電装置において、起動バーナーと合流点の間に止め弁が設けられたことを特徴とする。
【００６２】
請求項１７の発明は、請求項１６の発明にかかる固体高分子型燃料電池発電装置の運転方法であり、装置起動時の水蒸発器温度が予め設定された目標温度に未達であれば止め弁が開き、止め弁が開いた状態で燃料電池冷却媒体加熱器温度が予め設定された最高限界温度に達した場合には、燃料電池冷却媒体冷却器が運転されて温度制御を行い、水蒸発器温度が予め設定された目標温度に達したら止め弁が閉じて運転状態に移行し、運転時には止め弁が閉じ、かつ装置起動時には脱硫器、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の温度がそれぞれ個別に電力によって加熱されることを特徴とする。
【００６３】
上記の請求項１６及び１７の発明では、請求項１５記載の固体高分子型燃料電池発電装置において、各機器の昇温及び過剰昇温の防止、さらには装置の簡略化を実現することができる。
【００６４】
請求項１８の発明は、改質器に供給する水蒸気を発生させる水蒸発器と、酸素を含むガスと燃料と水蒸発器で発生した水蒸気との混合ガスを過熱する燃料混合ガス過熱器とが設けられ、排気ガスバーナーからの燃焼ガスが、燃料混合ガス過熱器、水蒸発器、水凝縮器の順に通過するように燃焼ガス流路が形成されたことを特徴とする。
【００６５】
以上のような請求項１８の発明では、燃料電池で消費されなかった可燃性物質を排気ガスバーナーで燃焼し、この燃焼ガスを燃料混合ガス過熱器、及び水蒸発器、水凝縮器と高温の機器から順に通過させることにより、排気ガスバーナーの燃焼熱を効率よく回収することができる。また、請求項１８の発明においては、燃料を空気と混合するだけではなく、水蒸気と混合した状態で過熱するため、請求項１の発明に比べて改質器へ導入する反応ガス温度を高く設定することができる。さらには、酸素を含むガスの改質器への投入量を減らすことが可能である。
【００６６】
請求項１９の発明は、請求項１８記載の固体高分子型燃料電池発電装置において、改質器の外筒部に水素リッチガス冷却器が設置され、改質器及び水素リッチガス冷却器が複合一体化されたことを特徴とする。
【００６７】
以上のような請求項１９の発明では、改質器及び水素リッチガス冷却器を複合一体化させることで発電装置の体積を減少させることができ、改質器と水素リッチガス冷却器との接続流路の極小化と、改質器表面から大気への放熱損失の抑制を図ることができる。
【００６８】
請求項２０の発明は、請求項１８または１９記載の固体高分子型燃料電池発電装置において、排気ガスバーナーの外筒部に燃料混合ガス過熱器が設置され、排気ガスバーナー及び燃料混合ガス過熱器が複合一体化されたことを特徴とする。
【００６９】
以上の請求項２０の発明では、燃料混合ガス過熱器を排気ガスバーナーと複合一体化させることで発電装置体積の減少が可能である。また、排気ガスバーナーと燃料混合ガス過熱器との間の接続流路を極小化できる。さらに、排気ガスバーナーを燃料混合ガス過熱器で囲むことにより、排気ガスバーナー表面から大気への放熱損失を抑えることができる。
【００７０】
請求項２１の発明は、請求項１９または２０記載の固体高分子型燃料電池発電装置において、改質器外筒部に水素リッチガス冷却器と共に水蒸発器が設置され、改質器と水素リッチガス冷却器と水蒸発器とが複合一体化されたことを特徴とする。
【００７１】
上記の請求項２１の発明では、改質器に水素リッチガス冷却器及び水蒸発器を複合一体化させることで、前記請求項１９の発明の持つ作用効果をいっそう進めることができる。
【００７２】
請求項２２の発明は、請求項１８、１９、２０または２１記載の固体高分子型燃料電池発電装置において、脱硫器が水素リッチガス流路の水素リッチガス冷却器と低温一酸化炭素変成器の中間に設置され、低温一酸化炭素変成器及び脱硫器が複合一体化されたことを特徴とする。
【００７３】
以上の請求項２２の発明では、低温一酸化炭素変成器及び脱硫器を複合一体化させることにより、装置体積の減少、並びに低温一酸化炭素変成器における放熱損失の抑制を実現することができる。
【００７４】
請求項２３の発明は、請求項１８、１９、２０、２１または２２記載の固体高分子型燃料電池発電装置において、燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する第１の合流点が形成され、燃料混合ガス過熱器の下流に燃焼ガスが分れる分岐点が形成され、分岐点の下流に燃焼ガスが合流する第２の合流点が形成され、装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、次いで燃料混合ガス過熱器を通過した後、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過し、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器を通過するように構成され、かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置されたことを特徴とする。
【００７５】
以上の構成を有する請求項２３の発明は、前述した請求項７の発明と同様の作用効果を有している。すなわち、装置起動時に起動バーナーからの燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器、水凝縮器の順に通過する。このことにより、改質器に原料となるガスが供給される前に予め各機器を充分高温に昇温することができ、しかも起動時に生成した一酸化炭素の吸着による燃料極触媒被毒を防止することができる。と同時に、燃料電池冷却媒体を昇温する。
【００７６】
また、改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層、すなわち燃料電池燃料極の上流に位置する機器については、水素リッチガスが流通する経路とは独立して起動バーナー燃焼ガスの流通経路を設置したので、燃焼ガスの流通による酸化及び結露の心配がなく、活性低下が起こらず、かつ起動前に還元操作を行う必要もない。
【００７７】
請求項２４の発明は、請求項２３記載の固体高分子型燃料電池発電装置において、改質器の改質触媒層と第１の合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられ、選択酸化式一酸化炭素除去触媒層と第２の合流点の間に第３止め弁が設けられたことを特徴とする。
【００７８】
このような請求項２４の発明では、前記請求項８の発明と同じく、流路の切替えを止め弁の開閉で行うので、起動バーナーの燃焼ガス流路と排気バーナーの燃焼ガス流路を共通化でき、機器を簡素化することができる。
【００７９】
請求項２５の発明は、請求項２４の発明にかかる固体高分子型燃料電池発電装置の運転方法であり、装置起動時でかつ水蒸発器温度、燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁、第２止め弁及び第３止め弁が開き、装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかの温度が予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第１止め弁が開いて第２止め弁及び第３止め弁が閉じ、第２止め弁及び第３止め弁が開いた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、第２止め弁及び第３止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて運転状態に移行し、運転時には第１止め弁、第２止め弁及び第３止め弁が閉じ、停止時には第１止め弁が閉じて第２止め弁及び第３止め弁が開くことを特徴とする。
【００８０】
請求項２５の発明では、以上のような運転方法を実施することにより、各機器をほぼ同調して所定の温度にまで昇温することができ、さらには過剰な昇温を防止することができる。
【００８１】
請求項２６の発明は、請求項２４記載の固体高分子型燃料電池発電装置において、第２止め弁と第３止め弁の間の流路のいずれかの箇所に第２の分岐点が形成され、第２の分岐点には外気に開放される配管が接続され、この配管に第４止め弁が設けられたことを特徴とする。
【００８２】
請求項２７の発明は、請求項２６の発明にかかる固体高分子型燃料電池発電装置の運転方法であり、装置起動時でかつ燃料電池冷却媒体加熱器、脱硫器温度、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁、第２止め弁及び第３止め弁が開いて第４止め弁が閉じ、装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかが予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第２止め弁及び第３止め弁が閉じて第１止め弁及び第４止め弁が開き、第２止め弁及び第３止め弁が開いて第４止め弁が閉じた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、第２止め弁及び第３止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて第４止め弁が開いて運転状態に移行し、運転時には第１止め弁、第２止め弁及び第３止め弁が閉じて第４止め弁が開き、装置停止時には第２止め弁または第３止め弁の少なくとも一方と第４止め弁が開くことを特徴とする。
【００８３】
上記請求項２６及び２７の発明によれば、各機器をほぼ同調して所定の温度にまで昇温でき、過剰昇温を防ぐと共に、第４止め弁の働きにより起動バーナー燃焼ガス流路の減圧を防止することができる。
【００８４】
請求項２８の発明は、請求項１８、１９、２０、２１または２２記載の固体高分子型燃料電池発電装置において、燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、燃料混合ガス過熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入した後、燃料混合ガス過熱器を通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、大気中に出て、一方、分岐点にて分岐された残余の起動バーナーからの燃焼ガスは更に水蒸発器、水凝縮器の順に通過するように構成され、かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置されたことを特徴とする。
【００８５】
上記請求項２８の発明においては、装置起動時に起動バーナーからの燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過するまでは、前記請求項２２の発明と同じであるが、それ以降熱交換に使用されることなく大気中に放出される点が異なっている。このような請求項２８の発明によれば、各機器を充分高温に昇温することができると同時に、簡易な装置を構築することができる。
【００８６】
請求項２９の発明は、請求項２８記載の固体高分子型燃料電池発電装置において、改質触媒層と合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられたことを特徴とする。
【００８７】
請求項３０の発明は、請求項２９の発明にかかる固体高分子型燃料電池発電装置の運転方法であり、装置起動時でかつ脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達しない場合には第１止め弁及び第２止め弁が開き、装置起動時でかつ脱硫器温度温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達した場合には第１止め弁が開いて第２止め弁が閉じ、運転時には第１止め弁及び第２止め弁が閉じることを特徴とする。
【００８８】
上記の請求項２９及び３０の発明では、請求項２８記載の固体高分子型燃料電池発電装置において、各機器をほぼ同調して所定の温度にまで昇温でき、過剰昇温を防ぎながら、装置の簡略化を図ることができる。
【００８９】
請求項３１の発明は、請求項１８、１９、２０、２１または２２記載の固体高分子型燃料電池発電装置において、燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、燃料混合ガス過熱器、水蒸発器、燃料電池冷却媒体加熱器、水凝縮器の順に通過するように構成されたことを特徴とする。
【００９０】
以上の請求項３１の発明では、１つの合流点を形成するだけで、請求項２２の発明と同様の作用効果を得ることができ、装置の簡易化をいっそう進めることができる。
【００９１】
請求項３２の発明は、請求項３１記載の固体高分子型燃料電池発電装置において、改質器の改質触媒層と合流点の間に止め弁が設けられたことを特徴とする。
【００９２】
請求項３３の発明は、請求項３２の発明にかかる固体高分子型燃料電池発電装置の運転方法であり、装置起動時の水蒸発器温度が予め設定された目標温度に未達であれば止め弁が開き、止め弁が開いた状態で燃料電池冷却媒体加熱器温度が予め設定された最高限界温度に達した場合には、燃料電池冷却媒体冷却器が運転されて温度制御を行い、水蒸発器温度が予め設定された目標温度に達したら止め弁が閉じて運転状態に移行し、運転時には止め弁が閉じ、かつ装置起動時には脱硫器、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の温度がそれぞれ個別に電力によって加熱されることを特徴とする。
【００９３】
上記の請求項３２及び３３の発明では、請求項３１記載の固体高分子型燃料電池発電装置において、各機器の昇温及び過剰昇温の防止、さらには装置の簡略化を実現することができる。
【００９４】
【発明の実施の形態】
（１）第１の実施の形態
［構成］
以下、本発明の実施の形態の一例について図面を参照して具体的に説明する。なお、図２６に示した従来例の構成要素と同一の部材に関しては同一符号を付して説明は省略する。
【００９５】
まず、請求項１にかかる第１の実施の形態を図１に示す。排気ガスバーナー４の下流側には水蒸気を過熱する水蒸気過熱器６２が設けられ、その下流側には改質器２に供給する燃料を酸素を含むガスと混合した状態で加熱する燃料混合ガス予熱器６３、改質器２に供給する水蒸気を発生させる水蒸発器６１が順次設けられている。これらの機器には排気ガスバーナー４からの燃焼ガスが、水蒸気過熱器６２、燃料混合ガス予熱器６３、水蒸発器６１、水凝縮器５の順に通過するように燃焼ガス流路が形成されている。
【００９６】
水蒸気は水蒸発器６１で生成され、途中水蒸気過熱器６２に入ってここで加熱され、その後、改質器２に送られる。燃料は酸素を含むガスと混合された後、燃料混合ガス予熱器６３を通じて予熱され、改質器２に送られる。改質器２での部分酸化型水蒸気改質反応を可能な限り水蒸気改質側に近づけるため、改質器２入口における原料ガス濃度は高い方が良い。従って、水蒸気過熱器６２及び燃料混合ガス予熱器６３での出口温度は高い方が望ましい。
【００９７】
燃料には炭素原子と水素原子を分子中に少なくとも各々一個以上含む気体が適用されている。具体的にはメタン、エタン、プロパン、ブタンなどの気体状炭化水素、及びこれらを主成分とする都市ガス、ガソリン、灯油、軽油などの液体状炭化水素の蒸気、及びメタノール、エタノール、ジメチルエーテル、イソプロパノール、アセトンなどの酸素を含む有機化合物が挙げられる。有機珪素化合物、有機金属化合物など、不揮発性物質が生成する物質は改質器２内部に生成物を沈着させるので燃料として相応しくない。またチオール類などの硫黄を含む化合物、ビニルクロライドをはじめとする有機塩素化合物などのハロゲンを含む化合物、アミン類、アミド類などの窒素を含む化合物は燃料電池１や後段の機器に被毒などの悪影響を与えるので相応しくない。酸素を含むガスとしては空気が挙げられるがこれに限らず、ほかに酸素ガス、燃料電池酸化剤極１２排気ガス、排気ガスバーナー４からのガス及びこれらの間の混合物が適当である。
【００９８】
燃料混合ガス予熱器６３での燃料混合ガスの予熱は、発火しない条件で行われる。可燃性ガスの発火は温度、燃料と酸素を含むガスとの混合比、不活性成分の存在によって変化する。例えば燃料が純メタンで酸素を含むガスが空気である場合についてH.F.Cowardらによる"Limits of Inflammability"を参照すると、常温での燃料／空気混合気の発火範囲は５．３％から１３．５％だが、６００℃での燃料／空気混合気の発火範囲は３．３％から１６．５％に広がる。上述した反応（２）の部分酸化反応のみを想定した、最も低い燃料／空気混合割合でも２０．９％であるので、６００℃程度では混合気は発火せず、局所的に酸素濃度が上昇して発火しても火炎は伝播しないことがわかる。しかしながら局所的に着火して周囲の温度が上昇すると発火条件を満たすおそれがあるので、上限を４００℃程度に抑制することが望ましい。また、一般に分子量が大きくなるほど発火温度は低下する傾向にあるので、導入される燃料に応じて加熱温度上限を変更する必要がある。
【００９９】
水蒸気の温度は高い方が良いが、高温水蒸気に耐える材料は高価であるため、水蒸気温度は６５０℃以下に抑制することが安価な装置を製作する上で望ましい。また、高温の水蒸気を燃料混合ガスに導入すると温度上昇により発火限界に入る可能性もある。温度一定下では水蒸気のような不活性ガスの導入は発火の濃度限界範囲を縮小させる役割を果たすが、加熱が伴う場合はこの限りではない。そのため、燃料の組成、加熱温度、導入蒸気量といった各種の要因を考慮しながら水蒸気過熱温度を決定する必要がある。以上に見られるように、望ましい燃料混合ガス予熱温度は望ましい水蒸気過熱温度よりも低く、同一の熱源として排気ガスバーナー４を用いる場合には燃料混合ガス予熱器６３を水蒸気過熱器６２の下流側に置くべきことが分かる。
【０１００】
改質器２の投入された水蒸気、酸素を含むガス及び燃料は、改質器２にて部分酸化反応により水素リッチガスに変換される。改質反応を維持するため、改質触媒層２１の温度は６００℃以上であることが望ましい。部分酸化型水蒸気改質反応では通常改質触媒層２１入口で酸化反応が優先して発生し、大きな発熱があることが一般的であるので、通常入口から出口にかけて温度が単調に減少する傾向が見られる。従って改質触媒層２１の温度を６００℃以上に保つために改質器２出口ガス温度を６００℃以上に保つことが望ましい。
【０１０１】
一方、改質器２から出た水素リッチガスは水素リッチガス冷却器２２及び脱硫器３３を経て低温一酸化炭素変成器３１に導入される。低温一酸化炭素変成器３１の温度は、通常使用されるＣｕ−ＺｎＯ系触媒について２００℃程度であることが望ましい。このため、水素リッチガスの温度６００℃以上から２００℃程度にまでを低下させる必要があり、水素リッチガス冷却器２２によって対応する。第１の実施の形態では制御の安定性の面から冷媒として燃料処理系冷却媒体径路１３３を流通する燃料処理系冷却媒体を使用する。
【０１０２】
水素リッチガス冷却器２２にて昇温された燃料電池冷却媒体は、燃料電池１の発熱により昇温された燃料電池冷却媒体と合流し、燃料電池冷却媒体冷却器１３４にて所定の温度にまで冷却され、再び燃料電池１及び水素リッチガス冷却器２２に供給される。燃料電池冷却媒体冷却器１３４は単なる冷却器に限らず、適当な媒体と組合せることで熱回収を行ってもよい。
【０１０３】
改質器２出口でＣＯ濃度は数％であるが、低温一酸化炭素変成器３１を通過する間に上記反応（３）のシフト反応により、ＣＯ濃度は出口で数千ｐｐｍ程度にまで低下する。反応（３）は発熱反応であるため低温で平衡上有利であるが、反応速度は反対に低温ほど低下するので低温一酸化炭素変成触媒に固有の最適温度が存在する。かかる低温一酸化炭素変成触媒としては、日産ガードラー社製Ｇ−６６Ｂを代表例とするＣｕ−ＺｎＯ系触媒が一般的である。これの最適運転温度は２００℃程度である。
【０１０４】
一般に低温一酸化炭素変成触媒は、上記Ｃｕ−ＺｎＯ系触媒に見られるように、Ｓで被毒するものが多い。そのため脱硫器３３が低温一酸化炭素変成器３１の上流に設置されている。図１では脱硫器３３は水素リッチガス冷却器２２と低温一酸化炭素変成器３１の間に設置されているが、設置場所はここに限らず、低温一酸化炭素変成器３１の上流のいかなる場所でもよい。但し、代表的な脱硫器３３吸収材であるＺｎＯは揮発性であるので、使用温度は４５０℃以下、更には３００℃以下であることが望ましく、従って水素リッチガス冷却器２２と低温一酸化炭素変成器３１の間もしくは燃料混合ガス予熱器６３の上流が望ましい。
【０１０５】
低温一酸化炭素変成器３１を通過した水素リッチガスは、空気などの酸素を含むガスと共に選択酸化式一酸化炭素除去器３２に導入され、ここで更に一酸化炭素濃度が数十ｐｐｍまでに低減される。前述したように、これは特に低温で顕著である燃料極１１の電極触媒の一酸化炭素による被毒を低減するためである。
【０１０６】
この選択酸化式一酸化炭素除去器３２は特定触媒上で一酸化炭素の酸化反応速度が水素の酸化反応速度より速いことを利用するものであり、高温では両者の差が狭まるため、２００℃以下の低温で運転することが望ましい。つまり通常、選択酸化式一酸化炭素除去器３２の運転温度は低温一酸化炭素変成器３１のそれより低く設定される。
【０１０７】
選択酸化式一酸化炭素除去器３２は１つの反応器からなっていてもよいし、２つ以上の複数の反応器からなっていてもよい。また、空気は均一に混合される必要があるため、特開平０８−１５７２０１号公報に見られるように反応器前の配管に空気を吹き込んでもよいし、特開平０８−１３３７０１号公報に見られるように反応器前に混合マニホールドを設置してそこに空気を吹き込んでもよい。
【０１０８】
燃料極１１で水素リッチガスの水素の約８割が電気化学反応に使用された後、残余の水素及び未改質燃料などのその他可燃性物質を含む燃料極１１排気ガスが排気ガスバーナー４に送られ、ここで酸化剤極１２排気ガスの一部と混合されて燃焼される。
【０１０９】
燃焼により生成した高温ガスは水蒸気過熱器６２に導入され、ここで原料水蒸気を過熱する。然る後に燃料混合ガス予熱器６３に導入され、燃料と酸素を含んだガスの混合ガスを予熱する。その後、水蒸発器６１に導入され、原料となる水の蒸発に使用される。上記機器の加熱に使用された排気ガスバーナー４の燃焼ガス及び排気ガスバーナー４に導入されなかった酸化剤極１２の排気ガスは水凝縮器５を通過し、含有する水分の回収が行われる。
【０１１０】
［作用効果］
上記のような構成を有する第１の実施の形態に関して、下記の条件で温度及び効率を見積もった。
【０１１１】
▲１▼燃料：純メタン ▲２▼酸素を含むガス：空気 ▲３▼水蒸気／メタン：３．０
▲４▼メタン／空気：０．４７ ▲５▼水、空気、メタンの温度：２０℃
▲６▼水蒸気過熱温度：６５０℃ ▲７▼燃料混合ガス予熱温度：４００℃
▲８▼燃料極水素利用率：８０％ ▲９▼放熱損失：なし
その結果、水素の生成効率はＨＨＶで７２％に達した。また、水蒸気混合後の燃料混合ガス温度は５００℃であり、メタン／空気が４７％でかつ不活性ガスとして水蒸気が４９％導入されているため、発火限界外であった。改質器２の出口温度は６４０℃であり、反応温度は確保されていた。
【０１１２】
各機器の温度についてみると、水蒸気過熱器６２での排気ガスバーナー４からの燃焼ガスの温度は入口側で８２０℃、出口側で６８０℃であり、これにより水蒸気が１０２℃から６５０℃まで昇温された。燃料混合ガス予熱器６３での排気ガスバーナー４からの燃焼ガス温度は入口側で６８０℃、出口側で５３０℃であり、これにより燃料混合ガスが２０℃から４００℃まで昇温された。
【０１１３】
次に水蒸発器６１については、排気ガスバーナー４の燃焼ガス温度は入口側で５３０℃、出口側で１９０℃であり、これにより２０℃の水が１０２℃の水蒸気に転換された。各機器については所定温度への昇温が可能であり、かつピンチ温度も確保されていた。
【０１１４】
以上述べたように、第１の実施の形態によれば、燃料極１１排気ガス中に含まれる可燃性ガスを排気ガスバーナー４で燃焼させ、この燃焼ガスを水蒸気過熱器、燃料混合ガス予熱器、水蒸発器、水凝縮器と高温の機器から順に通過させることにより、改質器２での反応を確保しながら、排気ガスバーナーの燃焼熱を効率的かつ安全に回収できる。第１の実施の形態においては高温が必要とされる機器から順に加熱していくことにより、高温が必要な機器の加熱源温度が不足する事態を防ぐことができる。
【０１１５】
また、第１の実施の形態では水蒸発器６１と水蒸気過熱器６２とを分離しているので流量制御が容易であり、簡略化を進めることができる。しかも、水蒸発器６１にて多くの熱量が奪われる前段で燃料混合ガス予熱器６３の加熱を実施するため、排気ガスバーナー４の燃焼ガスから高効率で熱回収を実施できる。
【０１１６】
（２）第２の実施の形態
［構成］
次に請求項２にかかる第２の実施の形態について図２を参照して説明する。なお、以下の実施の形態において使用されるガス及びガス流通の順序、各機器における望ましい温度などは第１の実施の形態と同一である。
【０１１７】
第２の実施の形態では、改質器２の外筒部に水素リッチガス冷却器２２が設置され複合一体化された点に特徴がある。
【０１１８】
［作用効果］
第２の実施の形態によれば、改質器２と水素リッチガス冷却器２２の間の配管を省いて発電装置の体積を減少させ、装置のコンパクト化を図ることができる。また高温で運転される改質器２の外筒部を、より低温で運転される水素リッチガス冷却器２２にて包囲するので、改質器２表面から大気への放熱損失を減少させることができる。燃料電池発電装置が小型化するに従って放熱損失を抑えることの重要さは増すため、このような構成は有効である。
【０１１９】
（３）第３の実施の形態
［構成］
第３の実施の形態の構成を図３に示す。第３の実施の形態は請求項３に対応し、その特徴は、排気ガスバーナー４の外筒部に水蒸気過熱器６２が設置されて複合一体化された点にある。
【０１２０】
［作用効果］
上記第２の実施の形態では改質器２での放熱損失低減に成功したが、排気ガスバーナー４の出口ガスは８００℃前後という高温であり、かつ熱回収の必要があるため、この部分の放熱損失を低減することが求められている。この要求に応えるべく、第３の実施の形態では、高温で運転される排気ガスバーナー４を、より低温で運転される水蒸気過熱器６２で囲み、排気ガスバーナー４表面から大気への放熱損失を抑えている。また、水蒸気過熱器６２を排気ガスバーナー４と複合一体化させることで両者間の接続流路が極小化するため、発電装置全体の体積も減り、装置のコンパクト化を進めることができる。
【０１２１】
（４）第４の実施の形態
［構成］
図４は請求項４にかかる第４の実施の形態を示している。第４の実施の形態は上記第３の実施の形態に改良を加えたもので、排気ガスバーナー４と複合一体化された水蒸気過熱器６２の外筒部に混合ガス予熱器６３が設置され、排気ガスバーナー４と水蒸気過熱器６２と混合ガス予熱器６３という３つの機器が複合一体化されたことに特徴がある。
【０１２２】
［作用効果］
前記第１の実施の形態での見積で明らかなように、水蒸気過熱器６２加熱後の排気ガスバーナー４の燃焼ガスの温度は未だ６８０℃以上の高温であり、排気ガスバーナー４の放熱損失は無視できない。熱回収効率を高めるためは、排気ガスバーナー４及びその下流の機器の一体化を更に進めることが有効である。
【０１２３】
第４の実施の形態では、排気ガスバーナー４、水蒸気過熱器６２及び混合ガス予熱器６３を複合一体化したことにより、機器間の接続流路を極小化でき、排気ガスバーナー４から大気への放熱損失を大幅に抑えて、熱回収効率を高めることができる。
【０１２４】
（５）第５の実施の形態
［構成］
請求項５にかかる第５の実施の形態について図５を用いて説明する。第５の実施の形態では、改質器２の外筒部下部に水素リッチガス冷却器２２が設置されると共に、改質器２の外筒部上部に水蒸発器６１が設置され、改質器２と水素リッチガス冷却器２２と水蒸発器６１という３つの機器が複合一体化されたことを特徴としている。なお、図５では水蒸発器６１を改質器２外筒部に直接設置しているが、これを水素リッチガス冷却器２２外側に設置してもよい。
【０１２５】
［作用効果］
このような第５の実施の形態では、改質器２に水素リッチガス冷却器２２及び水蒸発器６１を複合一体化させることで、装置のコンパクト化をより高めることが可能である。
【０１２６】
（６）第６の実施の形態
［構成］
第６の実施の形態は請求項６にかかり、図６に示すように、脱硫器３３が水素リッチガス流路の水素リッチガス冷却器２２と低温一酸化炭素変成器３１の中間に設置された点に構成上の特徴がある。なお、図６では脱硫器３３が低温一酸化炭素変成器３１の前段に置かれた形になっているが、脱硫器３３の外筒部に低温一酸化炭素変成器３１を設置する、もしくは低温一酸化炭素変成器３１の外筒に脱硫器３３を設置するなどして両者を複合一体化させ放熱損失の低減を図ってもよいし、他の方法をとってもよい。
【０１２７】
［作用効果］
脱硫器３３の運転温度は脱硫反応を促進するために高温が望ましいが、ＺｎＯなどからなる脱硫器３３吸収材の昇華損失を抑制する上でその上限を３００℃程度に抑制する必要がある。一方、低温一酸化炭素変成器３１の運転温度は２００℃程度であるが、低温では反応速度が低下するため、放熱損失により低温一酸化炭素変成器３１温度が低温側に傾くことは望ましくない。低温一酸化炭素変成器３１でおこるシフト反応は発熱反応であるが、低負荷で反応ガス流量が少ない場合には放熱が発熱に勝り運転温度が維持できないおそれがある。
【０１２８】
第６の実施の形態においては、脱硫器３３と低温一酸化炭素変成器３１とを複合一体化することにより、放熱損失を低減させて一酸化炭素変成器３１の運転温度を維持することができる。また、機器の複合一体化により装置体積の減少を図ることができる。
【０１２９】
（７）第７の実施の形態
［構成］
第７の実施の形態は請求項７に対応しており、図７は第７の実施の形態の構成図である。なお、図７では改質器２、水素リッチガス冷却器２２、低温一酸化炭素変成器３１、脱硫器３３、排気ガスバーナー４、水蒸発器６１、水蒸気過熱器６２、燃料混合ガス予熱器６３の関係は請求項１に基づいて各々独立に記述したが、請求項２、請求項３、請求項４、請求項５もしくは請求項６の発明に基づいて複合一体化させてもよい。
【０１３０】
第７の実施の形態の特徴は次の点にある。すなわち、燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナー７０と、燃料電池１の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器１３５とが設けられている。起動バーナー７０は改質器２とは独立に設置してもよいし、改質器２と複合一体化するような構造であってもよい。
【０１３１】
起動バーナー７０では、すすなどが生成しないよう燃焼ガスが確実に完全燃焼する必要がある。そのため燃料に対して酸素過多で発生させなくてはならない。また、改質触媒層２１は還元性雰囲気が望ましい。したがって、起動バーナー７０燃焼ガスは改質触媒層２１及びその雰囲気から隔絶され、リークなどによる相互の流通が存在しないように製作されている。
【０１３２】
起動バーナー７０の燃焼ガス温度は改質器２が運転可能となる温度以上である必要があり、ニッケル系改質触媒を使用する場合には４００℃以上であることが望ましい。但し、下流の機器に高温に弱いものがあるので過剰な高温化は回避し、４００〜５００℃程度であることが望ましい。これを達成するための起動バーナー７０としては、燃料が11,000kcal/m3(HHV)の都市ガスの場合に少なくとも燃料体積の６０倍程度の空気を導入し、かつこの混合比で安定に燃焼させるような触媒燃焼器が好適である。
【０１３３】
また、排気ガスバーナー４と水蒸気過熱器６２の間には起動バーナー７０からの燃焼ガスが排気ガスバーナー４からの燃焼ガス流路に合流する第１の合流点７３が形成されている。さらに、燃料混合ガス予熱器６３と水蒸発器６１の間には燃焼ガスが分れる分岐点７１が形成され、この分岐点７１の下流には再度燃焼ガス流路に燃焼ガスが合流する第２の合流点７４が形成されている。
【０１３４】
装置起動時には起動バーナー７０が動作して燃焼ガスが発生し、この燃焼ガスが改質器２の改質触媒層２１を通過した後（図中の＊）、第１の合流点７３にて排気ガスバーナー４からの燃焼ガス流路に入る。このガス流路には元来、排気ガスバーナー４からの燃焼ガスが流れているため、雰囲気還元性である必要はなく、起動バーナー７０の燃焼ガスラインと共通化している。
【０１３５】
さらに、起動バーナー７０からの燃焼ガスは、水蒸気過熱器６２、燃料混合ガス予熱器６３の順に通過する。そして、燃料混合ガス予熱器６３を通過した起動バーナー７０の燃焼ガスは、分岐点７１にて直接水蒸発器６１に通じる通常の流路から一部が分岐し（図中の＊＊）、燃料電池冷却媒体加熱器１３５、脱硫器３３の吸収材層、低温一酸化炭素変成器３１の触媒層、選択酸化式一酸化炭素除去器３２の触媒層を貫流する。改質触媒層２１と同じくこれらは還元性雰囲気が望ましいため、起動バーナー７０燃焼ガスは脱硫器３３吸収材、低温一酸化炭素変成器３１の触媒、選択酸化式一酸化炭素除去器３２の触媒及びその雰囲気から隔絶され、リークなどによる相互の流通が存在しないよう製作されている。その後、選択酸化式一酸化炭素除去器３２の触媒層を貫流した起動バーナー７０燃焼ガスは、第２の合流点７４で再び残余の起動バーナー７０からの燃焼ガスに合流し、水蒸発器６１、水凝縮器５の順に通過する。
【０１３６】
なお、選択酸化式一酸化炭素除去器３２の触媒層は、反応器が複数から成る場合には２つ以上に分かれていてもよい。また、燃料電池冷却媒体加熱器１３５は図７では燃料処理系冷却媒体循環径路１３３の水素リッチガス冷却器２２上流に設置されているが、設置位置はここに限定されず、燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流の部分を除けば、燃料処理系冷却媒体循環径路１３３を含む燃料電池冷却媒体径路１３１のいずれの位置でもよい。燃料電池冷却媒体加熱器１３５の設置位置として燃料電池冷却媒体加熱器１３４の下流及び燃料電池１の上流の部分を除くのは、この部分で測定した燃料電池冷却媒体温度で燃料電池冷却媒体冷却器１３４での熱交換量を制御することが多いため、この位置に燃料電池加熱器１３５を設置すると擾乱要因となるからである。また、図７では脱硫器３３を水素リッチガス冷却器２２と低温一酸化炭素変成器３１の中間に設置しているが、ここに限定されず例えば改質器２導入前の燃料流路に設置してもよい。
【０１３７】
［作用効果］
以上のような構成を有する第７の実施の形態の作用効果は次の通りである。すなわち、装置起動時に発生した燃焼ガス起動バーナー７０の燃焼ガスは、水蒸気過熱器６２、燃料混合ガス予熱器６３の順に通過してこれらの機器を暖める。起動バーナー７０の燃焼ガス温度が高々５００℃程度であるので、これら機器の昇温限度は４００℃程度と考えられ、水蒸気過熱器６２及び燃料混合ガス予熱器６３の望ましい運転温度には未達である。しかしながら、これらの機器は熱回収のために存在し、起動時には効率は度外視するので、運転温度程度にまで昇温する必要はない。つまり、反応ガスを流通させた際に凝縮が発生しない程度に暖管すればよいので、この条件で機能を充分に果たすことができる。
【０１３８】
燃料混合ガス予熱器６３を通過した起動バーナー７０燃焼ガスの温度は３００〜４００℃程度である。これをこのまま脱硫器３３吸収材、低温一酸化炭素変成器３１触媒層などの加熱に使用すると、これらは昇華性のＺｎＯを含む場合が多いため、損傷する可能性がある。そこで、分岐点７１にて分かれた起動バーナー７０燃焼ガスは脱硫器３３吸収材を通過させる前に燃料電池冷却媒体加熱器１３５にて燃料電池冷却媒体と熱交換し、２５０℃程度にまで温度を低下させる。と同時に、燃料電池冷却媒体の昇温に使用する。これ以降の加熱目標温度は脱硫器３３が２００〜２５０℃、低温一酸化炭素変成器３１が２００℃程度、選択酸化式一酸化炭素除去器３２が２００℃以下であるので、この順に起動バーナー７０の燃焼ガスを通過させれば、各機器をほぼ同時に目標温度を達成することが可能である。燃料電池冷却媒体の加熱目標温度は高々８５℃程度で低いが、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２に比較して熱容量が大きいため、過度に昇温することはない。
【０１３９】
一方、水蒸発器６１では発電開始までに多量の水を沸点まで加熱しかつ水蒸気を発生させなければならないので、起動に大量の熱量が必要である。必要な温度は１００℃強で、脱硫器３３などの目標温度に比較して低いが、熱容量が大きいのでこれら機器の下流に配置すると昇温が遅れるおそれがある。そのため、第７の実施の形態では起動バーナー７０燃焼ガスが分岐点７１で分かれ、一方は燃料電池冷却媒体加熱器１３５以下の加熱を行い、他方は熱量を維持して水蒸発器６１の加熱に使用することができる。これにより水蒸発器６１の昇温を他の機器と同調して確実に行うことが可能となった。
【０１４０】
また、第７の実施の形態では、改質触媒層２１、脱硫器３３吸収材層、低温一酸化炭素変成器３１触媒層、選択酸化式一酸化炭素除去器３２触媒層といった燃料電池１燃料極１１の上流に位置する機器については、水素リッチガスが流通する経路とは独立して起動バーナー７０燃焼ガスの流通経路を設置している。そのため、燃料処理系の触媒層において高温・還元性雰囲気での使用が想定されていても、燃焼ガスの流通により酸化及び結露が生じて活性低下が起きるおそれがなく、起動前の昇温に加えて還元操作を行う必要がない。
【０１４１】
（８）第８の実施の形態
［構成］
請求項８及び９にかかる第８の実施の形態について図８を参照して説明する。第８の実施の形態は前記第７の実施の形態（請求項７の発明に対応）において、起動バーナー７０燃焼ガスと排気ガスバーナー４燃焼ガスの流路切替えを行う機構を設けた点に特徴があり、切替えを請求項９の発明にかかる運転方法で実施している。
【０１４２】
すなわち、起動バーナー７０と第１の合流点７３の間に第１止め弁７５が設けられ、分岐点７１と燃料電池冷却媒体加熱器１３５の間に第２止め弁７６が設けられ、選択酸化式一酸化炭素除去器３２の触媒層と第２の合流点７４の間に第３止め弁７７が設けられている。これら３つの止め弁７５、７６及び７７を請求項１１の発明にかかる運転方法により開閉し、燃焼ガスの流路切替えを行うようになっている。
【０１４３】
［止め弁の開閉］
装置起動時には起動バーナー７０が点火されると共に、３つすべての止め弁７５、７６、７７が開き、起動バーナー７０燃焼ガスが流通する。分岐点７１と第２の合流点７４の間には止め弁は無く、燃料混合ガス予熱器６３出口側の高温ガスの一部は直接、水蒸発器６１を加熱する。なお、分岐点７１で分岐するガス流量を最適に配分するため、分岐点７１と第２の合流点７４の間にはオリフィスなどの圧損要素を設置してもよい。
【０１４４】
燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２のすべての昇温が完了したら、第２止め弁７６及び第３止め弁７７を閉じる。但し、何らかの原因でいずれかの機器の温度が過度に上昇し、予め設定された最高限界温度を越えた場合には他の機器の昇温が完了していなくとも、第２止め弁７６及び第３止め弁７７を閉じる。
【０１４５】
第２止め弁７６と第３止め弁７７の間に設置してある機器には温度の上限があるものが多い。例えば、燃料電池冷却媒体加熱器１３５の温度が沸点に近づくことは燃料電池冷却媒体全体がこの温度まで昇温することを意味するので、固体高分子電解質膜を初めとする燃料電池１の構成部材に損傷を与える可能性がある。また、脱硫器３３と低温一酸化炭素変成器３１は前述したように昇華性のＺｎＯを含む場合があり、選択酸化式一酸化炭素除去器３２では高温で反応の選択性が悪化する傾向が見られている。そのため、これら機器に最高限界温度を設定し、いづれかが限界に達したら第２止め弁７６及び第３止め弁７７を閉じて、機器の昇温を中断する。
【０１４６】
一方、水蒸発器６１は第２の合流点７４で合流した起動バーナー７０燃焼ガスで昇温される。この温度が目標温度に達しない間は第１止め弁７５が開いて起動バーナー７０燃焼ガスが送り込まれ、目標温度に達してかつ第２止め弁７６及び第３止め弁７７が閉じていたら、起動のための加熱を終了して第１止め弁７５が閉り、起動バーナー７０が停止して発電運転に移行する。
【０１４７】
運転中はこれらすべての弁７５、７６、７７が閉じて通常運転時の熱バランスを擾乱させない。停止時には第２止め弁７６及び第３止め弁７７が開いて起動バーナー燃焼ガス流路が水凝縮などで減圧し、リークなどの不適合の原因となることを防ぐことができる。
【０１４８】
但し、燃料電池冷却媒体加熱器１３５から選択酸化式一酸化炭素除去器３２の間の機器の加熱が未了であっても、水蒸発器６１の温度が沸点を越えて過度に上昇すると危険であるので、水蒸発器６１温度が予め設定された最高限界温度に達した場合は第２止め弁７６及び第３止め弁７７を開けたままで第１止め弁７５を閉め、起動バーナー７０を停止して新たな熱量の供給を停止し、残熱で昇温未了の機器を加熱する。水蒸発器６１の過度の昇温を防ぐため、安全弁を設置してもよい。
【０１４９】
［作用効果］
第８の実施の形態では、上記の機構と制御により、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつ過剰昇温を防ぐことが可能となった。また、止め弁の開閉により燃焼ガス流路の切替えることができるので、起動バーナー７０の燃焼ガス流路と排気ガスバーナー４の燃焼ガス流路を共通化でき、装置の簡素化を図ることができる。
【０１５０】
（９）第９の実施の形態
［構成］
請求項１０、１１にかかる第９の実施の形態について図９を用いて説明する。第９の実施の形態と前記第８の実施の形態との相違点は、第９の実施の形態では第２止め弁７６と第３止め弁７７の間に第２の分岐点７２があり、ここから大気に開放するベント配管が設置されていて、これに第４止め弁７８が設置されていることである。これは第２止め弁７６と第３止め弁７７が閉じた時にこの間を封じ切りにしないためのものである。これら４つの止め弁７５、７６、７７及び７８を請求項１１の発明にかかる運転方法により開閉し、前記第８の実施の形態と同じく、起動バーナー７０燃焼ガスと排気ガスバーナー４燃焼ガスの流路切替えるになっている。なお、前記分岐点７１をここでは第１の分岐点７１とする。
【０１５１】
［止め弁の開閉］
装置起動時には起動バーナー７０が点火されると共に、第４止め弁７８以外の３つの止め弁７５、７６及び７７が開き、起動バーナー７０燃焼ガスが流通する。第１の分岐点７１と第２の合流点７４の間には止め弁が無い点、分岐点７１と第２の合流点７４の間にはオリフィスなどの圧損要素を設置してもよい点などは第８の実施の形態と同様である。
【０１５２】
燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２すべての昇温が完了したら、第２止め弁７６及び第３止め弁７７を閉じ、第１止め弁７５及び第４止め弁７８を開く。但し、何らかの原因でいずれかの機器の温度が過度に上昇し、予め設定された最高限界温度を越えた場合は他の機器の昇温が完了していなくとも第２止め弁７６及び第３止め弁７７を閉じ、第４止め弁７８を開く。これは第８の実施の形態にて説明したように、機器の安全性を確保するためである。
【０１５３】
一方、水蒸発器６１の温度が目標温度に達しない間は第１止め弁７５が開いて起動バーナー７０燃焼ガスが送り込まれ、目標温度に達してかつ第２止め弁７６及び第３止め弁７７が閉じかつ第４止め弁７８が開いていたら、起動のための加熱を終了して第１止め弁７５が閉り、起動バーナー７０が停止して発電運転に移行する。
【０１５４】
運転中はこれらすべての止め弁７５、７６、７７及び７８が閉じて通常運転時の熱バランスの擾乱を防ぐようになっている。停止時には第２止め弁７６か第３止め弁７７のどちらかと第４止め弁７８が開いて起動バーナー７０燃焼ガス流路の減圧を防ぐことができる。
【０１５５】
但し、燃料電池冷却媒体加熱器１３５から選択酸化式一酸化炭素除去器３２の間の機器の加熱が未了であっても、水蒸発器６１の温度が沸点を越えて過度に上昇すると危険であるので、水蒸発器６１温度が予め設定された最高限界温度に達した場合には第２止め弁７６及び第３止め弁７７を開け、かつ第４止め弁７８を閉めた状態で第１止め弁７５を閉める。これにより、起動バーナー７０を停止して新たな熱量の供給を停止し、残熱で昇温未了の機器を加熱するものとする。なお、水蒸発器６１の過度の昇温を防ぐため、安全弁を設置してもよい点は第８の実施の形態と同然である。
【０１５６】
［作用効果］
以上の第９の実施の形態では、上記の機構と制御により、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつ過剰昇温を防ぐことができる。また、燃焼ガス流路が切替可能であるため起動バーナー７０の燃焼ガス流路と排気ガスバーナー４の燃焼ガス流路を共通化でき、装置を簡素化できる。さらには、第４止め弁７８の働きにより起動バーナー７０燃焼ガス流路の減圧を防止することができる。
【０１５７】
（１０）第１０の実施の形態
［構成］
請求項１２にかかる第１０の実施の形態について、図１０を参照して説明する。第１０の実施の形態は第７の実施の形態（請求項７の発明に対応）の変形である。選択酸化式一酸化炭素変成器３２は比較的低温で運転され、Ａｕ系やＲｕ系触媒を使用した場合には運転温度が水の沸点以下である場合も有る。このような場合、選択酸化式一酸化炭素変成器３２出口での起動バーナー７０燃焼ガスの温度は水蒸発器６１の加熱に利用可能な水準には無い。従って第２の合流点７４を設けてまでしてこれを水蒸気器６１に導入する必要はなく、大気開放することが望ましい。
【０１５８】
第１０の実施の形態は起動バーナー７０燃焼ガス流路が分岐点７１で分岐され、燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２を加熱した起動バーナー７０燃焼ガスが以降熱交換に使用されること無く大気中に放出されることを特徴とする。
【０１５９】
選択酸化式一酸化炭素除去器３２の触媒層は、反応器が複数から成る場合には２つ以上に分かれていてもよい。また、燃料電池冷却媒体加熱器１３５は図１０では燃料処理系冷却媒体循環径路１３３の水素リッチガス冷却器２２上流に設置されているが、設置位置はここに限定されず、燃料処理系冷却媒体循環径路１３３を含む燃料電池冷却媒体径路１３１のいずれの位置でもよい。但し、燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流の部分は、ここで測定した燃料電池冷却媒体温度で燃料電池冷却媒体冷却器１３４での熱交換量を制御することが多く、擾乱要因となるため、この位置に燃料電池加熱器１３５を設置するこは避ける。また、図１０では脱硫器３３は水素リッチガス冷却器２２と低温一酸化炭素変成器３１の中間に設置されているが、ここに限定されず例えば改質器２導入前の燃料流路に設置してもよい。
【０１６０】
［作用効果］
以上のような第１０の実施の形態によれば、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつより簡易かつ効果的な燃料電池発電装置を構築することが可能となった。
【０１６１】
なお、第７の実施の形態（請求項７の発明に対応）と第１０の実施の形態（請求項１２の発明に対応）の長短は、選択酸化式一酸化炭素変成器３２の目標運転温度、特にこれが複数段に分割されている場合には最終段の目標運転温度に依存する。すなわち、目標運転温度が高ければ前者の方が有利であり、水の沸点前後の低温であれば後者の方がより効果的である。
【０１６２】
（１１）第１１の実施の形態
［構成］
図１１に示す第１１の実施の形態は、請求項１３及び１４に対応するものであり、第１０の実施の形態（請求項１２の発明に対応）において、起動バーナー７０燃焼ガスと排気ガスバーナー４燃焼ガスの流路切替えを行う機構を設けた点に特徴がある。すなわち、起動バーナー７０と第１の合流点７３の間に第１止め弁７５が設けられ、分岐点７１と脱硫器３３の吸収材層の間に第２止め弁７６が設けられている。これら止め弁７５、７６の開閉を請求項１４の発明にかかる運転方法で実施している。
【０１６３】
［止め弁の開閉］
装置起動時には起動バーナー７０が点火されると共に、２つの止め弁７５、７６が開き、起動バーナー７０燃焼ガスが流通する。流量配分最適化のための圧損要素は水蒸発器６１の上流に設置する必要が無く、かつ圧損要素として水蒸発器６１及び水凝縮器５をカウントすることができるので、第２の合流点７４を有する場合より設置する圧損要素を低減し、排気ガスライン全体の圧損を低下させることが可能である。
【０１６４】
燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２すべての昇温が完了したら、第２止め弁７６を閉じる。但し、何らかの原因でいづれかの機器の温度が過度に上昇し、予め設定された最高限界温度を越えた場合は他の機器の昇温が完了していなくとも第２止め弁７６を閉じ、安全性を確保する。
【０１６５】
一方、水蒸発器６１は温度が目標温度に達しない間は第１止め弁７５が開いて起動バーナー７０燃焼ガスが送り込まれ、目標温度に達してかつ第２止め弁７６が閉じていたら起動のための加熱を終了して第１止め弁７５が閉り、起動バーナー７０が停止して発電運転に移行する。
【０１６６】
運転中は止め弁７５及び７６が両方とも閉じて通常運転時の熱バランスの擾乱を防止する。停止時には第２止め弁７６が開いても閉じていても起動バーナー７０燃焼ガス流路は大気に開放されるので、減圧のおそれはない。但し、燃料電池冷却媒体加熱器１３５から選択酸化式一酸化炭素除去器３２の間の機器の加熱が未了であっても、水蒸発器６１の温度が沸点を越えて過度に上昇すると危険であるので、水蒸発器６１温度が予め設定された最高限界温度に達した場合には第２止め弁７６を開けたままで第１止め弁７５を閉め、起動バーナー７０を停止して新たな熱量の供給を停止し、残熱で昇温未了の機器を加熱する。なお、水蒸発器６１の過度の昇温を防ぐため、安全弁を設置してもよい。
【０１６７】
［作用効果］
第１１の実施の形態では、上記のような機構と制御により、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつ過剰昇温を防ぎながら、より簡易かつ効果的な燃料電池発電装置を構築することが可能となった。
【０１６８】
（１２）第１２の実施の形態
［構成］
第１２の実施の形態は請求項１５に対応しており、図１２は第１２の実施の形態の構成図を示している。これまで第７の実施の形態から第１１の実施の形態にかけては、起動バーナー７０燃焼ガスを脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２の昇温に使用する場合を例示した。しかしながら、装置及び各反応器が小規模である場合、各反応器に特段の起動用加熱配管を設けることは困難であり、かつ運転中にこれを通じての放熱損失も無視できない。
【０１６９】
そこで、請求項１５の発明にかかる第１２の実施の形態では、起動バーナー７０燃焼ガスが改質器２の改質触媒層２１を通過した後、合流点７３にて排気ガスバーナー４からの燃焼ガス流路に流入し、水蒸気過熱器６２、燃料混合ガス予熱器６３、水蒸発器６１、燃料電池冷却媒体加熱器１３５、水凝縮器５の順に通過するように構成されたことを特徴とする。
【０１７０】
起動バーナー７０で発生した起動バーナー７０燃焼ガスは改質触媒層２１を貫流して加熱した後、水蒸気過熱器６２と燃料混合ガス予熱器６３を加熱し、水蒸発器６１を加熱する。ここでガス温度が比較的低位になってから、燃料電池冷却媒体加熱器１３５を加熱する。燃料電池冷却媒体は通常水の沸点以下高々８５℃程度なので、水蒸発器６１加熱後のガスでも加熱可能である。燃料電池冷却媒体加熱器１３５を出た起動バーナー７０燃焼ガスは水凝縮器５を経て大気に放出される。なお、目標昇温温度が比較的低くかつ加熱に必要な熱量が比較的少ない脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２の昇温は電力で行うようになっている。
【０１７１】
選択酸化式一酸化炭素除去器３２の触媒層は、反応器が複数から成る場合には２つ以上に分かれていてもよい。また、燃料電池冷却媒体加熱器１３５は図１２では燃料処理系冷却媒体循環径路１３３の水素リッチガス冷却器２２上流に設置されているが、設置位置はここに限定されず、燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流の部分を除く、燃料処理系冷却媒体循環径路１３３を含む燃料電池冷却媒体径路１３１のいずれの位置でもよい。燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流部分は通常、燃料電池冷却媒体温度の測定箇所であり、測定結果に基づいて燃料電池冷却媒体冷却器１３４での熱交換量を制御する。したがって、前記の位置を燃料電池加熱器１３５の設置位置に選ぶと擾乱要因となり易い。そのためこの部分は外す。また、図１２では脱硫器３３は水素リッチガス冷却器２２と低温一酸化炭素変成器３１の中間に設置されているが、ここに限定されず例えば改質器２導入前の燃料流路に設置してもよい。
【０１７２】
［作用効果］
以上の第１２の実施の形態では、高温が必要な改質器２２の昇温及び昇温に多くの熱量を必要とする燃料電池冷却媒体加熱器１３５及び水蒸発器６１の加熱にのみ起動バーナー７０燃焼ガスを使用している。すなわち、機器を選んで燃焼ガスを供給することにより燃焼ガス流路をシンプルに構成することができ、装置の簡略化を進めることができる。
【０１７３】
なお、請求項７もしくは請求項１２の発明と請求項１５の発明のどちらを採用するかは、装置の規模に依存する。装置規模が大きければ請求項７もしくは請求項１２の発明が有利であり、装置規模が小さければ請求項１５の発明の方がより効果的である。
【０１７４】
（１３）第１３の実施の形態
［構成］
請求項１６及び１７に対応する第１３の実施の形態について、図１３を用いて説明する。第１３の実施の形態は第１２の実施の形態（請求項１５の発明に対応）において、起動バーナー７０燃焼ガスと排気ガスバーナー４燃焼ガスの流路切替えを行う機構を設けている。すなわち、起動バーナー７０と第１の合流点７３の間に第１止め弁７５が設けられ、請求項１７の発明にかかる運転方法により第１止め弁７５を開閉してガス流路の切替えを行っている。
【０１７５】
［止め弁の開閉］
装置起動時には起動バーナー７０が点火されると共に、第１止め弁７５が開き、起動バーナー７０燃焼ガスが流通する。流量配分最適化の必要が無いのでそのための圧損要素は不要である。水蒸発器６１は温度が目標温度に達しない間は止め弁７５が開いて起動バーナー７０燃焼ガスが送り込まれ、目標温度に達したら起動のための加熱を終了して第１止め弁７５が閉り、起動バーナー７０が停止して発電運転に移行する。
【０１７６】
運転中は第１止め弁７５が閉じて通常運転時の熱バランスを擾乱させない。停止時には第１止め弁７５が開いても閉じていてもその両側とも大気に開放されるので減圧のおそれはない。但し、水蒸発器６１の昇温が未了であるのに燃料電池冷却媒体加熱器１３５の昇温が最高限界温度に達した場合は、燃料電池１の冷却水温度調節を目的に設置された燃料電池冷却媒体冷却器１３４により熱を放出する。これにより水蒸発器６１の昇温を継続しながら燃料電池冷却媒体の過度の昇温を防ぐ。
【０１７７】
［作用効果］
第１３の実施の形態では、上記のような機構と制御により、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつ過剰昇温を防ぎながら、より簡易かつ効果的な燃料電池発電装置を構築することができる。
【０１７８】
（１４）第１４の実施の形態
［構成］
請求項１８にかかる第１４の実施の形態を図１４に示す。第１４の実施の形態は請求項１の発明にかかる第１の実施の形態の変形であり、水蒸気過熱器６１と燃料混合ガス予熱器６２を統合して燃料混合ガス過熱器６４が設けられている点に特徴がある。燃料混合ガス過熱器６４は、酸素を含むガスと燃料と水蒸発器６１で発生した水蒸気との混合ガスを過熱する機器である。排気ガスバーナー４の燃焼ガスは燃料混合ガス過熱器６４、水蒸発器６１、水凝縮器５の順に通過するようになっている。以上の点以外では第１の実施の形態の構成と同様である。
【０１７９】
［作用効果］
上記のような構成を有する第１４の実施の形態に関して、下記の条件で温度及び効率を見積もった。
【０１８０】
▲１▼燃料：純メタン ▲２▼酸素を含むガス：空気 ▲３▼水蒸気／メタン：３．０
▲４▼メタン／空気：０．５０ ▲５▼水、空気、メタンの温度：２０℃
▲６▼燃料混合ガス過熱温度：４５０℃ ▲７▼燃料極水素利用率：８０％
▲８▼放熱損失：なし
その結果、水素の生成効率はＨＨＶで７０％強で、第１の実施の形態での見積と大きな相違はなかった。また、第１４の実施の形態では、燃料を空気と混合するだけでなく、水蒸気と混合した状態で燃料混合ガス過熱器６４にて過熱するため、請求項１の発明に比較して改質器２へ導入する反応ガスの温度を高く設定でき、酸素を含むガスの改質器２への投入量を減らすことができる。但し、燃料及び空気と水蒸気が混合された時に凝縮が発生しない程度に水蒸気温度を上昇させなければならず、水蒸発器６１から排出される排気ガスバーナー４燃焼ガスの熱量は増大するため、効率の優劣は場合により相違する。
【０１８１】
（１５）第１５の実施の形態
［構成］
次に請求項１９にかかる第１５の実施の形態について図１５を参照して説明する。第１５の実施の形態では、改質器２の外筒部に水素リッチガス冷却器２２が設置され複合一体化された点に特徴がある。
【０１８２】
［作用効果］
第１９の実施の形態によれば、改質器２と水素リッチガス冷却器２２の間の配管を省いて発電装置の体積を減少させ、装置のコンパクト化を図ることができる。また高温で運転される改質器２の外筒部を、より低温で運転される水素リッチガス冷却器２２にて包囲するので、改質器２表面から大気への放熱損失を減少させることができる。
【０１８３】
（１６）第１６の実施の形態
［構成］
第１６の実施の形態の構成を図１６に示す。第１６の実施の形態は請求項２０に対応し、その特徴は、排気ガスバーナー４の外筒部に燃料混合ガス過熱器６４が設置されて複合一体化された点にある。
【０１８４】
［作用効果］
第１６の実施の形態では、高温で運転される排気ガスバーナー４を燃料混合ガス過熱器６４で囲むことにより、排気ガスバーナー４表面から大気への放熱損失を抑えている。また、燃料混合ガス過熱器６４と排気ガスバーナー４とを複合一体化させることで両者間の接続流路が極小化し、装置をコンパクト化することができる。
【０１８５】
（１７）第１７の実施の形態
［構成］
請求項２１にかかる第１７の実施の形態について図１７を用いて説明する。第２１の実施の形態では、前記第５の実施の形態と同様、改質器２の外筒部下部に水素リッチガス冷却器２２が設置されると共に、改質器２の外筒部上部に水蒸発器６１が設置され、改質器２と水素リッチガス冷却器２２と水蒸発器６１という３つの機器が複合一体化されている。なお、図１７では水蒸発器６１を改質器２外筒部に直接設置しているが、これを水素リッチガス冷却器２２外側に設置してもよい。
【０１８６】
［作用効果］
このような第１７の実施の形態では、改質器２に水素リッチガス冷却器２２及び水蒸発器６１を複合一体化させることで、装置のコンパクト化をより高めることが可能とである。
【０１８７】
（１８）第１８の実施の形態
［構成］
図１８に示す第１８の実施の形態は請求項２２にかかり、前記第６の実施の形態と同様に、脱硫器３３の位置を水素リッチガス冷却器２２と低温一酸化炭素変成器３１の間に限定された点に特徴がある。なお、図１８では脱硫器３３が低温一酸化炭素変成器３１の前段に置かれた形になっているが、脱硫器３３の外筒部に低温一酸化炭素変成器３１を設置する、もしくは低温一酸化炭素変成器３１の外筒に脱硫器３３を設置するなどして両者を複合一体化させ放熱損失の低減を図ってもよいし、他の方法をとってもよい。
【０１８８】
［作用効果］
第１８の実施の形態においては、脱硫器３３と低温一酸化炭素変成器３１とを複合一体化することにより、放熱損失を低減させて一酸化炭素変成器３１の運転温度を維持することができる。また、機器の複合一体化により装置体積の減少を図ることができる。
【０１８９】
（１９）第１９の実施の形態
［構成］
第１９の実施の形態は請求項２３に対応しており、図１９は第１９の実施の形態の構成図である。第１９の実施の形態には、前記第７の実施の形態と同じく起動バーナー７０と、燃料電池１の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器１３５とが設けられている。起動バーナー７０は改質器２とは独立に設置してもよいし、改質器２と複合一体化するような構造であってもよい。また、改質器２、水素リッチガス冷却器２２、低温一酸化炭素変成器３１、脱硫器３３、排気ガスバーナー４、水蒸発器６１、燃料混合ガス過熱器６４の関係は請求項１８に基づいて各々独立に記述したが、請求項１９、請求項２０、請求項２１、請求項２２の発明に基づいて複合一体化させてもよい。
【０１９０】
起動バーナー７０燃焼ガスは酸素過多で発生させる必要があるが、改質触媒層２１は還元性雰囲気が望ましいため、起動バーナー７０燃焼ガスは改質触媒及びその雰囲気から隔絶され、リークなどによる相互の流通が存在しないよう製作されている。改質器２は４００℃以上に昇温することが望ましいが、下流の機器に高温に弱いものがあるので起動バーナー７０の燃焼ガス温度は４００〜５００℃程度であることが望ましい。これを達成するため、起動バーナー７０は少なくとも燃料体積の６０倍程度の空気を導入し、かつこの混合比で安定に燃焼させるために触媒燃焼器を使用することが好適である。
【０１９１】
また、排気ガスバーナー４と燃料混合ガス過熱器６４の間には起動バーナー７０からの燃焼ガスが排気ガスバーナー４からの燃焼ガス流路に合流する第１の合流点７３が形成され、燃料混合ガス過熱器６４と水蒸発器６１の間には燃焼ガスが分れる分岐点７１が形成され、さらには分岐点７１の下流には再度燃焼ガス流路に燃焼ガスが合流する第２の合流点７４が形成されている。
【０１９２】
装置起動時には起動バーナー７０が動作して燃焼ガスが発生し、この燃焼ガスが改質器２の改質触媒層２１を通過した後（図中の＊）、第１の合流点７３にて排気ガスバーナー４からの燃焼ガス流路に入る。このガス流路には元来、排気ガスバーナー４からの燃焼ガスが流れているため、雰囲気還元性である必要はなく、起動バーナー７０の燃焼ガスラインと共通化している。
【０１９３】
さらに、起動バーナー７０からの燃焼ガスは燃料混合ガス過熱器６４を通過し、分岐点７１にて直接水蒸発器６１に通じる通常の流路から一部が分岐し（図中の＊＊）、燃料電池冷却媒体加熱器１３５、脱硫器３３の吸収材層、低温一酸化炭素変成器３１の触媒層、選択酸化式一酸化炭素除去器３２の触媒層を貫流する。起動バーナー７０燃焼ガスは脱硫器３３吸収材、低温一酸化炭素変成器３１触媒、選択酸化式一酸化炭素除去器３２触媒及びその雰囲気から隔絶され、リークなどによる相互の流通が存在しないよう製作されている。選択酸化式一酸化炭素除去器３２の触媒層を貫流した起動バーナー７０燃焼ガスは、合流点７２にて分岐点７１にて分岐した残余の起動バーナー７０燃焼ガスと合流し、水蒸発器６１、水凝縮器５の順に送られる。
【０１９４】
なお、選択酸化式一酸化炭素除去器３２の触媒層は、反応器が複数から成る場合には２つ以上に分かれていてもよい。また、燃料電池冷却媒体加熱器１３５は図１９では燃料処理系冷却媒体循環径路１３３の水素リッチガス冷却器２２上流に設置されているが、設置位置はここに限定されず、燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流の部分を除く、燃料処理系冷却媒体循環径路１３３を含む燃料電池冷却媒体径路１３１のいずれの位置でもよい。燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流の部分は、この部分で測定した燃料電池冷却媒体温度で燃料電池冷却媒体冷却器１３４での熱交換量を制御することが多い。そのため、この位置に燃料電池加熱器１３５を設置すると擾乱要因となり易い。また、図１９では脱硫器３３は水素リッチガス冷却器２２と低温一酸化炭素変成器３１の中間に設置されているが、ここに限定されず例えば改質器２導入前の燃料流路に設置してもよい。
【０１９５】
［作用効果］
以上のような構成を有する第１９の実施の形態の作用効果は次の通りである。すなわち、装置起動時に発生した燃焼ガス起動バーナー７０の燃焼ガスは、燃料混合ガス過熱器６４を通過してこれを暖める。このとき燃料混合ガス過熱器６４の望ましい運転温度には未達であるが、燃料混合ガス過熱器６４は熱回収のために存在し、起動時には効率は度外視するので、運転温度程度にまで昇温する必要はなく、この条件で機能を充分に果たすことができる。
【０１９６】
このような流路構成を取ることで、起動バーナー７０燃焼ガスという同一の加熱源を用いながら、燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２、水蒸発器６１の昇温を同調して行うことができる。
【０１９７】
また、第１９の実施の形態では、改質触媒層２１、脱硫器３３吸収材層、低温一酸化炭素変成器３１触媒層、選択酸化式一酸化炭素除去器３２触媒層といった燃料電池１燃料極１１の上流に位置する機器について、水素リッチガスが流通する経路とは独立して起動バーナー７０燃焼ガスの流通経路を設置している。そのため、燃料処理系の触媒層において高温・還元性雰囲気での使用が想定されていても、燃焼ガスの流通により酸化及び結露が生じて活性低下が起きるおそれがなく、起動前の昇温に加えて還元操作を行う必要がない。
【０１９８】
（２０）第２０の実施の形態
［構成］
請求項２４及び２５にかかる第２０の実施の形態について図２０を参照して説明する。第２０の実施の形態は前記第１９の実施の形態（請求項２３の発明に対応）において、起動バーナー７０燃焼ガスと排気ガスバーナー４燃焼ガスの流路切替えを行う機構を設けた点に特徴があり、切替えを請求項２５の発明にかかる運転方法で実施している。
【０１９９】
すなわち、第８の実施の形態と同じく、起動バーナー７０と第１の合流点７３の間に第１止め弁７５が設けられ、分岐点７１と燃料電池冷却媒体加熱器１３５の間に第２止め弁７６が設けられ、選択酸化式一酸化炭素除去器３２の触媒層と第２の合流点７４の間に第３止め弁７７が設けられている。これら３つの止め弁７５、７６及び７７を請求項２５の発明にかかる運転方法により開閉し、燃焼ガスの流路切替えを行うようになっている。
【０２００】
［止め弁の開閉］
装置起動時には起動バーナー７０が点火されると共に、３つすべての止め弁７５、７６、７７が開き、起動バーナー７０燃焼ガスが流通する。分岐点７１と第２の合流点７４の間には止め弁は無く、燃料混合ガス過熱器６４出口側の高温ガスの一部は直接、水蒸発器６１を加熱する。なお、分岐点７１で分岐するガス流量を最適に配分するため、分岐点７１と第２の合流点７４の間にはオリフィスなどの圧損要素を設置してもよい。
【０２０１】
燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２のすべての昇温が完了したら、第２止め弁７６及び第３止め弁７７を閉じる。但し、何らかの原因でいずれかの機器の温度が過度に上昇し、予め設定された最高限界温度を越えた場合には他の機器の昇温が完了していなくとも、第２止め弁７６及び第３止め弁７７を閉じる。
【０２０２】
第２止め弁７６と第３止め弁７７の間に設置してある機器には温度の上限があるものが多い。例えば、燃料電池冷却媒体加熱器１３５の温度が沸点に近づくことは燃料電池冷却媒体全体がこの温度まで昇温することを意味するので、固体高分子電解質膜を初めとする燃料電池１の構成部材に損傷を与える可能性がある。また、脱硫器３３と低温一酸化炭素変成器３１は前述したように昇華性のＺｎＯを含む場合があり、選択酸化式一酸化炭素除去器３２では高温で反応の選択性が悪化する傾向が見られている。そのため、これら機器に最高限界温度を設定し、いづれかが限界に達したら第２止め弁７６及び第３止め弁７７を閉じて、機器の昇温を中断する。
【０２０３】
一方、水蒸発器６１は第２の合流点７４で合流した起動バーナー７０燃焼ガスで昇温される。この温度が目標温度に達しない間は第１止め弁７５が開いて起動バーナー７０燃焼ガスが送り込まれ、目標温度に達してかつ第２止め弁７６及び第３止め弁７７が閉じていたら、起動のための加熱を終了して第１止め弁７５が閉り、起動バーナー７０が停止して発電運転に移行する。
【０２０４】
運転中はこれらすべての弁７５、７６、７７が閉じて通常運転時の熱バランスを擾乱させない。停止時には第２止め弁７６及び第３止め弁７７が開いて起動バーナー燃焼ガス流路が水凝縮などで減圧し、リークなどの不適合の原因となることを防ぐことができる。
【０２０５】
但し、燃料電池冷却媒体加熱器１３５から選択酸化式一酸化炭素除去器３２の間の機器の加熱が未了であっても、水蒸発器６１の温度が沸点を越えて過度に上昇すると危険であるので、水蒸発器６１温度が予め設定された最高限界温度に達した場合は第２止め弁７６及び第３止め弁７７を開けたままで第１止め弁７５を閉め、起動バーナー７０を停止して新たな熱量の供給を停止し、残熱で昇温未了の機器を加熱する。水蒸発器６１の過度の昇温を防ぐため、安全弁を設置してもよい。
【０２０６】
［作用効果］
第２０の実施の形態では、上記の機構と制御により、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつ過剰昇温を防ぐことが可能となった。また、止め弁の開閉により燃焼ガス流路の切替えることができるので、起動バーナー７０の燃焼ガス流路と排気ガスバーナー４の燃焼ガス流路を共通化でき、装置の簡素化を図ることができる。
【０２０７】
（２１）第２１の実施の形態
［構成］
請求項２６、２７にかかる第２１の実施の形態について図２１を用いて説明する。第２１の実施の形態と前記第２０の実施の形態との相違点は、第２１の実施の形態では第２止め弁７６と第３止め弁７７の間に第２の分岐点７２があり、ここから大気に開放するベント配管が設置されていて、これに第４止め弁７８が設置されていることである。これは第２止め弁７６と第３止め弁７７が閉じた時にこの間を封じ切りにしないためのものである。これら４つの止め弁７５、７６、７７及び７８を請求項２７の発明にかかる運転方法により開閉し、前記第２０の実施の形態と同じく、起動バーナー７０燃焼ガスと排気ガスバーナー４燃焼ガスの流路切替えるになっている。なお、前記分岐点７１をここでは第１の分岐点７１とする。
【０２０８】
［止め弁の開閉］
装置起動時には起動バーナー７０が点火されると共に、第４止め弁７８以外の３つの止め弁７５、７６及び７７が開き、起動バーナー７０燃焼ガスが流通する。第１の分岐点７１と第２の合流点７４の間には止め弁が無い点、分岐点７１と第２の合流点７４の間にはオリフィスなどの圧損要素を設置してもよい点などは第２０の実施の形態と同様である。
【０２０９】
燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２すべての昇温が完了したら、第２止め弁７６及び第３止め弁７７を閉じ、第１止め弁７５及び第４止め弁７８を開く。但し、何らかの原因でいずれかの機器の温度が過度に上昇し、予め設定された最高限界温度を越えた場合は他の機器の昇温が完了していなくとも第２止め弁７６及び第３止め弁７７を閉じ、第４止め弁７８を開いて、機器の安全性を確保する。
【０２１０】
一方、水蒸発器６１の温度が目標温度に達しない間は第１止め弁７５が開いて起動バーナー７０燃焼ガスが送り込まれ、目標温度に達してかつ第２止め弁７６及び第３止め弁７７が閉じかつ第４止め弁７８が開いていたら、起動のための加熱を終了して第１止め弁７５が閉り、起動バーナー７０が停止して発電運転に移行する。
【０２１１】
運転中はこれらすべての止め弁７５、７６、７７及び７８が閉じて通常運転時の熱バランスの擾乱を防ぐようになっている。停止時には第２止め弁７６か第３止め弁７７のどちらかと第４止め弁７８が開いて起動バーナー７０燃焼ガス流路の減圧を防ぐことができる。
【０２１２】
但し、燃料電池冷却媒体加熱器１３５から選択酸化式一酸化炭素除去器３２の間の機器の加熱が未了であっても、水蒸発器６１の温度が沸点を越えて過度に上昇すると危険であるので、水蒸発器６１温度が予め設定された最高限界温度に達した場合には第２止め弁７６及び第３止め弁７７を開け、かつ第４止め弁７８を閉めた状態で第１止め弁７５を閉める。これにより、起動バーナー７０を停止して新たな熱量の供給を停止し、残熱で昇温未了の機器を加熱するものとする。なお、水蒸発器６１の過度の昇温を防ぐため、安全弁を設置してもよい点は第８の実施の形態と同然である。
【０２１３】
［作用効果］
以上の第２１の実施の形態では、上記の機構と制御により、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつ過剰昇温を防ぐことができる。また、燃焼ガス流路が切替可能であるため起動バーナー７０の燃焼ガス流路と排気ガスバーナー４の燃焼ガス流路を共通化でき、装置を簡素化できる。さらには、第４止め弁７８の働きにより起動バーナー７０燃焼ガス流路の減圧を防止することができる。
【０２１４】
（２２）第２２の実施の形態
［構成］
請求項２８にかかる第２２の実施の形態について、図２２を参照して説明する。第２２の実施の形態は第１９の実施の形態（請求項２３の発明に対応）の変形である。第２２の実施の形態は第１０の実施の形態と同様、起動バーナー７０燃焼ガス流路が分岐点７１で分岐され、燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２を加熱した起動バーナー７０燃焼ガスが以降熱交換に使用されること無く大気中に放出されることを特徴とする。
【０２１５】
選択酸化式一酸化炭素除去器３２の触媒層は、反応器が複数から成る場合には２つ以上に分かれていてもよい。また、燃料電池冷却媒体加熱器１３５は図２２では燃料処理系冷却媒体循環径路１３３の水素リッチガス冷却器２２上流に設置されているが、設置位置はここに限定されず、燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流の部分を除く、燃料処理系冷却媒体循環径路１３３を含む燃料電池冷却媒体径路１３１のいずれの位置でもよい。また、図２２では脱硫器は水素リッチガス冷却器２２と低温一酸化炭素変成器３１の中間に設置されているが、ここに限定されず例えば改質器２導入前の燃料流路に設置してもよい。
【０２１６】
［作用効果］
以上のような第２２の実施の形態によれば、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつより簡易かつ効果的な燃料電池発電装置を構築することが可能となった。
【０２１７】
なお、第１９の実施の形態（請求項２３の発明に対応）と第２２の実施の形態（請求項２８の発明に対応）の長短は、選択酸化式一酸化炭素変成器３２の目標運転温度、特にこれが複数段に分割されている場合には最終段の目標運転温度に依存する。目標運転温度が高ければ前者の方が有利であり、水の沸点前後の低温であれば後者の方がより効果的である。
【０２１８】
（２３）第２３の実施の形態
［構成］
図２３に示す第２３の実施の形態は、請求項２９及び３０に対応するものであり、第２２の実施の形態（請求項２８の発明に対応）において、起動バーナー７０燃焼ガスと排気ガスバーナー４燃焼ガスの流路切替えを行う機構を設けた点に特徴がある。すなわち、起動バーナー７０と第１の合流点７３の間に第１止め弁７５が設けられ、分岐点７１と脱硫器３３の吸収材層の間に第２止め弁７６が設けられている。これら止め弁７５、７６の開閉を請求項３０の発明にかかる運転方法で実施している。
【０２１９】
［止め弁の開閉］
装置起動時には起動バーナー７０が点火されると共に、２つの止め弁７５、７６が開き、起動バーナー７０燃焼ガスが流通する。流量配分最適化のための圧損要素は水蒸発器６１の上流に設置する必要が無く、かつ圧損要素として水蒸発器６１及び水凝縮器５をカウントすることができるので、第２の合流点７４を有する場合より設置する圧損要素を低減し、排気ガスライン全体の圧損を低下させることが可能である。
【０２２０】
燃料電池冷却媒体加熱器１３５、脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２すべての昇温が完了したら、第２止め弁７６を閉じる。但し、何らかの原因でいづれかの機器の温度が過度に上昇し、予め設定された最高限界温度を越えた場合は他の機器の昇温が完了していなくとも第２止め弁７６を閉じ、安全性を確保する。
【０２２１】
一方、水蒸発器６１は温度が目標温度に達しない間は第１止め弁７５が開いて起動バーナー７０燃焼ガスが送り込まれ、目標温度に達してかつ第２止め弁７６が閉じていたら起動のための加熱を終了して第１止め弁７５が閉り、起動バーナー７０が停止して発電運転に移行する。
【０２２２】
運転中は止め弁７５及び７６が両方とも閉じて通常運転時の熱バランスの擾乱を防止する。停止時には第２止め弁７６が開いても閉じていても起動バーナー７０燃焼ガス流路は大気に開放されるので、減圧のおそれはない。但し、燃料電池冷却媒体加熱器１３５から選択酸化式一酸化炭素除去器３２の間の機器の加熱が未了であっても、水蒸発器６１の温度が沸点を越えて過度に上昇すると危険であるので、水蒸発器６１温度が予め設定された最高限界温度に達した場合には第２止め弁７６を開けたままで第１止め弁７５を閉め、起動バーナー７０を停止して新たな熱量の供給を停止し、残熱で昇温未了の機器を加熱する。なお、水蒸発器６１の過度の昇温を防ぐため、安全弁を設置してもよい。
【０２２３】
［作用効果］
第２３の実施の形態では、上記のような機構と制御により、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつ過剰昇温を防ぎながら、より簡易かつ効果的な燃料電池発電装置を構築することが可能となった。
【０２２４】
（２４）第２４の実施の形態
［構成］
第２４の実施の形態は請求項３１に対応しており、図２４は第２４の実施の形態の構成図を示している。第２４の実施の形態では、起動バーナー７０燃焼ガスが改質器２の改質触媒層２１を通過した後、合流点７３にて排気ガスバーナー４からの燃焼ガス流路に流入し、燃料混合ガス過熱器６４、水蒸発器６１、燃料電池冷却媒体加熱器１３５、水凝縮器５の順に通過するように構成されたことを特徴とする。
【０２２５】
起動バーナー７０で発生した起動バーナー７０燃焼ガスは改質触媒層２１を貫流して加熱した後、燃料混合ガス過熱器６４を過熱し、さらに水蒸発器６１を加熱する。ここでガス温度が比較的低位になってから、燃料電池冷却媒体加熱器１３５を加熱する。燃料電池冷却媒体は通常水の沸点以下高々８５℃程度なので、水蒸発器６１加熱後のガスでも加熱可能である。燃料電池冷却媒体加熱器１３５を出た起動バーナー７０燃焼ガスは水凝縮器５を経て大気に放出される。なお、目標昇温温度が比較的低くかつ加熱に必要な熱量が比較的少ない脱硫器３３、低温一酸化炭素変成器３１、選択酸化式一酸化炭素除去器３２の昇温は電力で行うようになっている。
【０２２６】
選択酸化式一酸化炭素除去器３２の触媒層は、反応器が複数から成る場合には２つ以上に分かれていてもよい。また、燃料電池冷却媒体加熱器１３５は図１２では燃料処理系冷却媒体循環径路１３３の水素リッチガス冷却器２２上流に設置されているが、設置位置はここに限定されず、燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流の部分を除く、燃料処理系冷却媒体循環径路１３３を含む燃料電池冷却媒体径路１３１のいずれの位置でもよい。燃料電池冷却媒体加熱器１３４の下流かつ燃料電池１の上流部分は通常、燃料電池冷却媒体温度の測定箇所であり、測定結果に基づいて燃料電池冷却媒体冷却器１３４での熱交換量を制御する。したがって、前記の位置を燃料電池加熱器１３５の設置位置に選ぶと擾乱要因となり易い。そのためこの部分は外す。また、図２４では脱硫器３３は水素リッチガス冷却器２２と低温一酸化炭素変成器３１の中間に設置されているが、ここに限定されず例えば改質器２導入前の燃料流路に設置してもよい。
【０２２７】
［作用効果］
以上の第２４の実施の形態では、高温が必要な改質器２２の昇温及び昇温に多くの熱量を必要とする燃料電池冷却媒体加熱器１３５及び水蒸発器６１の加熱にのみ起動バーナー７０燃焼ガスを使用している。つまり、機器を選んで燃焼ガスを供給することにより燃焼ガス流路をシンプルに構成することができ、装置の簡略化を進めることができる。
【０２２８】
なお、請求項２３もしくは請求項２８の発明と請求項３１の発明のどちらを採用するかは、装置の規模に依存する。装置規模が大きければ請求項２３もしくは請求項２８の発明が有利であり、装置規模が小さければ請求項３１の発明の方がより効果的である。
【０２２９】
（２５）第２５の実施の形態
［構成］
請求項３２及び３３に対応する第２５の実施の形態について、図２５を用いて説明する。第２５の実施の形態は第２４の実施の形態（請求項３１の発明に対応）において、起動バーナー７０燃焼ガスと排気ガスバーナー４燃焼ガスの流路切替えを行う機構を設けている。すなわち、起動バーナー７０と第１の合流点７３の間に第１止め弁７５が設けられ、請求項３３の発明にかかる運転方法により第１止め弁７５を開閉してガス流路の切替えを行っている。
【０２３０】
［止め弁の開閉］
装置起動時には起動バーナー７０が点火されると共に、第１止め弁７５が開き、起動バーナー７０燃焼ガスが流通する。流量配分最適化の必要が無いのでそのための圧損要素は不要である。水蒸発器６１は温度が目標温度に達しない間は止め弁７５が開いて起動バーナー７０燃焼ガスが送り込まれ、目標温度に達したら起動のための加熱を終了して第１止め弁７５が閉り、起動バーナー７０が停止して発電運転に移行する。
【０２３１】
運転中は第１止め弁７５が閉じて通常運転時の熱バランスを擾乱させない。停止時には第１止め弁７５が開いても閉じていてもその両側とも大気に開放されるので減圧のおそれはない。但し、水蒸発器６１の昇温が未了であるのに燃料電池冷却媒体加熱器１３５の昇温が最高限界温度に達した場合は、燃料電池１の冷却水温度調節を目的に設置された燃料電池冷却媒体冷却器１３４により熱を放出する。これにより水蒸発器６１の昇温を継続しながら燃料電池冷却媒体の過度の昇温を防ぐ。
【０２３２】
［作用効果］
第２５の実施の形態では、上記のような機構と制御により、燃料電池発電装置の各機器をほぼ同調して所定の温度に昇温し、かつ過剰昇温を防ぎながら、より簡易かつ効果的な燃料電池発電装置を構築することができる。
【０２３３】
【発明の効果】
以上説明したように、本発明によれば、コンパクトで機器構成が簡素でありながら、停止状態から短時間で起動でき、かつ排熱を有効に回収する高効率の固体高分子型燃料電池発電装置及びその運転方法を提供することができる。
【図面の簡単な説明】
【図１】本発明の第１の実施の形態の構成図。
【図２】本発明の第２の実施の形態の構成図。
【図３】本発明の第３の実施の形態の構成図。
【図４】本発明の第４の実施の形態の構成図。
【図５】本発明の第５の実施の形態の構成図。
【図６】本発明の第６の実施の形態の構成図。
【図７】本発明の第７の実施の形態の構成図。
【図８】本発明の第８の実施の形態の構成図。
【図９】本発明の第９の実施の形態の構成図。
【図１０】本発明の第１０の実施の形態の構成図。
【図１１】本発明の第１１の実施の形態の構成図。
【図１２】本発明の第１２の実施の形態の構成図。
【図１３】本発明の第１３の実施の形態の構成図。
【図１４】本発明の第１４の実施の形態の構成図。
【図１５】本発明の第１５の実施の形態の構成図。
【図１６】本発明の第１６の実施の形態の構成図。
【図１７】本発明の第１７の実施の形態の構成図。
【図１８】本発明の第１８の実施の形態の構成図。
【図１９】本発明の第１９実施の形態の構成図。
【図２０】本発明の第２０の実施の形態の構成図。
【図２１】本発明の第２１の実施の形態の構成図。
【図２２】本発明の第２２の実施の形態の構成図。
【図２３】本発明の第２３の実施の形態の構成図。
【図２４】本発明の第２４の実施の形態の構成図。
【図２５】本発明の第２５の実施の形態の構成図。
【図２６】従来の固体高分子型燃料電池発電装置の構成図。
【符号の説明】
１：燃料電池
１１：燃料極
１２：酸化剤極
１３：冷却装置
１３１：燃料電池冷却媒体径路
１３２：冷却媒体循環ポンプ
１３３：燃料処理系冷却媒体循環径路
１３４：燃料電池冷却媒体冷却器
１３５：燃料電池冷却媒体加熱器
２：改質器
２１：改質触媒層
２２：水素リッチガス冷却器
３：一酸化炭素変成器
３１：低温一酸化炭素変成器
３２：選択酸化式一酸化炭素除去器
３３：脱硫器
４：排気ガスバーナー
５：水凝縮器
６１：水蒸発器
６２：水蒸気過熱器
６３：燃料混合ガス予熱器
６４：燃料混合ガス過熱器
７０：起動バーナー
７１：第１の分岐点
７２：第２の分岐点
７３：第１の合流点
７４：第２の合流点
７５：第１止め弁
７６：第２止め弁
７７：第３止め弁
７８：第４止め弁[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer electrolyte fuel cell power generator whose operating temperature is lower than the boiling point of water, and in particular, a polymer electrolyte fuel cell generator using a gas containing oxygen such as water vapor and air for fuel reforming. And the operation method thereof.
[0002]
[Prior art]
A fuel cell power generation device is a power generation device that directly converts chemical energy into electrical energy by performing an electrochemical reaction using a continuously supplied fluid as a raw material. FIG. 26 shows the basic equipment configuration. As shown in the figure, a fuel cell 1, a reformer 2, a carbon monoxide converter 3, an exhaust gas burner 4, and a water condenser 5 are provided as main components of the fuel cell power generator.
[0003]
The fuel cell 1 has an ion conductive electrolyte layer and a fuel electrode 11 and an oxidant electrode 12 arranged on both sides thereof as basic structural units, and is usually configured by laminating a plurality of units. The gas supplied to the fuel electrode 11 contains hydrogen, and the hydrogen is oxidized into water by an electrochemical reaction that generates electric power in the fuel cell 1. The gas containing hydrogen supplied to the fuel cell 1 is produced by the reformer 2.
[0004]
The reformer 2 has a reforming catalyst layer 21 where fuel is reformed together with water vapor by a catalytic reaction in the gas phase to provide a hydrogen-rich gas mainly composed of hydrogen, carbon monoxide, carbon dioxide, and water. To do. The fuel is composed of molecules each containing at least one hydrogen atom and carbon atom.
[0005]
The fuel may contain oxygen atoms, but it reacts with hydrogen or water such as nitrogen to produce a basic compound, which may be deactivated when an acidic electrolyte layer is used, or modified with sulfur or halogen. A compound containing an atom that may poison a catalyst or the like, or an atom in which an oxide such as a metal element is non-volatile is not desirable as a fuel. These low-concentration substances are selected as fuel, and at the same time, if such undesirable substances are included in the fuel, they should be removed at least before reaching equipment that may be affected by poisoning. There is a need. Examples of the fuel suitable for the fuel cell include city gas, LPG, methanol, and kerosene.
[0006]
Typical reforming methods for fuel include steam reforming using only steam and partial oxidation steam reforming using oxygen or air in combination with steam. The partial oxidation steam reforming reaction in the reformer 2 will be described by taking methane as an example.
[0007]
[Chemical 1]
CH Four + H 2 O → CO + 3H 2 ... (1)
[Chemical 2]
CH Four + O 2 → CO + H 2 O + H 2 ... (2)
[Chemical 3]
CO + H 2 O → CO 2 + H 2 ... (3)
Reaction (1) is an endothermic reaction of -206 kJ / mol, reaction (2) is an exothermic reaction of +278 kJ / mol under standard conditions, and reaction (3) called a CO shift reaction is an exothermic reaction of +41 kJ / mol. In the reformer 2 with only steam reforming, only the reactions (1) and (3) occur, so the total reforming reaction becomes an endothermic reaction of −165 kJ / mol, and CH Four 4 H per 2 Produces.
[0008]
However O 2 In the partial oxidation reformation in the narrow sense using only the gas containing oxygen as the oxidant, the total heat balance is an exothermic reaction of +319 kJ / mol from the reactions (2) and (3). Four 2 H per hit 2 Only generate. Water and O 2 The heat balance in partial oxidation steam reforming using both of these for reforming is intermediate between the above two examples. 2 / CH Four = 0.34 thermally balanced, CH in this case Four H per hit 2 The amount produced is 3.3. O 2 If the amount is greater than this balance value, the total heat balance in the reforming reaction will be exothermic and CH Four H per hit 2 The production amount is reduced from 3.3, and the efficiency is lowered. Conversely, if it is smaller than this value, it becomes endothermic and CH Four H per hit 2 The production increases from 3.3 and the efficiency increases.
[0009]
Since a pure steam reforming reaction is a large endothermic reaction, it is necessary to supply a large amount of heat from the outside in order to maintain the reaction. Therefore, a complicated mechanism is indispensable for heating the reformer 2, and the reformer 2 is generally expensive. On the other hand, O introduced in the partial oxidation steam reforming reaction. 2 By adjusting the amount and the like, the mechanism of the reformer 2 can be simplified and inexpensive, but on the other hand, H 2 The production efficiency is inferior to that of steam reforming.
[0010]
Examples of the reforming catalyst used for the reforming catalyst layer 21 include nickel-based catalysts such as G-90 manufactured by Nissan Gardler, and the Cu-ZnO-based low-temperature carbon monoxide conversion catalyst mentioned later and Poisoned with Cl. For this reason, it is desirable to generate the steam used for reforming from distilled water or ion exchange water.
[0011]
Since carbon monoxide poisons a catalyst that causes an electrochemical reaction at the fuel electrode 11 of the fuel cell 1, it is necessary to reduce its concentration as much as possible. The CO shift reaction also proceeds in the reformer 2, but the CO concentration at the outlet of the reformer 2 is on the order of several percent, which is not sufficient to avoid catalyst poisoning of the fuel electrode 11. Therefore, a carbon monoxide converter 3 is installed between the reformer 2 and the fuel cell fuel electrode 11. This carbon monoxide transformer 3 can reduce the carbon monoxide concentration to a desired level.
[0012]
In many cases, the carbon monoxide transformer 3 is configured by installing a plurality of carbon monoxide transformers in series according to a target carbon monoxide concentration. Examples of the carbon monoxide converter 3 include a low-temperature carbon monoxide converter 31 and a selective oxidation carbon monoxide remover 32. The low-temperature carbon monoxide converter 31 has a low-temperature carbon monoxide conversion catalyst layer made of a catalyst that promotes the CO shift reaction, and lowers the CO concentration by promoting the CO shift reaction. The low-temperature carbon monoxide converter 31 is advantageous in terms of hydrogen generation efficiency because hydrogen is generated with the shift of CO. However, since the reaction is an equilibrium reaction, the carbon monoxide concentration at the outlet is the outlet gas temperature. Will be constrained by the equilibrium concentration. On the other hand, the selective oxidation carbon monoxide remover 32 is a device that reduces the carbon monoxide concentration by a selective oxidation reaction between carbon monoxide and oxygen in the hydrogen-rich gas on the packed catalyst. Since the reaction in the selective oxidation carbon monoxide remover 32 is an irreversible reaction, the carbon monoxide concentration can be reduced as compared with the shift reaction. However, since carbon monoxide is not used for hydrogen generation, it is disadvantageous in terms of hydrogen generation efficiency. In addition, in order to secure the removal amount of carbon monoxide, an excessive amount of oxygen is supplied to the carbon monoxide, and a part of hydrogen is oxidized, so that the hydrogen generation efficiency is further lowered. Thus, it is disadvantageous in terms of hydrogen generation efficiency to perform selective oxidation carbon monoxide removal when the carbon monoxide concentration is high. Therefore, selective oxidation type carbon monoxide removal is usually used when the concentration of carbon monoxide is reduced to several tens of ppm or less.
[0013]
By the way, since the CO shift reaction in the low temperature carbon monoxide converter 31 is advantageous in terms of equilibrium at low temperature, the reaction temperature is preferably 300 ° C. or lower, more preferably about 200 ° C. On the other hand, since the operating temperature of the reformer 2 is at least 400 ° C. and usually a high temperature of 600 ° C. or higher, the temperature of the hydrogen-rich gas when the hydrogen-rich gas discharged from the reformer 2 is supplied to the low-temperature carbon monoxide converter 31. Must be reduced. Therefore, a hydrogen rich gas cooler 22 is installed between the reformer 2 and the low temperature carbon monoxide converter 31.
[0014]
The fuels such as city gas, LPG, and kerosene contain trace amounts of sulfur in the form of organic compounds, which can poison various catalysts used in the above reactors, particularly at low temperatures. is there. An example of such a catalyst is a Cu—ZnO-based low temperature carbon monoxide conversion catalyst. For this reason, a desulfurizer 33 for removing sulfur is provided in the previous stage of the low-temperature carbon monoxide converter 31. Unlike carbon monoxide, the sulfur content cannot be converted into a non-toxic gas by a chemical reaction. 2 S gas, SO 2 After changing to gas or the like, absorption removal by the absorbent layer is performed in the desulfurizer 33. ZnO etc. are known as an example of such a desulfurizer 33 absorber layer.
[0015]
The desulfurizer 33 may be placed before the reformer 2 or may be placed after the reformer 2. When the desulfurizer 33 is placed in front of the reformer 2, the sulfur-containing organic compound in the fuel is converted to H. 2 It is necessary to further install a reactor for changing to S or the like, and the equipment is complicated and difficult to downsize, but it is more reliable in avoiding sulfur poisoning of the reforming catalyst layer 21. On the other hand, when the desulfurizer 33 is placed at the rear stage of the reformer 2, the sulfur-containing organic compound is H in the reformer 2 without any special pretreatment. 2 Since it changes to S, simplification and cost reduction of an apparatus can be achieved. A reforming catalyst such as a Ni-based catalyst is less affected by sulfur poisoning at a high temperature, and such a form is possible, but ZnO, which is a typical absorbent material of the desulfurizer 33, is volatile at a high temperature. Is preferably installed between the hydrogen rich gas cooler 22 and the low temperature carbon monoxide converter 31. In FIG. 26, the desulfurizer 33 is installed between the hydrogen rich gas cooler 22 and the low-temperature carbon monoxide converter 31, but may be upstream of the reformer 2 as described above.
[0016]
The hydrogen-rich gas from which harmful impurities have been removed by the above-described means enters the fuel cell 1 and between oxygen contained in the air flowing through the fuel cell oxidant electrode 12 while passing through the fuel cell fuel electrode 11. The following electrochemical reaction occurs, generating electric power and heat, and consuming hydrogen contained therein. Although the generated electric power is direct current, it is usually converted into alternating current via an inverter and supplied to the demand end. Further, the generated heat is discharged out of the fuel cell by the cooling medium flowing through the fuel cell cooling medium path 13.
[0017]
[Formula 4]
Fuel electrode: 2H 2 → 4H + + 4e - (4)
[Chemical formula 5]
Oxidant electrode: O 2 + 4HH + + 4e - → 2H 2 O ... (5)
In terms of efficiency, it is better that the utilization rate of hydrogen in the hydrogen-rich gas due to electrochemical reaction is higher, but if the utilization rate becomes too high, factors such as fluctuations in the flow rate of hydrogen-rich gas and non-uniform distribution of hydrogen-rich gas in the fuel cell 1 There is a risk of fuel shortage. Therefore, the hydrogen utilization rate is desirably 80% or less.
[0018]
Part of the combustible gas supplied to the fuel cell fuel electrode 11 is discharged from the fuel cell fuel electrode 11 without being reacted. Such unreacted combustible gas includes hydrogen that has not been used in the electrochemical reaction, fuel that has not been reformed by the reformer 2, and hydrocarbons that are by-produced by the reformer 2 or the carbon monoxide converter 31. It is possible. There is a safety problem if these are discharged to the environment as they are. Therefore, an exhaust gas burner 4 is provided to burn them. As an oxidant for the exhaust gas burner 4, it is common to use a part of the exhaust gas from the fuel cell oxidant electrode 12 or the atmosphere. Since the combustion gas of the exhaust gas burner 4 has a high temperature, it can be used as a heating source for equipment.
[0019]
The combustion gas of the exhaust gas burner 4 and the exhaust gas of the fuel cell oxidant electrode 12 that has not been used in the burner 4 are obtained from the water added for the production of hydrogen rich gas and the fuel consumed in the fuel cell 1 and the exhaust gas burner 4. Contains generated water. In order to collect this water, a water condenser 5 is installed at the exhaust gas outlet.
[0020]
The fuel cell power generation apparatus having the above configuration is divided into several types depending on the electrolyte layer of the fuel cell. That is, a phosphoric acid fuel cell using phosphoric acid, an alkaline fuel cell using an alkaline aqueous solution, a molten carbonate fuel cell using a molten carbonate, a solid electrolyte fuel cell using a solid ceramic electrolyte, and a solid polymer electrolyte Examples thereof include solid polymer electrolyte fuel cells to be used. Among these, the solid polymer electrolyte fuel cell is operated at a relatively low temperature below the boiling point of water, so it can be started up in a relatively short time, and a high output density is expected. In recent years, it has attracted particular attention due to the absence of electrolyte depletion.
[0021]
[Problems to be solved by the invention]
However, the solid polymer electrolyte fuel cell has the following problems to be solved in order to increase the efficiency of the power generation device. Power generation efficiency is H from fuel 2 However, in order to increase this, the reaction in the reformer 2 must be close to steam reforming. However, this means that the reforming reaction is inclined toward the endothermic side, and heat supply from the outside is required. The device that shows the maximum calorific value in the power generation apparatus is the fuel cell 1, but since the operating temperature is a low temperature that is usually lower than the boiling point of water, heat to the reformer 2 that is normally operated at a high temperature of 600 ° C. or higher. Not available for supply. Therefore, it is necessary to use another heating source for supplying heat to the reformer 2. Therefore, the use of the exhaust gas burner 4 has been studied conventionally.
[0022]
In addition, a water evaporator that generates water vapor to be supplied to the reformer 2 is installed in the power generator, and an exhaust gas burner 4 is also expected as a heating source of the water evaporator. This is because the operating temperature of the fuel cell 1 is lower than the boiling point of water, so that the heat generated by the fuel cell 1 cannot be used for the generation of water vapor.
[0023]
Thus, although the demand as a heat source for the exhaust gas burner 4 is large, the heat generation is only about 50 to 60% of the heat generation of the fuel cell 1 at most. Normally, the fuel cell 1 has an H at the fuel electrode 11 inlet. 2 If the amount is 100, 80 is consumed for power generation, about 50 to 60% is converted to electric energy, and the remaining 40 to 50% is converted to heat. Therefore, the heat generation of the fuel cell 1 is caused by the H 2 It is about 32 to 40 in terms of quantity. However, the H burned by the exhaust gas burner 4 2 The amount is only 20 which is not consumed by power generation, and is smaller than the heat generation of the fuel cell 1. For this reason, efficient operation of the amount of heat generated from the exhaust gas burner 4 has been required.
[0024]
Further, in order to start the fuel cell power generator, it is necessary to raise the temperature to a temperature at which each device exhibits its function. The catalyst of the fuel electrode 11 is poisoned by carbon monoxide as described above, and this is because carbon monoxide is adsorbed on the catalyst surface and covers the catalytically active site. Therefore, if carbon monoxide is contained in the gas flowing through the fuel electrode 11 before operation, the catalytically active site is covered thereby, and the catalyst of the fuel electrode 11 may fall into a heavily poisoned state at the start of operation. is there. Of course, carbon monoxide contained in the hydrogen-rich gas during operation is reduced, but carbon monoxide must also be reduced in the gas flowing through the fuel electrode 11 before starting. Therefore, prior to the introduction of the raw material gas into the reformer 2 and the start of power generation, it is necessary to raise the temperature of the low-temperature carbon monoxide converter 31 and the selective oxidation carbon monoxide remover 32 to a temperature at which the operation can be sufficiently performed.
[0025]
Furthermore, it is necessary to raise the temperature of the reforming catalyst layer 21 to a certain temperature in order to start the reforming reaction. Taking a nickel-based reforming catalyst as an example, the operating temperature range is 400 ° C. to 1300 ° C., so it is considered necessary to raise the temperature to about 400 ° C. Even if the reforming catalyst acts as a combustion catalyst and a temperature rise due to combustion of the raw material gas can be expected, the temperature of the reforming catalyst layer 21 needs to be raised to a temperature at which the ignition conditions are met. Prior to gas introduction, it is necessary to raise the temperature of the reformer 2 to a temperature at which the reformer 2 can be sufficiently operated.
[0026]
As for the water evaporator, water vapor is not generated unless the temperature is raised. In the partial oxidation steam reforming reaction, hydrogen can be generated without using steam as a raw material gas. However, since the calorific value for the input fuel is remarkably increased compared with the assumption that steam is introduced during normal operation, reforming is possible. The catalyst layer 21 may be damaged by high heat. Taking a nickel-based reforming catalyst as an example, the service temperature is 1300 ° C., and it is necessary to avoid a higher temperature, whether temporarily or locally. Therefore, prior to the introduction of the raw material gas to the reformer 2, the water evaporator 61 must be heated to a state where steam can be generated.
[0027]
In a type other than the solid polymer type fuel cell, for example, a phosphoric acid type fuel cell, it was possible to raise the temperature using a fuel cell cooling medium circulating in each device. That is, when a Cu—ZnO-based low temperature carbon monoxide conversion catalyst is used in the low temperature carbon monoxide converter 31, the operating temperature is about 200 ° C. However, this is higher than the operating temperature of the polymer electrolyte fuel cell which is below the boiling point of water, and it cannot be raised to this temperature using the fuel cell cooling medium. Thus, in order to start the polymer electrolyte fuel cell power generator, a fuel cell cooling medium cannot be used, and a new method is required. Furthermore, in order to reduce the size and increase the efficiency of the entire power generation device, it has been required to reduce the size of each device and reduce the heat dissipation loss.
[0028]
The present invention has been proposed in order to solve the above-described problems of the prior art, and its main purpose is to be able to start from a stopped state in a short time while being compact and having a simple device configuration, and An object of the present invention is to provide a highly efficient polymer electrolyte fuel cell power generator that effectively recovers exhaust heat and an operation method thereof.
[0029]
Another object of the present invention is to propose a polymer electrolyte fuel cell power generation device that achieves downsizing of each device and reduction of heat dissipation loss, downsizing of the entire device, and higher efficiency. is there.
[0030]
[Means for Solving the Problems]
The present invention has been proposed in order to achieve the above object, and includes a fuel cell having a gas containing hydrogen as a fuel and a solid polymer as an electrolyte and an oxidizer electrode and a fuel electrode, and via the fuel cell. A fuel cell cooling medium path for circulating the cooling medium, and a fuel processing system cooling medium path for branching the fuel cell cooling medium from the fuel cell upstream of the fuel cell cooling medium path and joining the fuel cell cooling medium to the fuel cell cooling medium path downstream of the fuel cell A cooling medium circulation pump that circulates the cooling medium through the fuel cell cooling medium path, a fuel cell cooling medium cooler that removes heat from the cooling medium and adjusts the temperature of the cooling medium, and an upstream of the fuel cell fuel electrode. A reforming catalyst layer having a reforming catalyst layer containing at least one carbon atom and one hydrogen atom in the molecule, a gas containing oxygen, and a mixture of water vapor and hydrogen-rich gas A reformer to be reformed, a hydrogen rich gas cooler that is installed downstream of the reformer of the hydrogen rich gas flow path and performs heat exchange between the hydrogen rich gas and the fuel cell cooling medium flowing through the fuel processing system coolant path, and the hydrogen rich gas A low-temperature carbon monoxide converter having a low-temperature carbon monoxide conversion catalyst layer installed downstream of the cooler, and an absorbent layer installed upstream of the low-temperature carbon monoxide converter, and having the absorbent layer in the fuel or hydrogen rich gas From a desulfurizer that absorbs sulfur, one or more selective carbon monoxide removers that have a selective carbon monoxide removal catalyst layer installed downstream of the low-temperature carbon monoxide converter, and the fuel electrode of the fuel cell An exhaust gas burner that burns by mixing all or part of the exhaust gas from the exhaust gas and all or part of the exhaust gas from the oxidizer electrode, and a mixture of the combustion gas from the exhaust gas burner and the exhaust gas from the oxidizer electrode In the solid polymer fuel cell power plant and a water condenser to condense the provided water from the scan, it has the following characteristics.
[0031]
The invention of claim 1 includes a water evaporator that generates steam to be supplied to the reformer, a steam superheater that superheats steam generated by the water evaporator, and a gas that contains oxygen as fuel to be supplied to the reformer, A fuel mixed gas preheater that heats in a mixed state, and the combustion gas from the exhaust gas burner passes through the steam superheater, the fuel mixed gas preheater, the water evaporator, and the water condenser in this order. A flow path is formed.
[0032]
In the first aspect of the present invention, the combustible material that has not been consumed in the fuel cell is combusted by the exhaust gas burner, and this combustion gas is burned into the steam superheater, the fuel mixed gas preheater, the water evaporator, and the water condenser. And the heat of combustion of the exhaust gas burner can be efficiently recovered by passing through the high-temperature equipment in order. The operating temperature of these devices is the highest in the steam superheater, whose outlet temperature is the reaction gas temperature supplied to the reformer, then the fuel gas mixture preheater, and the exhaust gas temperature after heat exchange is about the boiling point of water The water evaporator and the water condenser in which the exhaust gas temperature after heat exchange falls below the dew point of the fuel cell exhaust gas are decreased in this order. On the other hand, in terms of efficiency, it is desirable to suppress heat generation in the partial oxidation reformer, and for that purpose, it is desirable to raise the temperature of the raw material gas as much as possible. Therefore, it is most desirable in terms of efficiency to distribute the high-temperature gas for heat recovery in this order.
[0033]
In addition, the operating temperature of the fuel gas mixture preheater that heats the gas mixture containing oxygen and gas, such as air, must be kept lower than that of the steam superheater. This is because, when a mixed gas of gas containing oxygen such as air and fuel is heated, it may ignite at a lower temperature than when coexisting with water vapor.
[0034]
By the way, since the amount of heat is large even though the temperature required in the water evaporator is lower than the temperature necessary for the superheating of water vapor and the preheating of the fuel mixed gas, if water evaporation is performed prior to the preheating of the fuel mixed gas, The combustion gas temperature of the exhaust gas burner that is the source is lowered, and the temperature of the fuel mixed gas is not raised, which is disadvantageous in terms of efficiency. In the present invention, since the water evaporator and the steam superheater are separated, such disadvantages in efficiency can be avoided, and the flow rate can be easily controlled.
[0035]
According to a second aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the first aspect, a hydrogen-rich gas cooler is installed in the outer cylinder portion of the reformer, and the reformer and the hydrogen-rich gas cooler are combined and integrated. It is characterized by that.
[0036]
In the invention of claim 2 as described above, the volume of the power generation device can be reduced by combining and integrating the reformer and the hydrogen rich gas cooler. Moreover, the connection flow path between the reformer and the hydrogen rich gas cooler that are continuous in the flow can be minimized. Furthermore, since the reformer operated at a higher temperature is surrounded by a hydrogen rich gas cooler operated at a lower temperature, there is also a function of suppressing heat dissipation loss from the reformer surface to the atmosphere.
[0037]
According to a third aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the first or second aspect, a steam superheater is installed in an outer cylinder portion of the exhaust gas burner, and the exhaust gas burner and the steam superheater are combined and integrated. It is characterized by that.
[0038]
According to a fourth aspect of the present invention, there is provided the polymer electrolyte fuel cell power generator according to the third aspect, wherein a mixed gas preheater is installed in an outer cylinder portion of a device in which an exhaust gas burner and a steam superheater are combined and integrated. A gas burner, a steam superheater, and a mixed gas preheater are combined and integrated.
[0039]
In the invention according to the third or fourth aspect, the volume of the power generation apparatus can be reduced by combining the steam superheater or the fuel mixed gas preheater with the exhaust gas burner. Further, the connection flow path between the exhaust gas burner continuous in the flow sequence and the steam superheater or the fuel mixed gas preheater can be minimized. Furthermore, since the exhaust gas burner operated at a higher temperature is surrounded by a steam superheater or a fuel mixed gas preheater operated at a lower temperature, a heat radiation loss from the exhaust gas burner surface to the atmosphere can be suppressed.
[0040]
According to a fifth aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the second, third or fourth aspect, a water evaporator and a hydrogen-rich gas cooler are installed in the reformer outer cylinder, and the reformer and the hydrogen The rich gas cooler and the water evaporator are combined and integrated.
[0041]
In the invention of claim 5, the hydrogen rich gas cooler and the water evaporator are combined and integrated in the reformer, so that the apparatus can be made more compact in addition to the function and effect of the invention of claim 2. be able to.
[0042]
A sixth aspect of the present invention is the polymer electrolyte fuel cell power generator according to the first, second, third, fourth or fifth aspect, wherein the desulfurizer comprises a hydrogen-rich gas cooler in a hydrogen-rich gas flow path and a low-temperature carbon monoxide converter. Installed in the middle, the low-temperature carbon monoxide transformer and desulfurizer are combined and integrated.
[0043]
In the above invention of claim 6, by integrating the low-temperature carbon monoxide transformer and the desulfurizer, it is possible to realize a reduction in apparatus volume and suppression of heat dissipation loss in the low-temperature carbon monoxide transformer.
[0044]
A seventh aspect of the present invention is the polymer electrolyte fuel cell power generator according to the first, second, third, fourth, fifth or sixth aspect, wherein the starting burner generates a combustion gas by reacting a fuel and a gas containing oxygen. A fuel cell cooling medium heater for exchanging heat between the cooling medium of the fuel cell and the gas body, and the combustion gas from the start burner is disposed between the exhaust gas burner and the steam superheater from the exhaust gas burner. A first junction that joins the flow path is formed, a branch point where the combustion gas is divided is formed between the fuel mixed gas preheater and the water evaporator, and a second gas that joins the combustion gas downstream of the branch point. A confluence is formed, and the start burner operates to generate combustion gas when the apparatus is started up. After the combustion gas passes through the reforming catalyst layer of the reformer, the exhaust gas burner is discharged from the exhaust gas burner at the first confluence. Steam superheater flows into the combustion gas flow path Combustion gas that has passed through the fuel gas mixture preheater in this order and branched at the branch point is a fuel cell coolant heater, a desulfurizer absorber layer, a low-temperature carbon monoxide shift catalyst layer, and a selective oxidation carbon monoxide removal catalyst. After passing in the order of the layers, the combustion gas from the remaining startup burner is joined again at the second junction, and the startup burner combustion gas passes through the water evaporator and the water condenser in this order. The path through which the startup burner combustion gas flows is independent of the path through which the hydrogen-rich gas flows in the porous catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer. It is characterized by being installed.
[0045]
In the invention of claim 7 having the above-described configuration, after the combustion gas from the start burner passes through the reforming catalyst layer of the reformer when the apparatus is started, the combustion gas from the exhaust gas burner at the first junction point The combustion gas that flows into the flow path, passes through the steam superheater and the fuel mixed gas preheater in this order, and branches at the branching point is the fuel cell cooling medium heater, the absorbent layer of the desulfurizer, and the low-temperature carbon monoxide conversion catalyst. And the selective oxidation type carbon monoxide removal catalyst layer in that order, and then merged again with the combustion gas from the remaining startup burner at the second junction, and further the startup burner combustion gas is passed through the water evaporator and water condenser. Pass in order. This makes it possible to raise the temperature of each device to a sufficiently high temperature before the raw material gas is supplied to the reformer, and to prevent poisoning of the fuel electrode catalyst due to the adsorption of carbon monoxide generated at startup. can do. At the same time, the temperature of the fuel cell cooling medium is increased.
[0046]
In addition, hydrogen-rich gas circulates in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, the selective oxidation carbon monoxide removal catalyst layer, that is, the equipment located upstream of the fuel cell fuel electrode. Since the start burner combustion gas flow path is installed independently of the flow path, there is concern about oxidation and condensation due to the flow of the combustion gas even if the catalyst layer of the fuel processing system is assumed to be used in a high-temperature, reducing atmosphere. There is no reduction in activity, and no reduction operation before starting is required.
[0047]
According to an eighth aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the seventh aspect, the first stop valve is provided between the start burner and the first junction, and the branch point and the fuel cell cooling medium heater are provided. A second stop valve is provided between the two, and a third stop valve is provided between the selective oxidation carbon monoxide removal catalyst layer and the second junction.
[0048]
In such an invention of claim 8, since the switching of the flow path is performed by opening and closing the stop valve, the combustion gas flow path of the start burner and the combustion gas flow path of the exhaust burner can be shared, and the equipment can be simplified. it can.
[0049]
The invention of claim 9 is a method for operating the polymer electrolyte fuel cell power generator according to the invention of claim 8, wherein the apparatus is activated and water evaporator temperature, fuel cell cooling medium heater temperature, desulfurizer temperature, When at least one of the low temperature carbon monoxide shift catalyst layer temperature and the selective oxidation carbon monoxide removal catalyst layer temperature does not reach the preset target temperature, and none of the temperatures reach the preset maximum limit temperature The first stop valve, the second stop valve, and the third stop valve are opened, and the fuel cell coolant heating temperature, the desulfurizer temperature, the low-temperature carbon monoxide shift catalyst layer temperature, and the selective oxidation carbon monoxide removal are performed at the time of starting the apparatus. If all of the catalyst bed temperature has reached or exceeded the preset target temperature, or any of the temperatures has reached the preset maximum limit temperature and the water evaporator temperature does not reach the preset target temperature The first stop valve When the second and third stop valves are closed and the second and third stop valves are opened and the water evaporator temperature reaches the preset maximum limit temperature, only the first stop valve is used. When the water evaporator temperature reaches a preset target temperature with the second stop valve and the third stop valve closed, the first stop valve closes and shifts to the operating state. The stop valve, the second stop valve, and the third stop valve are closed, and at the time of stop, the first stop valve is closed and the second stop valve and the third stop valve are opened.
[0050]
In the invention of claim 9, by carrying out the operation method as described above, it is possible to raise the temperature of each device to a predetermined temperature almost in synchronization, and to prevent excessive temperature rise. it can.
[0051]
According to a tenth aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the eighth aspect, a second branch point is formed at any location in the flow path between the second stop valve and the third stop valve. The second branch point is connected to a pipe that is open to the outside air, and a fourth stop valve is provided in the pipe.
[0052]
The invention of claim 11 is a method for operating the polymer electrolyte fuel cell power generator according to the invention of claim 10, wherein the fuel cell cooling medium heater temperature, desulfurizer temperature, low temperature carbon monoxide transformation at the time of starting the apparatus. A first stop valve if at least one of the catalyst layer temperature and the selective oxidation carbon monoxide removal catalyst layer temperature does not reach a preset target temperature and none of the temperatures reaches a preset maximum limit temperature; The second stop valve and the third stop valve are opened and the fourth stop valve is closed. At the time of starting the apparatus, the temperature of the fuel cell cooling medium heater, the temperature of the desulfurizer, the temperature of the low-temperature carbon monoxide shift catalyst layer, the selective oxidation type monoxide If all of the carbon removal catalyst layer temperatures have reached or exceeded the preset target temperature, or any of them has reached the preset maximum temperature limit and the water evaporator temperature does not reach the preset target temperature Second stop valve And the third stop valve is closed, the first stop valve and the fourth stop valve are opened, the second stop valve and the third stop valve are opened, and the water stop temperature is preset with the fourth stop valve closed. When the maximum limit temperature is reached, only the first stop valve is closed, and when the water evaporator temperature reaches a preset target temperature with the second and third stop valves closed, the first stop valve is closed. The valve is closed and the fourth stop valve is opened to enter the operating state. During operation, the first stop valve, the second stop valve and the third stop valve are closed and the fourth stop valve is opened, and when the apparatus is stopped, the second stop valve is opened. Alternatively, at least one of the third stop valve and the fourth stop valve are opened.
[0053]
According to the tenth and eleventh aspects of the invention, it is possible to raise the temperature of each device to a predetermined temperature almost in synchronism, prevent excessive temperature rise, and reduce the pressure of the starting burner combustion gas flow path by the function of the fourth stop valve. Can be prevented.
[0054]
A twelfth aspect of the present invention is the solid polymer fuel cell power generator according to the first, second, third, fourth, fifth or sixth aspect, wherein the starter burner generates a combustion gas by reacting a fuel and a gas containing oxygen. A fuel cell cooling medium heater for exchanging heat between the cooling medium of the fuel cell and the gas body, and the combustion gas from the start burner is disposed between the exhaust gas burner and the steam superheater from the exhaust gas burner. A junction where the gas flows into the flow path is formed, and a branch point where the combustion gas is divided is formed between the fuel gas mixture preheater and the water evaporator. After the combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the junction, passes in the order of the steam superheater and the fuel mixed gas preheater, and reaches the branch point. The combustion gas branched off After passing through the battery cooling medium heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer in this order, it exits into the atmosphere and is branched at the branch point. Combustion gas from the remaining start burner is further passed in the order of water evaporator and water condenser, and the reforming catalyst layer, desulfurizer absorber layer, low-temperature carbon monoxide shift catalyst layer, selective oxidation type The carbon monoxide removal catalyst layer is characterized in that a path through which the startup burner combustion gas flows is installed independently of a path through which the hydrogen rich gas flows.
[0055]
In the invention of claim 12 above, after the combustion gas from the start burner passes through the reforming catalyst layer of the reformer at the time of starting the apparatus, it flows into the combustion gas flow path from the exhaust gas burner at the junction, The combustion gas that has passed through the superheater and the fuel gas mixture preheater in this order and branched at the branch point is the fuel cell cooling medium heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide shift catalyst layer, and the selective oxidation type monoxide Until the carbon removal catalyst layer passes in the order, it is the same as the invention of claim 7 except that it is released to the atmosphere without being used for heat exchange thereafter. According to such a twelfth aspect of the present invention, each device can be heated to a sufficiently high temperature, and at the same time, a simple device can be constructed.
[0056]
A thirteenth aspect of the present invention is the polymer electrolyte fuel cell power generator according to the twelfth aspect, wherein the first stop valve is provided between the start burner and the junction, and the second stop valve is provided between the branch point and the desulfurizer absorbent layer. A valve is provided.
[0057]
A fourteenth aspect of the invention is a method for operating a polymer electrolyte fuel cell power generator according to the thirteenth aspect of the invention, and is activated at the time of starting the fuel cell cooling medium heater, desulfurizer temperature, low temperature carbon monoxide transformation. When at least one of the catalyst layer temperature and the selective oxidation type carbon monoxide removal catalyst layer temperature does not reach the preset target temperature, and none of the temperatures reaches the preset maximum limit temperature, the first stop valve and The second stop valve is opened and all of the fuel cell cooling medium heater temperature, desulfurizer temperature temperature, low temperature carbon monoxide shift catalyst layer temperature, and selective oxidation carbon monoxide removal catalyst layer temperature are preset when the apparatus is started. The first stop valve is opened and the second stop valve is reached when the target temperature is exceeded or any one of them reaches a preset maximum limit temperature and the water evaporator temperature does not reach the preset target temperature. Closes When the water evaporator temperature reaches the preset maximum temperature limit with the two stop valves open, only the first stop valve is closed, and the water evaporator temperature is preset with the second stop valve closed. When the target temperature is reached, the first stop valve is closed to shift to an operating state, and the first stop valve and the second stop valve are closed during operation.
[0058]
According to the inventions of claims 13 and 14, in the polymer electrolyte fuel cell power generator according to claim 12, the devices can be heated up to a predetermined temperature almost in synchronism with each other, while preventing excessive temperature rise. Can be simplified.
[0059]
The invention according to claim 15 is the solid polymer fuel cell power generator according to claim 1, 2, 3, 4, 5 or 6, wherein the starting burner generates a combustion gas by reacting the fuel and the gas containing oxygen. A fuel cell cooling medium heater for exchanging heat between the cooling medium of the fuel cell and the gas body, and the combustion gas from the start burner is disposed between the exhaust gas burner and the steam superheater from the exhaust gas burner. A confluence is formed that joins the flow path, and a starter burner operates when the apparatus is started to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, an exhaust gas burner is formed at the confluence. It is configured to flow into the combustion gas flow path from and to pass in the order of a steam superheater, a fuel mixed gas preheater, a water evaporator, a fuel cell cooling medium heater, and a water condenser.
[0060]
In the invention of the fifteenth aspect described above, the start-up burner combustion gas is used only for heating a reformer that requires a high temperature and for heating a fuel cell cooling medium heater or a water evaporator that requires a large amount of heat to raise the temperature. is doing. That is, by selectively performing the temperature rise by the start burner combustion gas, the combustion gas flow path can be simplified and the apparatus can be simplified.
[0061]
According to a sixteenth aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the fifteenth aspect, a stop valve is provided between the start burner and the junction.
[0062]
The invention of claim 17 is a method for operating a polymer electrolyte fuel cell power generator according to the invention of claim 16, and is stopped if the water evaporator temperature at the start of the apparatus does not reach a preset target temperature. If the fuel cell cooling medium heater temperature reaches the preset maximum limit temperature with the valve open and the stop valve open, the fuel cell cooling medium cooler is operated to perform temperature control and water evaporation When the reactor temperature reaches the preset target temperature, the stop valve closes and shifts to the operating state. The stop valve closes during operation, and the desulfurizer, the low-temperature carbon monoxide conversion catalyst layer, and selective oxidation type monoxide during operation The temperature of the carbon removal catalyst layer is individually heated by electric power.
[0063]
In the inventions of the sixteenth and seventeenth aspects described above, in the polymer electrolyte fuel cell power generator according to the fifteenth aspect, it is possible to prevent the temperature rise and excessive temperature rise of each device and to simplify the device. .
[0064]
According to an eighteenth aspect of the present invention, there is provided a water evaporator that generates steam supplied to the reformer, and a fuel mixed gas superheater that superheats a mixed gas of oxygen-containing gas, fuel, and water vapor generated in the water evaporator. The combustion gas flow path is formed so that the combustion gas from the exhaust gas burner passes through the fuel gas mixture superheater, the water evaporator, and the water condenser in this order.
[0065]
In the invention of claim 18 as described above, the combustible material that has not been consumed in the fuel cell is combusted by the exhaust gas burner, and this combustion gas is mixed with the fuel mixed gas superheater, the water evaporator, the water condenser, and the high temperature. By allowing the exhaust gas burner to pass through the devices in order, the combustion heat of the exhaust gas burner can be efficiently recovered. Further, in the invention of claim 18, since the fuel is not only mixed with air but is heated in a state of being mixed with water vapor, the temperature of the reaction gas introduced into the reformer is set higher than that of the invention of claim 1. can do. Furthermore, it is possible to reduce the amount of gas containing oxygen into the reformer.
[0066]
According to a nineteenth aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the eighteenth aspect, a hydrogen-rich gas cooler is installed in the outer cylinder portion of the reformer, and the reformer and the hydrogen-rich gas cooler are combined and integrated. It is characterized by that.
[0067]
In the invention of claim 19 as described above, the volume of the power generation device can be reduced by combining and integrating the reformer and the hydrogen rich gas cooler, and the connection flow path between the reformer and the hydrogen rich gas cooler. And minimizing heat dissipation loss from the reformer surface to the atmosphere.
[0068]
According to a twentieth aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the eighteenth or nineteenth aspect, a fuel mixed gas superheater is installed in an outer cylinder portion of the exhaust gas burner, and the exhaust gas burner and the fuel mixed gas superheater are provided. Is combined and integrated.
[0069]
In the above invention of claim 20, it is possible to reduce the volume of the power generator by integrating the fuel gas mixture superheater with the exhaust gas burner. In addition, the connection flow path between the exhaust gas burner and the fuel mixed gas superheater can be minimized. Furthermore, by surrounding the exhaust gas burner with a fuel mixture gas superheater, heat loss from the exhaust gas burner surface to the atmosphere can be suppressed.
[0070]
A twenty-first aspect of the present invention is the polymer electrolyte fuel cell power generator according to the nineteenth or twentieth aspect, wherein a water evaporator and a hydrogen rich gas cooler are installed in the reformer outer cylinder, and the reformer and the hydrogen rich gas cooling are installed. The apparatus and the water evaporator are combined and integrated.
[0071]
In the invention of claim 21, the function and effect of the invention of claim 19 can be further advanced by combining the hydrogen rich gas cooler and the water evaporator in the reformer.
[0072]
According to a twenty-second aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the eighteenth, nineteenth, twenty-first, or twenty-first aspect, the desulfurizer is located between the hydrogen-rich gas cooler and the low-temperature carbon monoxide converter in the hydrogen-rich gas passage. It is installed and the low-temperature carbon monoxide transformer and the desulfurizer are combined and integrated.
[0073]
In the invention of the twenty-second aspect described above, by integrating the low-temperature carbon monoxide converter and the desulfurizer, it is possible to reduce the apparatus volume and to suppress the heat dissipation loss in the low-temperature carbon monoxide converter.
[0074]
The invention according to claim 23 is the solid polymer fuel cell power generator according to claim 18, 19, 20, 21 or 22, a starting burner for generating a combustion gas by reacting a fuel and a gas containing oxygen, and a fuel A fuel cell cooling medium heater for exchanging heat between the battery cooling medium and the gas body is provided, and the combustion gas from the start burner is combusted from the exhaust gas burner between the exhaust gas burner and the fuel mixed gas superheater. A first junction that merges with the flow path is formed, a branch point where combustion gas is separated downstream of the fuel gas mixture superheater is formed, and a second junction where combustion gas merges downstream of the branch point is formed When the apparatus is started, the start burner operates to generate combustion gas, and after this combustion gas passes through the reforming catalyst layer of the reformer, the combustion gas flow path from the exhaust gas burner at the first junction point Then flow into After passing through the gas mixture gas superheater, the combustion gas branched at the branch point is a fuel cell coolant heater, a desulfurizer absorber layer, a low temperature carbon monoxide shift catalyst layer, and a selective oxidation carbon monoxide removal catalyst. And the reforming catalyst layer, the desulfurizer, and the reforming catalyst layer and the desulfurizer. The reforming catalyst layer and the desulfurizer are configured to pass through the water vaporizer. The absorbent layer, the low-temperature carbon monoxide shift catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer are characterized in that the path through which the startup burner combustion gas flows is installed independently of the path through which the hydrogen-rich gas flows. And
[0075]
The invention of claim 23 having the above configuration has the same effect as that of the invention of claim 7 described above. That is, when the apparatus is activated, the combustion gas from the activation burner passes through the reforming catalyst layer of the reformer, and then flows into the combustion gas flow path from the exhaust gas burner at the first merge point, and the steam superheater, fuel The combustion gas that has passed through the mixed gas preheater in this order and branched at the branch point is a fuel cell cooling medium heater, a desulfurizer absorber layer, a low-temperature carbon monoxide shift catalyst layer, and a selective oxidation carbon monoxide removal catalyst layer. Then, the remaining combustion gas from the remaining start burner joins again at the second confluence, and the start burner combustion gas passes through the water evaporator and the water condenser in this order. This makes it possible to raise the temperature of each device to a sufficiently high temperature before the raw material gas is supplied to the reformer, and to prevent poisoning of the fuel electrode catalyst due to the adsorption of carbon monoxide generated at startup. can do. At the same time, the temperature of the fuel cell cooling medium is increased.
[0076]
In addition, hydrogen-rich gas circulates in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, the selective oxidation carbon monoxide removal catalyst layer, that is, the equipment located upstream of the fuel cell fuel electrode. Since the flow path of the startup burner combustion gas is installed independently of the path, there is no fear of oxidation and dew condensation due to the flow of the combustion gas, there is no decrease in activity, and there is no need to perform a reduction operation before startup.
[0077]
According to a twenty-fourth aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the twenty-third aspect, a first stop valve is provided between the reforming catalyst layer of the reformer and the first junction, A second stop valve is provided between the desulfurizer absorbent layer, and a third stop valve is provided between the selective oxidation carbon monoxide removal catalyst layer and the second junction.
[0078]
In the invention of claim 24, as in the invention of claim 8, since the switching of the flow path is performed by opening and closing the stop valve, the combustion gas flow path of the start burner and the combustion gas flow path of the exhaust burner are made common. And the equipment can be simplified.
[0079]
The invention of claim 25 is a method for operating a polymer electrolyte fuel cell power generator according to the invention of claim 24, wherein the apparatus is activated and water evaporator temperature, fuel cell cooling medium heater temperature, desulfurizer temperature, When at least one of the low temperature carbon monoxide shift catalyst layer temperature and the selective oxidation carbon monoxide removal catalyst layer temperature does not reach the preset target temperature, and none of the temperatures reach the preset maximum limit temperature The first stop valve, the second stop valve, and the third stop valve are opened, and the fuel cell coolant heating temperature, the desulfurizer temperature, the low-temperature carbon monoxide shift catalyst layer temperature, and the selective oxidation carbon monoxide removal are performed at the time of starting the apparatus. If all of the catalyst bed temperature has reached or exceeded the preset target temperature, or any of the temperatures has reached the preset maximum limit temperature and the water evaporator temperature does not reach the preset target temperature First stop Is opened, the second stop valve and the third stop valve are closed, and when the water evaporator temperature reaches a preset maximum limit temperature with the second stop valve and the third stop valve open, the first stop When the water evaporator temperature reaches the preset target temperature with only the valve closed and the second stop valve and the third stop valve closed, the first stop valve closes and shifts to the operating state. The first stop valve, the second stop valve, and the third stop valve are closed, and at the time of stop, the first stop valve is closed and the second stop valve and the third stop valve are opened.
[0080]
In the invention of claim 25, by implementing the operation method as described above, it is possible to raise the temperature of each device to a predetermined temperature almost in synchronism, and to prevent excessive temperature rise. .
[0081]
According to a twenty-sixth aspect of the present invention, in the polymer electrolyte fuel cell power generator according to the twenty-fourth aspect, a second branch point is formed at any location in the flow path between the second stop valve and the third stop valve. The second branch point is connected to a pipe that is open to the outside air, and a fourth stop valve is provided in the pipe.
[0082]
A twenty-seventh aspect of the invention is a method for operating a polymer electrolyte fuel cell power generator according to the twenty-sixth aspect of the invention, and is a device for starting a fuel cell cooling medium heater, a desulfurizer temperature, a low temperature carbon monoxide conversion catalyst. And at least one of the selective oxidation type carbon monoxide removal catalyst layer temperatures does not reach a preset target temperature, and when none of the temperatures reaches a preset maximum limit temperature, the first stop valve, the second The stop valve and the third stop valve are opened and the fourth stop valve is closed. At the time of starting the apparatus, the temperature of the fuel cell cooling medium heater, the temperature of the desulfurizer, the temperature of the low-temperature carbon monoxide shift catalyst layer, the selective oxidation type carbon monoxide removal If all of the catalyst bed temperatures have reached or exceeded a preset target temperature or any of them has reached a preset maximum limit temperature and the water evaporator temperature has not reached the preset target temperature, the second Stop valve and third The maximum limit temperature at which the water evaporator temperature is set in advance with the first stop valve and the fourth stop valve open, the second stop valve and the third stop valve open and the fourth stop valve closed. When the water vaporizer temperature reaches the preset target temperature with the second stop valve and the third stop valve closed, the first stop valve is closed. The fourth stop valve opens and shifts to an operating state. During operation, the first stop valve, the second stop valve, and the third stop valve are closed and the fourth stop valve is opened, and when the apparatus is stopped, the second stop valve or the third stop valve is opened. At least one of the stop valves and the fourth stop valve are opened.
[0083]
According to the inventions of the above 26th and 27th aspects, each device can be heated up to a predetermined temperature almost in synchronism, and an excessive temperature rise is prevented, and the depressurization of the start burner combustion gas flow path is effected by the function of the fourth stop valve. Can be prevented.
[0084]
A twenty-eighth aspect of the present invention is the solid polymer fuel cell power generator according to the eighteenth, nineteenth, twenty-first, or twenty-second aspect of the present invention, and an activation burner that generates a combustion gas by reacting a fuel and a gas containing oxygen; A fuel cell cooling medium heater for exchanging heat between the battery cooling medium and the gas body is provided, and the combustion gas from the start burner is combusted from the exhaust gas burner between the exhaust gas burner and the fuel mixed gas superheater. A junction that joins the flow path is formed, a branch point is formed between the fuel gas mixture superheater and the water evaporator, and a combustion gas is generated when the start burner operates when the device is started. After the combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the junction, then passes through the fuel mixed gas superheater, and is branched at the branching point. Combustion gas is fuel After passing through the pond cooling medium heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer in this order, it exits into the atmosphere and is branched at the branch point. Combustion gas from the remaining start burner is further passed in the order of water evaporator and water condenser, and the reforming catalyst layer, desulfurizer absorber layer, low-temperature carbon monoxide shift catalyst layer, selective oxidation type The carbon monoxide removal catalyst layer is characterized in that a path through which the startup burner combustion gas flows is installed independently of a path through which the hydrogen rich gas flows.
[0085]
In the invention of claim 28, after the combustion gas from the start burner passes through the reforming catalyst layer of the reformer at the time of starting the apparatus, it flows into the combustion gas flow path from the exhaust gas burner at the junction, The combustion gas that has passed through the superheater and the fuel gas mixture preheater in this order and branched at the branch point is the fuel cell cooling medium heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide shift catalyst layer, and the selective oxidation type monoxide Until it passes through the carbon removal catalyst layer in the order, it is the same as the invention of claim 22 except that it is released to the atmosphere without being used for heat exchange thereafter. According to such a twenty-eighth aspect, each device can be heated to a sufficiently high temperature, and at the same time, a simple device can be constructed.
[0086]
A twenty-ninth aspect of the present invention is the polymer electrolyte fuel cell power generator according to the twenty-eighth aspect, wherein a first stop valve is provided between the reforming catalyst layer and the junction, and between the branch point and the desulfurizer absorbent layer. The second stop valve is provided in the above.
[0087]
A thirty-third aspect of the invention is a method for operating a polymer electrolyte fuel cell power generator according to the twenty-ninth aspect of the invention, wherein the apparatus is activated and the desulfurizer temperature, the low-temperature carbon monoxide shift catalyst layer temperature, the selective oxidation formula When at least one of the carbon oxide removal catalyst layer temperatures does not reach the preset target temperature, the first stop valve and the second stop valve are opened, and the desulfurizer temperature temperature, the low temperature carbon monoxide conversion catalyst is activated at the time of starting the apparatus. The first stop valve is opened and the second stop valve is closed when all of the bed temperature and the selective oxidation type carbon monoxide removal catalyst layer temperature have reached or exceeded the preset target temperature, and the first stop valve and the second stop valve are closed during operation. The second stop valve is closed.
[0088]
In the above inventions of claims 29 and 30, in the polymer electrolyte fuel cell power generator according to claim 28, each device can be heated substantially to a predetermined temperature in synchronism with each other, while preventing excessive temperature rise. Can be simplified.
[0089]
The invention according to claim 31 is the solid polymer fuel cell power generator according to claim 18, 19, 20, 21 or 22, wherein the starter burner generates a combustion gas by reacting the fuel and the gas containing oxygen, and the fuel. A fuel cell cooling medium heater for exchanging heat between the battery cooling medium and the gas body is provided, and the combustion gas from the start burner is combusted from the exhaust gas burner between the exhaust gas burner and the fuel mixed gas superheater. A confluence is formed that joins the flow path, and a starter burner operates when the apparatus is started to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, an exhaust gas burner is formed at the confluence. It flows into the combustion gas flow path from and is configured to pass through the fuel mixture gas superheater, the water evaporator, the fuel cell cooling medium heater, and the water condenser in this order.
[0090]
In the invention of the above-described claim 31, it is possible to obtain the same operation effect as that of the invention of claim 22 by forming only one confluence, and further simplification of the apparatus can be promoted.
[0091]
According to a thirty-second aspect of the invention, in the polymer electrolyte fuel cell power generator according to the thirty-first aspect, a stop valve is provided between the reforming catalyst layer of the reformer and the junction.
[0092]
A thirty-third aspect of the invention is a method for operating a polymer electrolyte fuel cell power generator according to the thirty-second aspect of the invention, and stops if the water evaporator temperature at the time of starting the apparatus does not reach a preset target temperature. If the fuel cell cooling medium heater temperature reaches the preset maximum limit temperature with the valve open and the stop valve open, the fuel cell cooling medium cooler is operated to perform temperature control and water evaporation When the reactor temperature reaches the preset target temperature, the stop valve closes and shifts to the operating state. The stop valve closes during operation, and the desulfurizer, the low-temperature carbon monoxide conversion catalyst layer, and selective oxidation type monoxide during operation The temperature of the carbon removal catalyst layer is individually heated by electric power.
[0093]
In the inventions of claims 32 and 33 described above, in the polymer electrolyte fuel cell power generator according to claim 31, it is possible to prevent the temperature rise and excessive temperature rise of each device and further simplify the device. .
[0094]
DETAILED DESCRIPTION OF THE INVENTION
(1) First embodiment
[Constitution]
Hereinafter, an example of an embodiment of the present invention will be specifically described with reference to the drawings. The same members as those of the conventional example shown in FIG.
[0095]
First, a first embodiment according to claim 1 is shown in FIG. A steam superheater 62 that superheats steam is provided on the downstream side of the exhaust gas burner 4, and a fuel mixed gas preheating that heats the fuel supplied to the reformer 2 in a state of being mixed with oxygen-containing gas on the downstream side thereof. A water evaporator 61 for generating steam supplied to the reformer 2 and the reformer 2 is sequentially provided. In these devices, a combustion gas flow path is formed so that the combustion gas from the exhaust gas burner 4 passes through the steam superheater 62, the fuel mixed gas preheater 63, the water evaporator 61, and the water condenser 5 in this order. Yes.
[0096]
Steam is generated in the water evaporator 61, enters the steam superheater 62 on the way, is heated there, and then sent to the reformer 2. After the fuel is mixed with a gas containing oxygen, the fuel is preheated through the fuel mixed gas preheater 63 and sent to the reformer 2. In order to make the partial oxidation steam reforming reaction in the reformer 2 as close to the steam reforming side as possible, the raw material gas concentration at the inlet of the reformer 2 should be high. Therefore, it is desirable that the outlet temperatures of the steam superheater 62 and the fuel mixed gas preheater 63 are higher.
[0097]
A gas containing at least one carbon atom and one hydrogen atom in the molecule is applied to the fuel. Specifically, gaseous hydrocarbons such as methane, ethane, propane, and butane, and vapors of liquid hydrocarbons such as city gas, gasoline, kerosene, and light oil mainly composed of these, and methanol, ethanol, dimethyl ether, and isopropanol And organic compounds containing oxygen such as acetone. Substances produced by non-volatile substances such as organosilicon compounds and organometallic compounds are not suitable as fuels because the products are deposited inside the reformer 2. Further, compounds containing sulfur such as thiols, compounds containing halogens such as organochlorine compounds such as vinyl chloride, and compounds containing nitrogen such as amines and amides may be poisoned in the fuel cell 1 and subsequent devices. It is not suitable because it adversely affects it. Examples of the gas containing oxygen include, but are not limited to, oxygen gas, fuel cell oxidant electrode 12 exhaust gas, gas from the exhaust gas burner 4, and a mixture thereof.
[0098]
The preheating of the fuel mixed gas in the fuel mixed gas preheater 63 is performed under conditions that do not ignite. The ignition of the combustible gas varies depending on the temperature, the mixing ratio of the fuel and the gas containing oxygen, and the presence of inert components. For example, referring to "Limits of Inflammability" by HFCoward et al. When the fuel is pure methane and the oxygen-containing gas is air, the ignition range of the fuel / air mixture at room temperature is 5.3% to 13.5%. The ignition range of the fuel / air mixture at 600 ° C. extends from 3.3% to 16.5%. Assuming only the partial oxidation reaction of reaction (2) described above, the lowest fuel / air mixture ratio is 20.9%, so the mixture does not ignite at about 600 ° C., and the oxygen concentration rises locally. It can be seen that the flame does not propagate even if ignited. However, if the surrounding temperature rises due to local ignition, the ignition condition may be satisfied, so it is desirable to suppress the upper limit to about 400 ° C. In general, since the ignition temperature tends to decrease as the molecular weight increases, it is necessary to change the upper limit of the heating temperature according to the fuel to be introduced.
[0099]
The temperature of the water vapor is preferably high, but the material that can withstand the high temperature water vapor is expensive. Therefore, it is desirable to control the water vapor temperature to 650 ° C. or less in order to manufacture an inexpensive apparatus. In addition, when high-temperature steam is introduced into the fuel gas mixture, there is a possibility that the ignition limit will be reached due to temperature rise. Introducing an inert gas such as water vapor at a constant temperature serves to reduce the concentration limit range of ignition, but this is not the case when heating is involved. For this reason, it is necessary to determine the steam superheating temperature in consideration of various factors such as the fuel composition, the heating temperature, and the amount of introduced steam. As can be seen from the above, the desired fuel mixture gas preheating temperature is lower than the desired steam superheat temperature, and when the exhaust gas burner 4 is used as the same heat source, the fuel mixture gas preheater 63 is placed downstream of the steam superheater 62. I know what to put.
[0100]
The steam and oxygen-containing gas and fuel charged into the reformer 2 are converted into hydrogen-rich gas by the partial oxidation reaction in the reformer 2. In order to maintain the reforming reaction, the temperature of the reforming catalyst layer 21 is desirably 600 ° C. or higher. In the partial oxidation type steam reforming reaction, the oxidation reaction is usually preferentially generated at the inlet of the reforming catalyst layer 21 and generally generates a large amount of heat. Therefore, the temperature tends to monotonously decrease from the normal inlet to the outlet. It can be seen. Therefore, in order to keep the temperature of the reforming catalyst layer 21 at 600 ° C. or higher, it is desirable to keep the reformer 2 outlet gas temperature at 600 ° C. or higher.
[0101]
On the other hand, the hydrogen-rich gas exiting the reformer 2 is introduced into the low-temperature carbon monoxide converter 31 via the hydrogen-rich gas cooler 22 and the desulfurizer 33. The temperature of the low-temperature carbon monoxide converter 31 is desirably about 200 ° C. for a commonly used Cu—ZnO-based catalyst. For this reason, it is necessary to lower the temperature of the hydrogen rich gas from 600 ° C. or higher to about 200 ° C., which is handled by the hydrogen rich gas cooler 22. In the first embodiment, a fuel processing system cooling medium that circulates in the fuel processing system cooling medium path 133 is used as a refrigerant in terms of control stability.
[0102]
The fuel cell cooling medium heated by the hydrogen-rich gas cooler 22 merges with the fuel cell cooling medium heated by the heat generation of the fuel cell 1, and cooled to a predetermined temperature by the fuel cell cooling medium cooler 134. Then, the fuel cell 1 and the hydrogen rich gas cooler 22 are supplied again. The fuel cell cooling medium cooler 134 is not limited to a simple cooler, and heat recovery may be performed by combining with an appropriate medium.
[0103]
Although the CO concentration at the outlet of the reformer 2 is several percent, the CO concentration is reduced to about several thousand ppm at the outlet by the shift reaction of the above reaction (3) while passing through the low temperature carbon monoxide converter 31. . Since reaction (3) is an exothermic reaction, it is advantageous in terms of equilibrium at low temperatures. However, since the reaction rate decreases as the temperature decreases, there exists an optimum temperature inherent in the low temperature carbon monoxide conversion catalyst. As such a low-temperature carbon monoxide conversion catalyst, a Cu—ZnO-based catalyst represented by G-66B manufactured by Nissan Gardler is a typical example. The optimum operating temperature is about 200 ° C.
[0104]
In general, many low temperature carbon monoxide conversion catalysts are poisoned with S as seen in the above Cu-ZnO-based catalysts. Therefore, the desulfurizer 33 is installed upstream of the low temperature carbon monoxide converter 31. In FIG. 1, the desulfurizer 33 is installed between the hydrogen-rich gas cooler 22 and the low temperature carbon monoxide converter 31, but the installation location is not limited to this, and any location upstream of the low temperature carbon monoxide converter 31. Good. However, since ZnO, which is a typical desulfurizer 33 absorbent material, is volatile, it is desirable that the operating temperature is 450 ° C. or lower, more preferably 300 ° C. or lower. Therefore, the hydrogen rich gas cooler 22 and the low-temperature carbon monoxide conversion are desirable. It is desirable to be between the reactors 31 or upstream of the fuel mixed gas preheater 63.
[0105]
The hydrogen-rich gas that has passed through the low-temperature carbon monoxide converter 31 is introduced into the selective oxidation carbon monoxide remover 32 together with a gas containing oxygen such as air, where the carbon monoxide concentration is further reduced to several tens of ppm. The As described above, this is to reduce poisoning of the electrode catalyst of the fuel electrode 11 due to carbon monoxide, which is particularly noticeable at low temperatures.
[0106]
This selective oxidation carbon monoxide remover 32 utilizes the fact that the oxidation reaction rate of carbon monoxide is higher than the oxidation reaction rate of hydrogen on a specific catalyst. It is desirable to operate at a low temperature. That is, normally, the operating temperature of the selective oxidation carbon monoxide remover 32 is set lower than that of the low temperature carbon monoxide converter 31.
[0107]
The selective oxidation carbon monoxide remover 32 may consist of one reactor or may consist of two or more reactors. Further, since air needs to be uniformly mixed, air may be blown into the piping before the reactor as seen in Japanese Patent Laid-Open No. 08-157201, or as seen in Japanese Patent Laid-Open No. 08-133701. Alternatively, a mixing manifold may be installed in front of the reactor and air may be blown into the mixing manifold.
[0108]
After about 80% of the hydrogen rich gas hydrogen is used in the electrochemical reaction at the fuel electrode 11, the fuel electrode 11 exhaust gas containing the remaining hydrogen and other combustible materials such as unreformed fuel is sent to the exhaust gas burner 4. Here, the oxidant electrode 12 is mixed with a part of the exhaust gas and burned.
[0109]
The high-temperature gas generated by the combustion is introduced into the steam superheater 62, where the raw material steam is superheated. Thereafter, it is introduced into the fuel mixed gas preheater 63 to preheat the mixed gas of the gas containing fuel and oxygen. Then, it introduce | transduces into the water evaporator 61 and is used for evaporation of the water used as a raw material. The combustion gas of the exhaust gas burner 4 used for heating the equipment and the exhaust gas of the oxidizer electrode 12 that has not been introduced into the exhaust gas burner 4 pass through the water condenser 5, and the contained moisture is recovered.
[0110]
[Function and effect]
Regarding the first embodiment having the above configuration, the temperature and efficiency were estimated under the following conditions.
[0111]
(1) Fuel: Pure methane (2) Gas containing oxygen: Air (3) Water vapor / methane: 3.0
(4) Methane / air: 0.47 (5) Temperature of water, air and methane: 20 ° C
(6) Steam overheating temperature: 650 ° C. (7) Fuel gas preheating temperature: 400 ° C.
(8) Fuel electrode hydrogen utilization rate: 80% (9) Heat dissipation loss: None
As a result, the production efficiency of hydrogen reached 72% with HHV. Further, the temperature of the fuel mixed gas after the steam mixing was 500 ° C., 47% of methane / air and 49% of steam as an inert gas were introduced. The outlet temperature of the reformer 2 was 640 ° C., and the reaction temperature was secured.
[0112]
As for the temperature of each device, the temperature of the combustion gas from the exhaust gas burner 4 in the steam superheater 62 is 820 ° C. on the inlet side and 680 ° C. on the outlet side, so that the steam rises from 102 ° C. to 650 ° C. Warmed. The combustion gas temperature from the exhaust gas burner 4 in the fuel mixed gas preheater 63 was 680 ° C. on the inlet side and 530 ° C. on the outlet side, whereby the fuel mixed gas was heated from 20 ° C. to 400 ° C.
[0113]
Next, with respect to the water evaporator 61, the combustion gas temperature of the exhaust gas burner 4 was 530 ° C. on the inlet side and 190 ° C. on the outlet side, whereby 20 ° C. water was converted into 102 ° C. water vapor. Each device can be heated to a predetermined temperature, and a pinch temperature is also secured.
[0114]
As described above, according to the first embodiment, the combustible gas contained in the exhaust gas of the fuel electrode 11 is combusted by the exhaust gas burner 4, and the combustion gas is steamed by the steam superheater and the fuel mixed gas preheater. By passing the water evaporator, the water condenser and the high-temperature equipment in order, the combustion heat of the exhaust gas burner can be efficiently and safely recovered while ensuring the reaction in the reformer 2. In the first embodiment, by sequentially heating the devices that require high temperatures, it is possible to prevent a situation where the heating source temperature of the devices that require high temperatures is insufficient.
[0115]
In the first embodiment, since the water evaporator 61 and the steam superheater 62 are separated, the flow rate control is easy, and simplification can be promoted. Moreover, since the fuel mixed gas preheater 63 is heated before the water evaporator 61 is deprived of a large amount of heat, heat recovery from the combustion gas of the exhaust gas burner 4 can be performed with high efficiency.
[0116]
(2) Second embodiment
[Constitution]
Next, a second embodiment according to claim 2 will be described with reference to FIG. Note that the gas used in the following embodiment, the order of gas circulation, the desired temperature in each device, and the like are the same as those in the first embodiment.
[0117]
The second embodiment is characterized in that a hydrogen-rich gas cooler 22 is installed in the outer cylinder portion of the reformer 2 and combined and integrated.
[0118]
[Function and effect]
According to the second embodiment, the piping between the reformer 2 and the hydrogen rich gas cooler 22 can be omitted, the volume of the power generation device can be reduced, and the device can be made compact. Further, since the outer cylinder portion of the reformer 2 operated at a high temperature is surrounded by the hydrogen rich gas cooler 22 operated at a lower temperature, a heat radiation loss from the surface of the reformer 2 to the atmosphere can be reduced. . Since the importance of suppressing heat dissipation loss increases as the fuel cell power generation device becomes smaller, such a configuration is effective.
[0119]
(3) Third embodiment
[Constitution]
The configuration of the third embodiment is shown in FIG. The third embodiment corresponds to claim 3 and is characterized in that a steam superheater 62 is installed in the outer cylinder portion of the exhaust gas burner 4 and integrated.
[0120]
[Function and effect]
In the second embodiment, the heat radiation loss in the reformer 2 was successfully reduced. However, the outlet gas of the exhaust gas burner 4 is as high as about 800 ° C., and heat recovery is necessary. There is a need to reduce heat dissipation loss. In order to meet this requirement, in the third embodiment, the exhaust gas burner 4 that is operated at a high temperature is surrounded by a steam superheater 62 that is operated at a lower temperature to reduce the heat dissipation loss from the surface of the exhaust gas burner 4 to the atmosphere. It is suppressed. Moreover, since the steam superheater 62 and the exhaust gas burner 4 are combined and integrated, the connection flow path between them is minimized, so that the volume of the entire power generation apparatus can be reduced and the apparatus can be made more compact.
[0121]
(4) Fourth embodiment
[Constitution]
FIG. 4 shows a fourth embodiment according to the fourth aspect. In the fourth embodiment, an improvement is added to the third embodiment, and a mixed gas preheater 63 is installed in the outer cylinder portion of the steam superheater 62 integrated with the exhaust gas burner 4, The exhaust gas burner 4, the steam superheater 62, and the mixed gas preheater 63 are combined and integrated.
[0122]
[Function and effect]
As is clear from the estimation in the first embodiment, the temperature of the combustion gas in the exhaust gas burner 4 after heating the steam superheater 62 is still a high temperature of 680 ° C. or higher, and the heat dissipation loss of the exhaust gas burner 4 is It cannot be ignored. In order to increase the heat recovery efficiency, it is effective to further integrate the exhaust gas burner 4 and the downstream equipment.
[0123]
In the fourth embodiment, the exhaust gas burner 4, the steam superheater 62, and the mixed gas preheater 63 are combined and integrated, so that the connection flow path between the devices can be minimized, and the exhaust gas burner 4 is connected to the atmosphere. Heat recovery efficiency can be increased by greatly reducing heat dissipation loss.
[0124]
(5) Fifth embodiment
[Constitution]
A fifth embodiment according to claim 5 will be described with reference to FIG. In the fifth embodiment, the hydrogen rich gas cooler 22 is installed at the lower part of the outer cylinder part of the reformer 2, and the water evaporator 61 is installed at the upper part of the outer cylinder part of the reformer 2. 2, a hydrogen rich gas cooler 22, and a water evaporator 61 are combined and integrated. In FIG. 5, the water evaporator 61 is directly installed on the outer cylinder portion of the reformer 2, but it may be installed outside the hydrogen rich gas cooler 22.
[0125]
[Function and effect]
In the fifth embodiment as described above, it is possible to further increase the compactness of the apparatus by integrating the hydrogen rich gas cooler 22 and the water evaporator 61 into the reformer 2.
[0126]
(6) Sixth embodiment
[Constitution]
The sixth embodiment is related to claim 6 and, as shown in FIG. 6, the desulfurizer 33 is installed in the middle of the hydrogen rich gas cooler 22 and the low temperature carbon monoxide converter 31 in the hydrogen rich gas flow path. There are structural features. In FIG. 6, the desulfurizer 33 is placed in front of the low-temperature carbon monoxide converter 31, but the low-temperature carbon monoxide converter 31 is installed in the outer cylinder portion of the desulfurizer 33 or the low-temperature carbon monoxide converter 31. The desulfurizer 33 may be installed on the outer cylinder of the carbon monoxide transformer 31 so that both are combined and integrated to reduce heat dissipation loss, or another method may be used.
[0127]
[Function and effect]
The operating temperature of the desulfurizer 33 is desirably a high temperature in order to promote the desulfurization reaction, but the upper limit thereof needs to be suppressed to about 300 ° C. in order to suppress sublimation loss of the desulfurizer 33 absorbent made of ZnO or the like. On the other hand, the operating temperature of the low-temperature carbon monoxide converter 31 is about 200 ° C. However, since the reaction rate decreases at low temperatures, it is not desirable that the temperature of the low-temperature carbon monoxide converter 31 is inclined to the low temperature side due to heat dissipation loss. The shift reaction that occurs in the low-temperature carbon monoxide converter 31 is an exothermic reaction. However, when the reaction gas flow rate is low at a low load, the heat release may be exothermic and the operating temperature may not be maintained.
[0128]
In the sixth embodiment, by integrating the desulfurizer 33 and the low temperature carbon monoxide converter 31, the heat dissipation loss can be reduced and the operating temperature of the carbon monoxide converter 31 can be maintained. . In addition, the volume of the apparatus can be reduced by integrating the devices.
[0129]
(7) Seventh embodiment
[Constitution]
The seventh embodiment corresponds to claim 7, and FIG. 7 is a configuration diagram of the seventh embodiment. In FIG. 7, the reformer 2, the hydrogen rich gas cooler 22, the low temperature carbon monoxide converter 31, the desulfurizer 33, the exhaust gas burner 4, the water evaporator 61, the steam superheater 62, and the fuel mixed gas preheater 63 are shown. Although the relationships are described independently based on claim 1, they may be combined and integrated based on the invention of claim 2, claim 3, claim 4, claim 5 or claim 6.
[0130]
The feature of the seventh embodiment is as follows. That is, an activation burner 70 that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater 135 that performs heat exchange between the cooling medium of the fuel cell 1 and the gas body are provided. . The activation burner 70 may be installed independently of the reformer 2 or may be structured so as to be integrated with the reformer 2.
[0131]
In the starter burner 70, it is necessary to ensure complete combustion of the combustion gas so as not to generate soot. Therefore, it must be generated due to excessive oxygen with respect to the fuel. The reforming catalyst layer 21 is preferably a reducing atmosphere. Therefore, the combustion gas of the starter burner 70 is isolated from the reforming catalyst layer 21 and its atmosphere, and is manufactured so that there is no mutual circulation due to leakage or the like.
[0132]
The combustion gas temperature of the start burner 70 needs to be equal to or higher than the temperature at which the reformer 2 can be operated, and is preferably 400 ° C. or higher when using a nickel-based reforming catalyst. However, since some downstream devices are vulnerable to high temperatures, excessive heating is avoided, and it is desirable that the temperature is about 400 to 500 ° C. In order to achieve this, as the starting burner 70, when the fuel is city gas of 11,000 kcal / m3 (HHV), air of at least about 60 times the fuel volume is introduced, and stable combustion is performed at this mixing ratio. A suitable catalytic combustor is preferred.
[0133]
A first junction 73 is formed between the exhaust gas burner 4 and the steam superheater 62 where the combustion gas from the start burner 70 joins the combustion gas flow path from the exhaust gas burner 4. Further, a branch point 71 where the combustion gas is divided is formed between the fuel mixed gas preheater 63 and the water evaporator 61, and the second part where the combustion gas joins the combustion gas flow path again downstream of the branch point 71. The confluence point 74 is formed.
[0134]
When the apparatus is activated, the activation burner 70 operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer 21 of the reformer 2 (* in the figure), it is exhausted at the first junction 73. The combustion gas flow path from the gas burner 4 is entered. Since the combustion gas from the exhaust gas burner 4 originally flows through this gas flow path, it does not need to be atmosphere reducing and is shared with the combustion gas line of the activation burner 70.
[0135]
Further, the combustion gas from the start burner 70 passes through the steam superheater 62 and the fuel mixed gas preheater 63 in this order. The combustion gas of the start burner 70 that has passed through the fuel gas mixture preheater 63 is partially branched from the normal flow path that directly leads to the water evaporator 61 at the branch point 71 (** in the figure). The battery cooling medium heater 135, the absorbent layer of the desulfurizer 33, the catalyst layer of the low temperature carbon monoxide converter 31, and the catalyst layer of the selective oxidation carbon monoxide remover 32 flow through. Like the reforming catalyst layer 21, these are preferably reducing atmospheres, so that the combustion gas of the starter burner 70 is a desulfurizer 33 absorbent, a catalyst for the low temperature carbon monoxide converter 31, a catalyst for the selective oxidation carbon monoxide remover 32, and It is isolated from the atmosphere and is manufactured so that there is no mutual circulation due to leaks. Thereafter, the combustion gas from the startup burner 70 that has flowed through the catalyst layer of the selective oxidation carbon monoxide remover 32 is joined again to the combustion gas from the remaining startup burner 70 at the second junction 74, and the water evaporator 61, It passes through the water condenser 5 in this order.
[0136]
In addition, the catalyst layer of the selective oxidation carbon monoxide remover 32 may be divided into two or more when a plurality of reactors are used. Further, the fuel cell cooling medium heater 135 is installed upstream of the hydrogen rich gas cooler 22 in the fuel processing system cooling medium circulation path 133 in FIG. 7, but the installation position is not limited to this, and the fuel cell cooling medium heater Any position of the fuel cell cooling medium path 131 including the fuel processing system cooling medium circulation path 133 may be used except for a portion downstream of 134 and upstream of the fuel cell 1. The positions where the fuel cell cooling medium heater 135 is installed except for the downstream portion of the fuel cell cooling medium heater 134 and the upstream portion of the fuel cell 1 are the fuel cell cooling medium temperature measured at this portion. This is because the amount of heat exchange at 134 is often controlled, and installing the fuel cell heater 135 at this position causes disturbance. In FIG. 7, the desulfurizer 33 is installed in the middle of the hydrogen rich gas cooler 22 and the low temperature carbon monoxide converter 31. However, the present invention is not limited to this. For example, the desulfurizer 33 is installed in the fuel flow path before introducing the reformer 2. May be.
[0137]
[Function and effect]
The operational effects of the seventh embodiment having the above-described configuration are as follows. That is, the combustion gas of the combustion gas starting burner 70 generated at the time of starting the apparatus passes through the steam superheater 62 and the fuel mixed gas preheater 63 in this order to warm these devices. Since the combustion gas temperature of the start burner 70 is at most about 500 ° C., the temperature rise limit of these devices is considered to be about 400 ° C., and the desired operating temperature of the steam superheater 62 and the fuel mixed gas preheater 63 has not been reached. is there. However, these devices exist for heat recovery, and efficiency is insignificant at the time of startup, so that it is not necessary to raise the temperature to the operating temperature. That is, it is only necessary to warm the tube so that condensation does not occur when the reaction gas is circulated, so that the function can be sufficiently performed under these conditions.
[0138]
The temperature of the combustion gas of the starting burner 70 that has passed through the fuel mixed gas preheater 63 is about 300 to 400 ° C. If this is used as it is for heating the desulfurizer 33 absorbent, the low-temperature carbon monoxide converter 31 catalyst layer, and the like, these often contain sublimable ZnO and may be damaged. Therefore, the starter burner 70 combustion gas separated at the branch point 71 exchanges heat with the fuel cell cooling medium in the fuel cell cooling medium heater 135 before passing through the desulfurizer 33 absorbent, and the temperature is increased to about 250 ° C. Reduce. At the same time, it is used to raise the temperature of the fuel cell cooling medium. The subsequent heating target temperatures are 200 to 250 ° C. for the desulfurizer 33, about 200 ° C. for the low temperature carbon monoxide converter 31, and 200 ° C. or less for the selective oxidation carbon monoxide remover 32. It is possible to achieve the target temperature almost at the same time by allowing the combustion gas to pass through. Although the target heating temperature of the fuel cell cooling medium is at most about 85 ° C. and low, the heat capacity is larger than that of the desulfurizer 33, the low temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32. There is no warming.
[0139]
On the other hand, since the water evaporator 61 has to heat a large amount of water to the boiling point and generate water vapor before the start of power generation, a large amount of heat is required for startup. The necessary temperature is a little over 100 ° C., which is lower than the target temperature of the desulfurizer 33 and the like, but since the heat capacity is large, there is a possibility that the temperature rise will be delayed if it is arranged downstream of these devices. Therefore, in the seventh embodiment, the combustion gas of the start burner 70 is divided at the branch point 71, one of which heats the fuel cell cooling medium heater 135 and below, while the other maintains the amount of heat and heats the water evaporator 61. Can be used. As a result, the temperature of the water evaporator 61 can be reliably increased in synchronism with other devices.
[0140]
Further, in the seventh embodiment, the fuel cell 1 fuel electrode such as the reforming catalyst layer 21, the desulfurizer 33 absorbent layer, the low temperature carbon monoxide converter 31 catalyst layer, and the selective oxidation carbon monoxide remover 32 catalyst layer. For the equipment located upstream of 11, the distribution path of the start burner 70 combustion gas is provided independently of the path through which the hydrogen rich gas flows. For this reason, even if it is assumed that the catalyst layer of the fuel processing system is used in a high temperature / reducing atmosphere, there is no possibility that oxidation and dew condensation will occur due to the flow of the combustion gas, resulting in a decrease in activity. There is no need to perform a reduction operation.
[0141]
(8) Eighth embodiment
[Constitution]
An eighth embodiment according to claims 8 and 9 will be described with reference to FIG. The eighth embodiment is characterized in that, in the seventh embodiment (corresponding to the invention of claim 7), there is provided a mechanism for switching the flow path of the starting burner 70 combustion gas and the exhaust gas burner 4 combustion gas. The switching is performed by the operation method according to the invention of claim 9.
[0142]
That is, a first stop valve 75 is provided between the start burner 70 and the first junction 73, and a second stop valve 76 is provided between the branch point 71 and the fuel cell cooling medium heater 135. A third stop valve 77 is provided between the catalyst layer of the carbon monoxide remover 32 and the second junction 74. These three stop valves 75, 76 and 77 are opened and closed by the operation method according to the invention of claim 11 to switch the flow path of the combustion gas.
[0143]
[Open / close stop valve]
When the apparatus is started, the start burner 70 is ignited, and all three stop valves 75, 76, 77 are opened, and the start burner 70 combustion gas flows. There is no stop valve between the branch point 71 and the second junction point 74, and a part of the high temperature gas on the outlet side of the fuel mixed gas preheater 63 directly heats the water evaporator 61. Note that a pressure loss element such as an orifice may be installed between the branch point 71 and the second junction 74 in order to optimally distribute the gas flow rate branched at the branch point 71.
[0144]
When the temperature increase of all of the fuel cell coolant heater 135, the desulfurizer 33, the low temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32 is completed, the second stop valve 76 and the third stop valve 77 are turned on. close. However, if the temperature of any device rises excessively for some reason and exceeds a preset maximum temperature limit, the second stop valve 76 and the second 3 Close the stop valve 77.
[0145]
Many devices installed between the second stop valve 76 and the third stop valve 77 have an upper temperature limit. For example, the fact that the temperature of the fuel cell cooling medium heater 135 approaches the boiling point means that the entire fuel cell cooling medium is heated to this temperature, so that the constituent members of the fuel cell 1 including the solid polymer electrolyte membrane are included. May cause damage. Further, as described above, the desulfurizer 33 and the low temperature carbon monoxide converter 31 may contain sublimable ZnO, and the selective oxidation carbon monoxide remover 32 tends to deteriorate the reaction selectivity at high temperatures. It has been. Therefore, the maximum limit temperature is set for these devices, and when any of them reaches the limit, the second stop valve 76 and the third stop valve 77 are closed, and the temperature rise of the devices is interrupted.
[0146]
On the other hand, the temperature of the water evaporator 61 is increased by the combustion gas of the starter burner 70 joined at the second junction 74. While this temperature does not reach the target temperature, the first stop valve 75 is opened and the start burner 70 combustion gas is sent, and when the target temperature is reached and the second stop valve 76 and the third stop valve 77 are closed, the start is started. The first stop valve 75 is closed after the heating for heating is completed, the start burner 70 is stopped, and the power generation operation is started.
[0147]
During operation, all these valves 75, 76 and 77 are closed, and the heat balance during normal operation is not disturbed. At the time of stoppage, the second stop valve 76 and the third stop valve 77 are opened, and the startup burner combustion gas flow path is depressurized due to water condensation or the like, thereby preventing the occurrence of nonconformity such as leakage.
[0148]
However, even if heating of the device between the fuel cell cooling medium heater 135 and the selective oxidation carbon monoxide remover 32 has not been completed, it is dangerous if the temperature of the water evaporator 61 rises excessively beyond the boiling point. Therefore, when the temperature of the water evaporator 61 reaches the preset maximum temperature limit, the first stop valve 75 is closed with the second stop valve 76 and the third stop valve 77 open, and the start burner 70 is stopped. The supply of new heat is stopped and the equipment whose temperature has not been heated is heated by the residual heat. In order to prevent excessive temperature rise of the water evaporator 61, a safety valve may be installed.
[0149]
[Function and effect]
In the eighth embodiment, the above-described mechanism and control make it possible to raise the temperature of each device of the fuel cell power generation device to a predetermined temperature almost in synchronization, and to prevent excessive temperature rise. Further, since the combustion gas flow path can be switched by opening and closing the stop valve, the combustion gas flow path of the start burner 70 and the combustion gas flow path of the exhaust gas burner 4 can be made common, and the apparatus can be simplified. .
[0150]
(9) Ninth embodiment
[Constitution]
A ninth embodiment according to claims 10 and 11 will be described with reference to FIG. The difference between the ninth embodiment and the eighth embodiment is that, in the ninth embodiment, there is a second branch point 72 between the second stop valve 76 and the third stop valve 77. A vent pipe that opens to the atmosphere from here is installed, and a fourth stop valve 78 is installed there. This is to prevent the second stop valve 76 and the third stop valve 77 from being sealed when the second stop valve 76 and the third stop valve 77 are closed. These four stop valves 75, 76, 77 and 78 are opened and closed by the operation method according to the invention of claim 11, and the flow of the start burner 70 combustion gas and the exhaust gas burner 4 combustion gas as in the eighth embodiment. The road is supposed to be switched. Here, the branch point 71 is a first branch point 71.
[0151]
[Open / close stop valve]
When the apparatus is activated, the activation burner 70 is ignited, and three stop valves 75, 76 and 77 other than the fourth stop valve 78 are opened, and the combustion gas of the activation burner 70 flows. A point where there is no stop valve between the first branch point 71 and the second junction point 74, a point where a pressure loss element such as an orifice may be installed between the branch point 71 and the second junction point 74, etc. Is the same as in the eighth embodiment.
[0152]
When the temperature of the fuel cell cooling medium heater 135, the desulfurizer 33, the low-temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32 is all increased, the second stop valve 76 and the third stop valve 77 are closed. The first stop valve 75 and the fourth stop valve 78 are opened. However, if the temperature of any device rises excessively for some reason and exceeds a preset maximum temperature limit, the second stop valve 76 and the third stop valve are not required even if the temperature rise of other devices is not completed. The valve 77 is closed and the fourth stop valve 78 is opened. This is to ensure the safety of the device as described in the eighth embodiment.
[0153]
On the other hand, while the temperature of the water evaporator 61 does not reach the target temperature, the first stop valve 75 is opened and the combustion gas of the start burner 70 is sent to reach the target temperature and the second stop valve 76 and the third stop valve 77. Is closed and the fourth stop valve 78 is open, the heating for starting is finished, the first stop valve 75 is closed, the starting burner 70 is stopped, and the power generation operation is started.
[0154]
During operation, all these stop valves 75, 76, 77 and 78 are closed to prevent disturbance of the heat balance during normal operation. At the time of stoppage, either the second stop valve 76 or the third stop valve 77 and the fourth stop valve 78 are opened to prevent the combustion gas flow path of the start burner 70 from being depressurized.
[0155]
However, even if heating of the device between the fuel cell cooling medium heater 135 and the selective oxidation carbon monoxide remover 32 has not been completed, it is dangerous if the temperature of the water evaporator 61 rises excessively beyond the boiling point. Therefore, when the temperature of the water evaporator 61 reaches a preset maximum temperature limit, the first stop valve 76 and the third stop valve 77 are opened and the fourth stop valve 78 is closed. The valve 75 is closed. As a result, the start burner 70 is stopped, the supply of a new amount of heat is stopped, and the device whose temperature has not been increased is heated by the residual heat. It should be noted that a safety valve may be installed in order to prevent the water evaporator 61 from being excessively heated, as in the eighth embodiment.
[0156]
[Function and effect]
In the ninth embodiment described above, by the mechanism and control described above, each device of the fuel cell power generation device can be substantially synchronized to raise the temperature to a predetermined temperature and to prevent excessive temperature rise. Further, since the combustion gas flow path can be switched, the combustion gas flow path of the start burner 70 and the combustion gas flow path of the exhaust gas burner 4 can be made common, and the apparatus can be simplified. Further, the operation of the fourth stop valve 78 can prevent decompression of the combustion gas flow path of the start burner 70.
[0157]
(10) Tenth embodiment
[Constitution]
A tenth embodiment according to claim 12 will be described with reference to FIG. The tenth embodiment is a modification of the seventh embodiment (corresponding to the invention of claim 7). The selective oxidation carbon monoxide converter 32 is operated at a relatively low temperature. When an Au-based or Ru-based catalyst is used, the operating temperature may be lower than the boiling point of water. In such a case, the temperature of the starting burner 70 combustion gas at the outlet of the selective oxidation carbon monoxide converter 32 is not at a level that can be used for heating the water evaporator 61. Therefore, it is not necessary to introduce the second junction point 74 to the steamer 61 until the second junction point 74 is provided, and it is desirable to open the atmosphere.
[0158]
In the tenth embodiment, the startup burner 70 combustion gas flow path is branched at a branch point 71, and the fuel cell coolant heater 135, the desulfurizer 33, the low temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover. The combustion gas of the starter burner 70 which heated 32 is discharged into the atmosphere without being used for heat exchange thereafter.
[0159]
The catalyst layer of the selective oxidation carbon monoxide remover 32 may be divided into two or more when the reactor is composed of a plurality of reactors. Further, in FIG. 10, the fuel cell cooling medium heater 135 is installed upstream of the hydrogen rich gas cooler 22 in the fuel processing system cooling medium circulation path 133, but the installation position is not limited to this, and the fuel processing system cooling medium circulation is performed. Any position of the fuel cell coolant passage 131 including the passage 133 may be used. However, the downstream portion of the fuel cell coolant heater 134 and the upstream portion of the fuel cell 1 often control the amount of heat exchange in the fuel cell coolant cooler 134 at the fuel cell coolant temperature measured here, Avoid installing the fuel cell heater 135 at this position because it causes disturbance. In FIG. 10, the desulfurizer 33 is installed between the hydrogen-rich gas cooler 22 and the low-temperature carbon monoxide converter 31. However, the present invention is not limited to this. For example, the desulfurizer 33 is installed in the fuel flow path before the reformer 2 is introduced. May be.
[0160]
[Function and effect]
According to the tenth embodiment as described above, it is possible to construct a simpler and more effective fuel cell power generation device by raising the temperature of each device of the fuel cell power generation device to a predetermined temperature substantially in synchronization. It has become possible.
[0161]
The lengths of the seventh embodiment (corresponding to the invention of claim 7) and the tenth embodiment (corresponding to the invention of claim 12) are the target operating temperatures of the selective oxidation carbon monoxide converter 32. In particular, when this is divided into a plurality of stages, it depends on the target operating temperature of the final stage. That is, the former is more advantageous if the target operating temperature is higher, and the latter is more effective if the temperature is around the boiling point of water.
[0162]
(11) Eleventh embodiment
[Constitution]
The eleventh embodiment shown in FIG. 11 corresponds to claims 13 and 14, and in the tenth embodiment (corresponding to the invention of claim 12), the start burner 70 combustion gas and the exhaust gas burner. There is a feature in that a mechanism for switching the flow path of four combustion gases is provided. That is, a first stop valve 75 is provided between the start burner 70 and the first junction 73, and a second stop valve 76 is provided between the branch point 71 and the absorbent layer of the desulfurizer 33. The stop valves 75 and 76 are opened and closed by the operating method according to the invention of claim 14.
[0163]
[Open / close stop valve]
When the apparatus is activated, the activation burner 70 is ignited, the two stop valves 75 and 76 are opened, and the activation burner 70 combustion gas flows. The pressure loss element for optimizing the flow distribution need not be installed upstream of the water evaporator 61, and the water evaporator 61 and the water condenser 5 can be counted as pressure loss elements. It is possible to reduce the pressure loss element to be installed compared with the case where the exhaust gas line is provided and to reduce the pressure loss of the entire exhaust gas line.
[0164]
When the temperature of all of the fuel cell cooling medium heater 135, the desulfurizer 33, the low temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32 has been increased, the second stop valve 76 is closed. However, if the temperature of any device rises excessively for some reason and exceeds the preset maximum temperature limit, the second stop valve 76 is closed even if the temperature rise of other devices has not been completed. Secure.
[0165]
On the other hand, when the temperature of the water evaporator 61 does not reach the target temperature, the first stop valve 75 is opened and the start burner 70 combustion gas is fed, and when the target temperature is reached and the second stop valve 76 is closed, the water evaporator 61 is started. For this reason, the first stop valve 75 is closed, the start burner 70 is stopped, and the power generation operation is started.
[0166]
During operation, both stop valves 75 and 76 are closed to prevent heat balance disturbance during normal operation. Even if the second stop valve 76 is opened or closed at the time of stop, the start burner 70 combustion gas passage is opened to the atmosphere, so there is no risk of decompression. However, even if heating of the device between the fuel cell cooling medium heater 135 and the selective oxidation carbon monoxide remover 32 has not been completed, it is dangerous if the temperature of the water evaporator 61 rises excessively beyond the boiling point. Therefore, when the temperature of the water evaporator 61 reaches the preset maximum limit temperature, the first stop valve 75 is closed while the second stop valve 76 is open, the start burner 70 is stopped, and a new amount of heat is generated. Stop the supply and heat the equipment whose temperature has not been increased with residual heat. In addition, in order to prevent the excessive temperature rise of the water evaporator 61, you may install a safety valve.
[0167]
[Function and effect]
In the eleventh embodiment, each device of the fuel cell power generation device is substantially tuned to a predetermined temperature by the mechanism and control as described above, and more easily and effectively while preventing excessive temperature rise. It became possible to construct a simple fuel cell power generator.
[0168]
(12) Twelfth embodiment
[Constitution]
The twelfth embodiment corresponds to the fifteenth aspect, and FIG. 12 shows a configuration diagram of the twelfth embodiment. Until now, from the seventh embodiment to the eleventh embodiment, the starter burner 70 combustion gas is used to raise the temperature of the desulfurizer 33, the low-temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32. The case of doing was illustrated. However, when the apparatus and each reactor are small-scale, it is difficult to provide a special start-up heating pipe in each reactor, and heat dissipation loss through this cannot be ignored during operation.
[0169]
Therefore, in the twelfth embodiment according to the invention of claim 15, after the start burner 70 combustion gas passes through the reforming catalyst layer 21 of the reformer 2, the combustion from the exhaust gas burner 4 at the junction 73 is performed. It is configured to flow into the gas flow path and pass through the steam superheater 62, the fuel mixed gas preheater 63, the water evaporator 61, the fuel cell cooling medium heater 135, and the water condenser 5 in this order. .
[0170]
The starter burner 70 combustion gas generated in the starter burner 70 flows through the reforming catalyst layer 21 and heats it, then heats the steam superheater 62 and the fuel mixed gas preheater 63, and heats the water evaporator 61. Here, after the gas temperature becomes relatively low, the fuel cell cooling medium heater 135 is heated. Since the fuel cell cooling medium is usually at most 85 ° C. below the boiling point of water, it can be heated even with the gas after heating the water evaporator 61. The combustion gas from the starting burner 70 exiting the fuel cell cooling medium heater 135 is discharged to the atmosphere through the water condenser 5. The temperature of the desulfurizer 33, the low-temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32, which have a relatively low target temperature rise and a relatively small amount of heat required for heating, is increased by electric power. It has become.
[0171]
The catalyst layer of the selective oxidation carbon monoxide remover 32 may be divided into two or more when the reactor is composed of a plurality of reactors. Further, the fuel cell cooling medium heater 135 is installed upstream of the hydrogen rich gas cooler 22 in the fuel processing system cooling medium circulation path 133 in FIG. 12, but the installation position is not limited to this, and the fuel cell cooling medium heater Any position of the fuel cell cooling medium path 131 including the fuel processing system cooling medium circulation path 133 except for a portion downstream of 134 and upstream of the fuel cell 1 may be used. The portion downstream of the fuel cell cooling medium heater 134 and the upstream portion of the fuel cell 1 is usually a fuel cell cooling medium temperature measurement location, and the amount of heat exchange in the fuel cell cooling medium cooler 134 is controlled based on the measurement result. . Therefore, if the above position is selected as the installation position of the fuel cell heater 135, it is likely to cause a disturbance. Therefore, remove this part. In FIG. 12, the desulfurizer 33 is installed between the hydrogen-rich gas cooler 22 and the low-temperature carbon monoxide converter 31. However, the desulfurizer 33 is not limited to this. For example, the desulfurizer 33 is installed in the fuel flow path before the reformer 2 is introduced. May be.
[0172]
[Function and effect]
In the above twelfth embodiment, the start-up burner is used only for heating the fuel cell cooling medium heater 135 and the water evaporator 61 that require a large amount of heat to raise the temperature of the reformer 22 that requires a high temperature. 70 combustion gases are used. That is, by selecting a device and supplying combustion gas, the combustion gas flow path can be simply configured, and simplification of the apparatus can be promoted.
[0173]
Note that whether to employ the invention of claim 7 or claim 12 or the invention of claim 15 depends on the scale of the apparatus. The invention of claim 7 or claim 12 is advantageous if the apparatus scale is large, and the invention of claim 15 is more effective if the apparatus scale is small.
[0174]
(13) Thirteenth embodiment
[Constitution]
A thirteenth embodiment corresponding to claims 16 and 17 will be described with reference to FIG. In the twelfth embodiment (corresponding to the invention of claim 15), the thirteenth embodiment is provided with a mechanism for switching the flow path of the starter burner 70 combustion gas and the exhaust gas burner 4 combustion gas. That is, a first stop valve 75 is provided between the start burner 70 and the first junction 73, and the first stop valve 75 is opened and closed by the operation method according to the invention of claim 17 to switch the gas flow path. ing.
[0175]
[Open / close stop valve]
When the apparatus is activated, the activation burner 70 is ignited, the first stop valve 75 is opened, and the combustion gas of the activation burner 70 flows. Since there is no need to optimize the flow distribution, no pressure loss element is required for this purpose. While the temperature of the water evaporator 61 does not reach the target temperature, the stop valve 75 is opened and the combustion gas from the start burner 70 is sent, and when the target temperature is reached, the heating for starting is finished and the first stop valve 75 is closed. As a result, the start burner 70 stops and shifts to power generation operation.
[0176]
During operation, the first stop valve 75 is closed, and the heat balance during normal operation is not disturbed. Even if the first stop valve 75 is opened or closed at the time of stoppage, both sides thereof are opened to the atmosphere, so there is no risk of decompression. However, when the temperature of the water evaporator 61 has not been increased, but the temperature of the fuel cell cooling medium heater 135 has reached the maximum limit temperature, it is installed for the purpose of adjusting the cooling water temperature of the fuel cell 1. Heat is released by the fuel cell cooling medium cooler 134. This prevents excessive temperature rise of the fuel cell cooling medium while continuing to raise the temperature of the water evaporator 61.
[0177]
[Function and effect]
In the thirteenth embodiment, with the mechanism and control as described above, each device of the fuel cell power generation apparatus is substantially tuned to increase the temperature to a predetermined temperature, and while preventing excessive temperature increase, it is simpler and more effective. A fuel cell power generator can be constructed.
[0178]
(14) Fourteenth embodiment
[Constitution]
FIG. 14 shows a fourteenth embodiment according to the eighteenth aspect. The fourteenth embodiment is a modification of the first embodiment according to the invention of claim 1, and the fuel gas superheater 64 is provided by integrating the steam superheater 61 and the fuel gas preheater 62. There is a feature in that. The fuel mixed gas superheater 64 is a device that superheats a mixed gas of oxygen-containing gas, fuel, and water vapor generated in the water evaporator 61. The combustion gas of the exhaust gas burner 4 passes through the fuel gas mixture superheater 64, the water evaporator 61, and the water condenser 5 in this order. Except for the above points, the configuration is the same as that of the first embodiment.
[0179]
[Function and effect]
Regarding the fourteenth embodiment having the above-described configuration, the temperature and efficiency were estimated under the following conditions.
[0180]
(1) Fuel: Pure methane (2) Gas containing oxygen: Air (3) Water vapor / methane: 3.0
(4) Methane / air: 0.50 (5) Water, air, methane temperature: 20 ° C
(6) Fuel mixture gas superheat temperature: 450 ° C (7) Fuel electrode hydrogen utilization rate: 80%
▲ 8 ▼ Heat dissipation loss: None
As a result, the hydrogen generation efficiency was slightly over 70% in HHV, which was not significantly different from the estimate in the first embodiment. In the fourteenth embodiment, the fuel is not only mixed with air, but is heated in the fuel mixed gas superheater 64 in a state of being mixed with water vapor, so that the reformer is compared with the invention of claim 1. The temperature of the reaction gas introduced into 2 can be set high, and the amount of gas containing oxygen to the reformer 2 can be reduced. However, the steam temperature must be raised to the extent that condensation does not occur when fuel, air and steam are mixed, and the amount of heat of the exhaust gas burner 4 combustion gas discharged from the water evaporator 61 increases. The superiority or inferiority depends on the case.
[0181]
(15) Fifteenth embodiment
[Constitution]
Next, a fifteenth embodiment according to claim 19 is described with reference to FIG. The fifteenth embodiment is characterized in that a hydrogen-rich gas cooler 22 is installed in the outer cylinder portion of the reformer 2 and integrated.
[0182]
[Function and effect]
According to the nineteenth embodiment, the piping between the reformer 2 and the hydrogen rich gas cooler 22 can be omitted, the volume of the power generation device can be reduced, and the device can be made compact. Further, since the outer cylinder portion of the reformer 2 operated at a high temperature is surrounded by the hydrogen rich gas cooler 22 operated at a lower temperature, a heat radiation loss from the surface of the reformer 2 to the atmosphere can be reduced. .
[0183]
(16) Sixteenth embodiment
[Constitution]
The configuration of the sixteenth embodiment is shown in FIG. The sixteenth embodiment corresponds to claim 20 and is characterized in that a fuel mixture gas superheater 64 is installed in the outer cylinder part of the exhaust gas burner 4 and integrated.
[0184]
[Function and effect]
In the sixteenth embodiment, the exhaust gas burner 4 operated at a high temperature is surrounded by the fuel mixed gas superheater 64 to suppress heat dissipation loss from the surface of the exhaust gas burner 4 to the atmosphere. In addition, by integrating the fuel mixed gas superheater 64 and the exhaust gas burner 4, the connection flow path between them can be minimized and the apparatus can be made compact.
[0185]
(17) Seventeenth embodiment
[Constitution]
A seventeenth embodiment according to the twenty-first aspect will be described with reference to FIG. In the twenty-first embodiment, as in the fifth embodiment, a hydrogen rich gas cooler 22 is installed at the lower portion of the outer cylinder portion of the reformer 2 and water is placed at the upper portion of the outer cylinder portion of the reformer 2. An evaporator 61 is installed, and three devices, the reformer 2, the hydrogen rich gas cooler 22, and the water evaporator 61, are combined and integrated. In FIG. 17, the water evaporator 61 is directly installed on the outer cylinder portion of the reformer 2, but it may be installed outside the hydrogen rich gas cooler 22.
[0186]
[Function and effect]
In the seventeenth embodiment, it is possible to further increase the compactness of the apparatus by integrating the hydrogen rich gas cooler 22 and the water evaporator 61 into the reformer 2.
[0187]
(18) Eighteenth embodiment
[Constitution]
The eighteenth embodiment shown in FIG. 18 is related to claim 22, and the position of the desulfurizer 33 is located between the hydrogen rich gas cooler 22 and the low temperature carbon monoxide converter 31 as in the sixth embodiment. It is characterized by limited points. In FIG. 18, the desulfurizer 33 is placed in front of the low-temperature carbon monoxide converter 31, but the low-temperature carbon monoxide converter 31 is installed in the outer cylinder portion of the desulfurizer 33 or the low-temperature carbon monoxide converter 31. The desulfurizer 33 may be installed on the outer cylinder of the carbon monoxide transformer 31 so that both are combined and integrated to reduce heat dissipation loss, or another method may be used.
[0188]
[Function and effect]
In the eighteenth embodiment, by integrating the desulfurizer 33 and the low-temperature carbon monoxide converter 31, the heat dissipation loss can be reduced and the operating temperature of the carbon monoxide converter 31 can be maintained. . In addition, the volume of the apparatus can be reduced by integrating the devices.
[0189]
(19) Nineteenth embodiment
[Constitution]
The nineteenth embodiment corresponds to the twenty-third aspect, and FIG. 19 is a configuration diagram of the nineteenth embodiment. As in the seventh embodiment, the nineteenth embodiment includes an activation burner 70 and a fuel cell cooling medium heater 135 that exchanges heat between the cooling medium of the fuel cell 1 and the gas body. Yes. The activation burner 70 may be installed independently of the reformer 2 or may be structured so as to be integrated with the reformer 2. The relationship among the reformer 2, the hydrogen rich gas cooler 22, the low temperature carbon monoxide converter 31, the desulfurizer 33, the exhaust gas burner 4, the water evaporator 61, and the fuel mixed gas superheater 64 is based on claim 18. Although described independently of each other, they may be combined and integrated based on the inventions of claims 19, 20, 21, and 22.
[0190]
The combustion gas of the starter burner 70 needs to be generated due to excessive oxygen. However, since the reforming catalyst layer 21 is preferably a reducing atmosphere, the combustion gas of the starter burner 70 is isolated from the reforming catalyst and its atmosphere, and is caused by mutual leakage due to leakage or the like. It is produced so that there is no distribution. The reformer 2 is desirably heated to 400 ° C. or more, but the combustion gas temperature of the start burner 70 is desirably about 400 to 500 ° C. because some downstream devices are vulnerable to high temperatures. In order to achieve this, it is preferable that the starting burner 70 introduces air at least about 60 times the fuel volume and uses a catalytic combustor to stably burn at this mixing ratio.
[0191]
A first junction 73 is formed between the exhaust gas burner 4 and the fuel mixed gas superheater 64 where the combustion gas from the start burner 70 joins the combustion gas flow path from the exhaust gas burner 4. A branch point 71 where the combustion gas is divided is formed between the gas superheater 64 and the water evaporator 61, and further, a second junction point where the combustion gas again joins the combustion gas flow path downstream of the branch point 71. 74 is formed.
[0192]
When the apparatus is activated, the activation burner 70 operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer 21 of the reformer 2 (* in the figure), it is exhausted at the first junction 73. The combustion gas flow path from the gas burner 4 is entered. Since the combustion gas from the exhaust gas burner 4 originally flows through this gas flow path, it does not need to be atmosphere reducing and is shared with the combustion gas line of the activation burner 70.
[0193]
Further, the combustion gas from the start burner 70 passes through the fuel gas mixture superheater 64, and partly branches from the normal flow path directly leading to the water evaporator 61 at the branch point 71 (** in the figure). The fuel cell cooling medium heater 135, the absorbent layer of the desulfurizer 33, the catalyst layer of the low temperature carbon monoxide converter 31, and the catalyst layer of the selective oxidation carbon monoxide remover 32 flow through. The combustion gas from the starter burner 70 is isolated from the desulfurizer 33 absorbent, the low-temperature carbon monoxide converter 31 catalyst, the selective oxidation carbon monoxide remover 32 catalyst, and the atmosphere thereof, and is manufactured so that there is no mutual flow due to leakage or the like. ing. The starter burner 70 combustion gas that has flowed through the catalyst layer of the selective oxidation carbon monoxide remover 32 joins the remaining starter burner 70 combustion gas branched at the branching point 71 at the junction 72, and the water evaporator 61, It is sent in the order of the water condenser 5.
[0194]
In addition, the catalyst layer of the selective oxidation carbon monoxide remover 32 may be divided into two or more when a plurality of reactors are used. Further, the fuel cell cooling medium heater 135 is installed upstream of the hydrogen rich gas cooler 22 in the fuel processing system cooling medium circulation path 133 in FIG. 19, but the installation position is not limited to this, and the fuel cell cooling medium heater Any position of the fuel cell cooling medium path 131 including the fuel processing system cooling medium circulation path 133 except for a portion downstream of 134 and upstream of the fuel cell 1 may be used. The portion downstream of the fuel cell cooling medium heater 134 and upstream of the fuel cell 1 often controls the amount of heat exchange in the fuel cell cooling medium cooler 134 with the fuel cell cooling medium temperature measured in this portion. Therefore, installing the fuel cell heater 135 at this position is likely to cause disturbance. In FIG. 19, the desulfurizer 33 is installed between the hydrogen-rich gas cooler 22 and the low-temperature carbon monoxide converter 31. However, the present invention is not limited to this. For example, the desulfurizer 33 is installed in the fuel flow path before the reformer 2 is introduced. May be.
[0195]
[Function and effect]
The operational effects of the nineteenth embodiment having the above-described configuration are as follows. That is, the combustion gas of the combustion gas activation burner 70 generated when the apparatus is activated passes through the fuel mixed gas superheater 64 and warms it. At this time, the desired operating temperature of the fuel mixed gas superheater 64 has not been reached, but the fuel mixed gas superheater 64 exists for heat recovery, and the efficiency is neglected at start-up, so the temperature is raised to about the operating temperature. It is not necessary to do this, and the function can be sufficiently performed under these conditions.
[0196]
By adopting such a flow path configuration, the fuel cell cooling medium heater 135, the desulfurizer 33, the low temperature carbon monoxide converter 31, the selective oxidation type monoxide, while using the same heating source as the starting burner 70 combustion gas. The temperature raising of the carbon remover 32 and the water evaporator 61 can be performed synchronously.
[0197]
In the nineteenth embodiment, the fuel cell 1 fuel electrode such as the reforming catalyst layer 21, the desulfurizer 33 absorbent layer, the low-temperature carbon monoxide converter 31 catalyst layer, and the selective oxidation carbon monoxide remover 32 catalyst layer. 11 is provided with a flow path of the starter burner 70 combustion gas independently of the path through which the hydrogen-rich gas flows. For this reason, even if it is assumed that the catalyst layer of the fuel processing system is used in a high temperature / reducing atmosphere, there is no possibility that oxidation and dew condensation will occur due to the flow of the combustion gas, resulting in a decrease in activity. There is no need to perform a reduction operation.
[0198]
(20) 20th embodiment
[Constitution]
A twentieth embodiment according to claims 24 and 25 will be described with reference to FIG. The twentieth embodiment is characterized in that, in the nineteenth embodiment (corresponding to the invention of claim 23), there is provided a mechanism for switching the flow path of the starting burner 70 combustion gas and the exhaust gas burner 4 combustion gas. The switching is performed by the operation method according to the invention of claim 25.
[0199]
That is, as in the eighth embodiment, the first stop valve 75 is provided between the activation burner 70 and the first junction 73, and the second stop is provided between the branch point 71 and the fuel cell coolant heater 135. A valve 76 is provided, and a third stop valve 77 is provided between the catalyst layer of the selective oxidation carbon monoxide remover 32 and the second junction 74. These three stop valves 75, 76 and 77 are opened and closed by the operation method according to the invention of claim 25 to switch the flow path of the combustion gas.
[0200]
[Open / close stop valve]
When the apparatus is started, the start burner 70 is ignited, and all three stop valves 75, 76, 77 are opened, and the start burner 70 combustion gas flows. There is no stop valve between the branch point 71 and the second junction point 74, and a part of the hot gas at the outlet side of the fuel mixed gas superheater 64 directly heats the water evaporator 61. Note that a pressure loss element such as an orifice may be installed between the branch point 71 and the second junction 74 in order to optimally distribute the gas flow rate branched at the branch point 71.
[0201]
When the temperature increase of all of the fuel cell coolant heater 135, the desulfurizer 33, the low temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32 is completed, the second stop valve 76 and the third stop valve 77 are turned on. close. However, if the temperature of any device rises excessively for some reason and exceeds a preset maximum temperature limit, the second stop valve 76 and the second 3 Close the stop valve 77.
[0202]
Many devices installed between the second stop valve 76 and the third stop valve 77 have an upper temperature limit. For example, the fact that the temperature of the fuel cell cooling medium heater 135 approaches the boiling point means that the entire fuel cell cooling medium is heated to this temperature, so that the constituent members of the fuel cell 1 including the solid polymer electrolyte membrane are included. May cause damage. Further, as described above, the desulfurizer 33 and the low temperature carbon monoxide converter 31 may contain sublimable ZnO, and the selective oxidation carbon monoxide remover 32 tends to deteriorate the reaction selectivity at high temperatures. It has been. Therefore, the maximum limit temperature is set for these devices, and when any of them reaches the limit, the second stop valve 76 and the third stop valve 77 are closed, and the temperature rise of the devices is interrupted.
[0203]
On the other hand, the temperature of the water evaporator 61 is increased by the combustion gas of the starter burner 70 joined at the second junction 74. While this temperature does not reach the target temperature, the first stop valve 75 is opened and the start burner 70 combustion gas is sent, and when the target temperature is reached and the second stop valve 76 and the third stop valve 77 are closed, the start is started. The first stop valve 75 is closed after the heating for heating is completed, the start burner 70 is stopped, and the power generation operation is started.
[0204]
During operation, all these valves 75, 76 and 77 are closed, and the heat balance during normal operation is not disturbed. At the time of stoppage, the second stop valve 76 and the third stop valve 77 are opened, and the startup burner combustion gas flow path is depressurized due to water condensation or the like, thereby preventing the occurrence of nonconformity such as leakage.
[0205]
However, even if heating of the device between the fuel cell cooling medium heater 135 and the selective oxidation carbon monoxide remover 32 has not been completed, it is dangerous if the temperature of the water evaporator 61 rises excessively beyond the boiling point. Therefore, when the temperature of the water evaporator 61 reaches the preset maximum temperature limit, the first stop valve 75 is closed with the second stop valve 76 and the third stop valve 77 open, and the start burner 70 is stopped. The supply of new heat is stopped and the equipment whose temperature has not been heated is heated by the residual heat. In order to prevent excessive temperature rise of the water evaporator 61, a safety valve may be installed.
[0206]
[Function and effect]
In the twentieth embodiment, it is possible to raise the temperature of each device of the fuel cell power generation device to a predetermined temperature substantially in synchronization with the above mechanism and control, and to prevent excessive temperature rise. Further, since the combustion gas flow path can be switched by opening and closing the stop valve, the combustion gas flow path of the start burner 70 and the combustion gas flow path of the exhaust gas burner 4 can be made common, and the apparatus can be simplified. .
[0207]
(21) Twenty-first embodiment
[Constitution]
A twenty-first embodiment according to claims 26 and 27 will be described with reference to FIG. The difference between the twenty-first embodiment and the twentieth embodiment is that in the twenty-first embodiment, there is a second branch point 72 between the second stop valve 76 and the third stop valve 77. A vent pipe that opens to the atmosphere from here is installed, and a fourth stop valve 78 is installed there. This is to prevent the second stop valve 76 and the third stop valve 77 from being sealed when the second stop valve 76 and the third stop valve 77 are closed. These four stop valves 75, 76, 77 and 78 are opened and closed by the operation method according to the invention of claim 27, and the flow of the start burner 70 combustion gas and the exhaust gas burner 4 combustion gas as in the twentieth embodiment. The road is supposed to be switched. Here, the branch point 71 is a first branch point 71.
[0208]
[Open / close stop valve]
When the apparatus is activated, the activation burner 70 is ignited, and three stop valves 75, 76 and 77 other than the fourth stop valve 78 are opened, and the combustion gas of the activation burner 70 flows. A point where there is no stop valve between the first branch point 71 and the second junction point 74, a point where a pressure loss element such as an orifice may be installed between the branch point 71 and the second junction point 74, etc. Is the same as in the twentieth embodiment.
[0209]
When the temperature of the fuel cell cooling medium heater 135, the desulfurizer 33, the low-temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32 is all increased, the second stop valve 76 and the third stop valve 77 are closed. The first stop valve 75 and the fourth stop valve 78 are opened. However, if the temperature of any device rises excessively for some reason and exceeds a preset maximum temperature limit, the second stop valve 76 and the third stop valve are not required even if the temperature rise of other devices is not completed. The valve 77 is closed and the fourth stop valve 78 is opened to ensure the safety of the device.
[0210]
On the other hand, while the temperature of the water evaporator 61 does not reach the target temperature, the first stop valve 75 is opened and the combustion gas of the start burner 70 is sent to reach the target temperature and the second stop valve 76 and the third stop valve 77. Is closed and the fourth stop valve 78 is open, the heating for starting is finished, the first stop valve 75 is closed, the starting burner 70 is stopped, and the power generation operation is started.
[0211]
During operation, all these stop valves 75, 76, 77 and 78 are closed to prevent disturbance of the heat balance during normal operation. At the time of stoppage, either the second stop valve 76 or the third stop valve 77 and the fourth stop valve 78 are opened to prevent the combustion gas flow path of the start burner 70 from being depressurized.
[0212]
However, even if heating of the device between the fuel cell cooling medium heater 135 and the selective oxidation carbon monoxide remover 32 has not been completed, it is dangerous if the temperature of the water evaporator 61 rises excessively beyond the boiling point. Therefore, when the temperature of the water evaporator 61 reaches a preset maximum temperature limit, the first stop valve 76 and the third stop valve 77 are opened and the fourth stop valve 78 is closed. The valve 75 is closed. As a result, the start burner 70 is stopped, the supply of a new amount of heat is stopped, and the device whose temperature has not been increased is heated by the residual heat. It should be noted that a safety valve may be installed in order to prevent the water evaporator 61 from being excessively heated, as in the eighth embodiment.
[0213]
[Function and effect]
In the twenty-first embodiment described above, each mechanism of the fuel cell power generation device can be substantially synchronized to raise the temperature to a predetermined temperature and prevent excessive temperature rise by the mechanism and control described above. Further, since the combustion gas flow path can be switched, the combustion gas flow path of the start burner 70 and the combustion gas flow path of the exhaust gas burner 4 can be made common, and the apparatus can be simplified. Further, the operation of the fourth stop valve 78 can prevent decompression of the combustion gas flow path of the start burner 70.
[0214]
(22) Twenty-second embodiment
[Constitution]
A twenty-second embodiment according to the twenty-eighth aspect is described with reference to FIG. The twenty-second embodiment is a modification of the nineteenth embodiment (corresponding to the invention of claim 23). In the twenty-second embodiment, similarly to the tenth embodiment, the combustion gas flow path of the start burner 70 is branched at a branch point 71, and the fuel cell cooling medium heater 135, the desulfurizer 33, and the low-temperature carbon monoxide converter 31. The combustion gas of the starter burner 70 that has heated the selective oxidation carbon monoxide remover 32 is released into the atmosphere without being used for heat exchange thereafter.
[0215]
The catalyst layer of the selective oxidation carbon monoxide remover 32 may be divided into two or more when the reactor is composed of a plurality of reactors. Further, in FIG. 22, the fuel cell cooling medium heater 135 is installed upstream of the hydrogen rich gas cooler 22 in the fuel processing system cooling medium circulation path 133, but the installation position is not limited to this, and the fuel cell cooling medium heater Any position of the fuel cell cooling medium path 131 including the fuel processing system cooling medium circulation path 133 except for a portion downstream of 134 and upstream of the fuel cell 1 may be used. In FIG. 22, the desulfurizer is installed in the middle of the hydrogen rich gas cooler 22 and the low temperature carbon monoxide converter 31. However, the desulfurizer is not limited to this, for example, installed in the fuel flow path before the reformer 2 is introduced. Also good.
[0216]
[Function and effect]
According to the twenty-second embodiment as described above, it is possible to construct a simpler and more effective fuel cell power generation device by raising the temperature of each device of the fuel cell power generation device to a predetermined temperature substantially in synchronization. It has become possible.
[0217]
The advantages and disadvantages of the nineteenth embodiment (corresponding to the invention of claim 23) and the twenty-second embodiment (corresponding to the invention of claim 28) are the target operating temperatures of the selective oxidation carbon monoxide converter 32. In particular, when this is divided into a plurality of stages, it depends on the target operating temperature of the final stage. The former is more advantageous if the target operating temperature is high, and the latter is more effective if the temperature is around the boiling point of water.
[0218]
(23) Twenty-third embodiment
[Constitution]
The twenty-third embodiment shown in FIG. 23 corresponds to claims 29 and 30, and in the twenty-second embodiment (corresponding to the invention of claim 28), the start burner 70 combustion gas and the exhaust gas burner. There is a feature in that a mechanism for switching the flow path of four combustion gases is provided. That is, a first stop valve 75 is provided between the start burner 70 and the first junction 73, and a second stop valve 76 is provided between the branch point 71 and the absorbent layer of the desulfurizer 33. The stop valves 75 and 76 are opened and closed by the operation method according to the invention of claim 30.
[0219]
[Open / close stop valve]
When the apparatus is activated, the activation burner 70 is ignited, the two stop valves 75 and 76 are opened, and the activation burner 70 combustion gas flows. The pressure loss element for optimizing the flow distribution need not be installed upstream of the water evaporator 61, and the water evaporator 61 and the water condenser 5 can be counted as pressure loss elements. It is possible to reduce the pressure loss element to be installed compared with the case where the exhaust gas line is provided and to reduce the pressure loss of the entire exhaust gas line.
[0220]
When the temperature of all of the fuel cell cooling medium heater 135, the desulfurizer 33, the low temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32 has been increased, the second stop valve 76 is closed. However, if the temperature of any device rises excessively for some reason and exceeds the preset maximum temperature limit, the second stop valve 76 is closed even if the temperature rise of other devices has not been completed. Secure.
[0221]
On the other hand, when the temperature of the water evaporator 61 does not reach the target temperature, the first stop valve 75 is opened and the start burner 70 combustion gas is fed, and when the target temperature is reached and the second stop valve 76 is closed, the water evaporator 61 is started. For this reason, the first stop valve 75 is closed, the start burner 70 is stopped, and the power generation operation is started.
[0222]
During operation, both stop valves 75 and 76 are closed to prevent heat balance disturbance during normal operation. Even if the second stop valve 76 is opened or closed at the time of stop, the start burner 70 combustion gas passage is opened to the atmosphere, so there is no risk of decompression. However, even if heating of the device between the fuel cell cooling medium heater 135 and the selective oxidation carbon monoxide remover 32 has not been completed, it is dangerous if the temperature of the water evaporator 61 rises excessively beyond the boiling point. Therefore, when the temperature of the water evaporator 61 reaches the preset maximum limit temperature, the first stop valve 75 is closed while the second stop valve 76 is open, the start burner 70 is stopped, and a new amount of heat is generated. Stop the supply and heat the equipment whose temperature has not been increased with residual heat. In addition, in order to prevent the excessive temperature rise of the water evaporator 61, you may install a safety valve.
[0223]
[Function and effect]
In the twenty-third embodiment, with the mechanism and control as described above, each device of the fuel cell power generation device is almost synchronized and heated to a predetermined temperature, and while preventing excessive temperature rise, it is simpler and more effective. It became possible to construct a simple fuel cell power generator.
[0224]
(24) Twenty-fourth embodiment
[Constitution]
The twenty-fourth embodiment corresponds to the thirty-first aspect, and FIG. 24 shows a configuration diagram of the twenty-fourth embodiment. In the twenty-fourth embodiment, after the starter burner 70 combustion gas passes through the reforming catalyst layer 21 of the reformer 2, it flows into the combustion gas flow path from the exhaust gas burner 4 at the junction 73 and mixes the fuel. The gas superheater 64, the water evaporator 61, the fuel cell cooling medium heater 135, and the water condenser 5 are configured to pass through in this order.
[0225]
The starter burner 70 combustion gas generated in the starter burner 70 flows through the reforming catalyst layer 21 and heats it, then superheats the fuel mixed gas superheater 64 and further heats the water evaporator 61. Here, after the gas temperature becomes relatively low, the fuel cell cooling medium heater 135 is heated. Since the fuel cell cooling medium is usually at most 85 ° C. below the boiling point of water, it can be heated even with the gas after heating the water evaporator 61. The combustion gas from the starting burner 70 exiting the fuel cell cooling medium heater 135 is discharged to the atmosphere through the water condenser 5. The temperature of the desulfurizer 33, the low-temperature carbon monoxide converter 31, and the selective oxidation carbon monoxide remover 32, which have a relatively low target temperature rise and a relatively small amount of heat required for heating, is increased by electric power. It has become.
[0226]
The catalyst layer of the selective oxidation carbon monoxide remover 32 may be divided into two or more when the reactor is composed of a plurality of reactors. Further, the fuel cell cooling medium heater 135 is installed upstream of the hydrogen rich gas cooler 22 in the fuel processing system cooling medium circulation path 133 in FIG. 12, but the installation position is not limited to this, and the fuel cell cooling medium heater Any position of the fuel cell cooling medium path 131 including the fuel processing system cooling medium circulation path 133 except for a portion downstream of 134 and upstream of the fuel cell 1 may be used. The portion downstream of the fuel cell cooling medium heater 134 and the upstream portion of the fuel cell 1 is usually a fuel cell cooling medium temperature measurement location, and the amount of heat exchange in the fuel cell cooling medium cooler 134 is controlled based on the measurement result. . Therefore, if the above position is selected as the installation position of the fuel cell heater 135, it is likely to cause a disturbance. Therefore, remove this part. In FIG. 24, the desulfurizer 33 is installed between the hydrogen-rich gas cooler 22 and the low-temperature carbon monoxide converter 31. However, the desulfurizer 33 is not limited to this. For example, the desulfurizer 33 is installed in the fuel flow path before the reformer 2 is introduced. May be.
[0227]
[Function and effect]
In the twenty-fourth embodiment described above, the start-up burner is used only for heating the fuel cell cooling medium heater 135 and the water evaporator 61 that require a large amount of heat for raising the temperature of the reformer 22 that requires a high temperature. 70 combustion gases are used. That is, the combustion gas flow path can be simply configured by selecting the equipment and supplying the combustion gas, and the device can be simplified.
[0228]
Note that whether to adopt the invention of claim 23 or claim 28 or the invention of claim 31 depends on the scale of the apparatus. The invention of claim 23 or claim 28 is advantageous if the device scale is large, and the invention of claim 31 is more effective if the device scale is small.
[0229]
(25) Twenty-fifth embodiment
[Constitution]
A twenty-fifth embodiment corresponding to claims 32 and 33 will be described with reference to FIG. The twenty-fifth embodiment is the same as the twenty-fourth embodiment (corresponding to the invention of claim 31), but is provided with a mechanism for switching the flow path of the combustion gas from the starter burner 70 and the exhaust gas burner 4. That is, a first stop valve 75 is provided between the start burner 70 and the first junction 73, and the first stop valve 75 is opened and closed by the operation method according to the invention of claim 33 to switch the gas flow path. ing.
[0230]
[Open / close stop valve]
When the apparatus is activated, the activation burner 70 is ignited, the first stop valve 75 is opened, and the combustion gas of the activation burner 70 flows. Since there is no need to optimize the flow distribution, no pressure loss element is required for this purpose. While the temperature of the water evaporator 61 does not reach the target temperature, the stop valve 75 is opened and the combustion gas from the start burner 70 is sent, and when the target temperature is reached, the heating for starting is finished and the first stop valve 75 is closed. As a result, the start burner 70 stops and shifts to power generation operation.
[0231]
During operation, the first stop valve 75 is closed, and the heat balance during normal operation is not disturbed. Even if the first stop valve 75 is opened or closed at the time of stoppage, both sides thereof are opened to the atmosphere, so there is no risk of decompression. However, when the temperature of the water evaporator 61 has not been increased, but the temperature of the fuel cell cooling medium heater 135 has reached the maximum limit temperature, it is installed for the purpose of adjusting the cooling water temperature of the fuel cell 1. Heat is released by the fuel cell cooling medium cooler 134. This prevents excessive temperature rise of the fuel cell cooling medium while continuing to raise the temperature of the water evaporator 61.
[0232]
[Function and effect]
In the twenty-fifth embodiment, with the mechanism and control as described above, each device of the fuel cell power generation apparatus is substantially tuned to increase the temperature to a predetermined temperature, and while preventing excessive temperature increase, it is simpler and more effective. A fuel cell power generator can be constructed.
[0233]
【The invention's effect】
As described above, according to the present invention, a high-efficiency polymer electrolyte fuel cell power generator capable of starting in a short time from a stopped state and effectively recovering exhaust heat while being compact and having a simple device configuration. And an operation method thereof.
[Brief description of the drawings]
FIG. 1 is a configuration diagram of a first embodiment of the present invention.
FIG. 2 is a configuration diagram of a second embodiment of the present invention.
FIG. 3 is a configuration diagram of a third embodiment of the present invention.
FIG. 4 is a configuration diagram of a fourth embodiment of the present invention.
FIG. 5 is a configuration diagram of a fifth embodiment of the present invention.
FIG. 6 is a configuration diagram of a sixth embodiment of the present invention.
FIG. 7 is a configuration diagram of a seventh embodiment of the present invention.
FIG. 8 is a configuration diagram of an eighth embodiment of the present invention.
FIG. 9 is a configuration diagram of a ninth embodiment of the present invention.
FIG. 10 is a configuration diagram of a tenth embodiment of the present invention.
FIG. 11 is a configuration diagram of an eleventh embodiment of the present invention.
FIG. 12 is a configuration diagram of a twelfth embodiment of the present invention.
FIG. 13 is a configuration diagram of a thirteenth embodiment of the present invention.
FIG. 14 is a configuration diagram of a fourteenth embodiment of the present invention.
FIG. 15 is a configuration diagram of a fifteenth embodiment of the present invention.
FIG. 16 is a configuration diagram of a sixteenth embodiment of the present invention.
FIG. 17 is a configuration diagram of a seventeenth embodiment of the present invention.
FIG. 18 is a configuration diagram of an eighteenth embodiment of the present invention.
FIG. 19 is a configuration diagram of a nineteenth embodiment of the present invention.
FIG. 20 is a configuration diagram of a twentieth embodiment of the present invention.
FIG. 21 is a configuration diagram of a twenty-first embodiment of the present invention.
FIG. 22 is a configuration diagram of a twenty-second embodiment of the present invention.
FIG. 23 is a configuration diagram of a twenty-third embodiment of the present invention.
FIG. 24 is a configuration diagram of a twenty-fourth embodiment of the present invention.
FIG. 25 is a configuration diagram of a twenty-fifth embodiment of the present invention.
FIG. 26 is a configuration diagram of a conventional polymer electrolyte fuel cell power generator.
[Explanation of symbols]
1: Fuel cell
11: Fuel electrode
12: Oxidizer electrode
13: Cooling device
131: Fuel cell cooling medium path
132: Cooling medium circulation pump
133: Fuel processing system coolant circulation path
134: Fuel cell cooling medium cooler
135: Fuel cell cooling medium heater
2: Reformer
21: Reforming catalyst layer
22: Hydrogen rich gas cooler
3: Carbon monoxide transformer
31: Low temperature carbon monoxide transformer
32: Selective oxidation type carbon monoxide remover
33: Desulfurizer
4: Exhaust gas burner
5: Water condenser
61: Water evaporator
62: Steam superheater
63: Fuel mixed gas preheater
64: Fuel gas mixture superheater
70: Activation burner
71: First branch point
72: Second branch point
73: First confluence
74: Second confluence
75: First stop valve
76: Second stop valve
77: Third stop valve
78: Fourth stop valve

Claims (33)

水素を含むガスを燃料とし固体高分子を電解質として酸化剤極と燃料極を有する燃料電池と、燃料電池を経由して冷却媒体を循環させる燃料電池冷却媒体径路と、燃料電池冷却媒体径路の燃料電池上流から燃料電池冷却媒体を分岐しこれを燃料電池冷却媒体径路に燃料電池下流にて合流させる燃料処理系冷却媒体径路と、燃料電池冷却媒体径路で冷却媒体を循環させる冷却媒体循環ポンプと、これら冷却媒体から熱量を除去し冷却媒体の温度を調整する燃料電池冷却媒体冷却器と、燃料電池燃料極上流に設置され改質触媒層を有しこの改質触媒層において炭素原子と水素原子を分子中に少なくとも各々一個以上含む燃料及び酸素を含む気体及び水蒸気の混合気を水素リッチガスに改質する改質器と、水素リッチガス流路の改質器下流に設置され水素リッチガスと燃料処理系冷却媒体径路を流通する燃料電池冷却媒体との熱交換を行う水素リッチガス冷却器と、水素リッチガス冷却器下流に設置され低温一酸化炭素変成触媒層を有する低温一酸化炭素変成器と、低温一酸化炭素変成器上流に設置され吸収材層を有しこの吸収材層により燃料もしくは水素リッチガス中の硫黄分を吸収する脱硫器と、低温一酸化炭素変成器下流に設置され選択酸化式一酸化炭素除去触媒層を有する単数もしくは複数の選択酸化式一酸化炭素除去器と、燃料電池の燃料極からの排気ガスの全量と酸化剤極からの排気ガスの全量もしくは一部を混合して燃焼する排気ガスバーナーと、排気ガスバーナーの燃焼ガス及び酸化剤極の排気ガスの混合ガスから水を凝縮させる水凝縮器とが備えられた固体高分子型燃料電池発電装置において、
改質器に供給する水蒸気を発生させる水蒸発器と、
水蒸発器で発生した水蒸気を過熱する水蒸気過熱器と、
改質器に供給する燃料を酸素を含むガスと混合した状態で加熱する燃料混合ガス予熱器とが設けられ、
排気ガスバーナーからの燃焼ガスが、水蒸気過熱器、燃料混合ガス予熱器、水蒸発器、水凝縮器の順に通過するように燃焼ガス流路が形成されたことを特徴とする固体高分子型燃料電池発電装置。A fuel cell having a gas containing hydrogen and a solid polymer as an electrolyte and having an oxidant electrode and a fuel electrode, a fuel cell cooling medium path for circulating a cooling medium via the fuel cell, and a fuel in the fuel cell cooling medium path A fuel processing system cooling medium path that branches the fuel cell cooling medium from the upstream side of the battery and joins it to the fuel cell cooling medium path downstream of the fuel cell; a cooling medium circulation pump that circulates the cooling medium in the fuel cell cooling medium path; A fuel cell cooling medium cooler that removes heat from these cooling media and adjusts the temperature of the cooling medium, and a reforming catalyst layer installed upstream of the fuel cell fuel electrode, in which carbon atoms and hydrogen atoms are removed. Installed in the downstream of the reformer of the hydrogen rich gas flow path, and the reformer for reforming the gas mixture containing at least one fuel in the molecule and the gas containing oxygen and water vapor to hydrogen rich gas Low-temperature carbon monoxide conversion having a low-temperature carbon monoxide conversion catalyst layer installed downstream of the hydrogen-rich gas cooler and a hydrogen-rich gas cooler that exchanges heat between the hydrogen-rich gas and the fuel cell coolant flowing through the fuel treatment system coolant path A desulfurizer that is installed upstream of the low-temperature carbon monoxide converter and has an absorbent layer that absorbs sulfur in fuel or hydrogen-rich gas, and is installed downstream of the low-temperature carbon monoxide converter. Mix one or more selective oxidation carbon monoxide removers with an oxidized carbon monoxide removal catalyst layer and all or part of the exhaust gas from the fuel electrode of the fuel cell and all or part of the exhaust gas from the oxidizer electrode A solid polymer type fuel comprising an exhaust gas burner that burns and a water condenser that condenses water from a mixed gas of the exhaust gas of the exhaust gas burner and the exhaust gas of the oxidizer electrode In cell power plant,
A water evaporator for generating water vapor to be supplied to the reformer;
A steam superheater that superheats the steam generated in the water evaporator;
A fuel mixed gas preheater for heating the fuel supplied to the reformer in a state of being mixed with a gas containing oxygen;
Solid polymer fuel characterized in that a combustion gas flow path is formed so that the combustion gas from the exhaust gas burner passes in the order of a steam superheater, a fuel mixture gas preheater, a water evaporator, and a water condenser Battery power generator. 改質器の外筒部に水素リッチガス冷却器が設置され、改質器及び水素リッチガス冷却器が複合一体化されたことを特徴とする請求項１記載の固体高分子型燃料電池発電装置。2. The polymer electrolyte fuel cell power generator according to claim 1, wherein a hydrogen-rich gas cooler is installed in an outer cylinder portion of the reformer, and the reformer and the hydrogen-rich gas cooler are combined and integrated. 排気ガスバーナーの外筒部に水蒸気過熱器が設置され、排気ガスバーナー及び水蒸気過熱器が複合一体化されたことを特徴とする請求項１または２記載の固体高分子型燃料電池発電装置。The solid polymer fuel cell power generator according to claim 1 or 2, wherein a steam superheater is installed in an outer cylinder portion of the exhaust gas burner, and the exhaust gas burner and the steam superheater are combined and integrated. 排気ガスバーナー及び水蒸気過熱器が複合一体化された機器の外筒部に混合ガス予熱器が設置され、排気ガスバーナーと水蒸気過熱器と混合ガス予熱器とが複合一体化されたことを特徴とする請求項３記載の固体高分子型燃料電池発電装置。A mixed gas preheater is installed in the outer cylinder part of a device in which an exhaust gas burner and a steam superheater are combined and integrated, and the exhaust gas burner, the steam superheater and the mixed gas preheater are combined and integrated. The polymer electrolyte fuel cell power generator according to claim 3. 改質器外筒部に水素リッチガス冷却器と共に水蒸発器が設置され、改質器と水素リッチガス冷却器と水蒸発器とが複合一体化されたことを特徴とする請求項２、３または４記載の固体高分子型燃料電池発電装置。5. A water evaporator and a hydrogen rich gas cooler are installed in the reformer outer cylinder, and the reformer, the hydrogen rich gas cooler, and the water evaporator are combined and integrated. The solid polymer fuel cell power generator described in the paragraph. 脱硫器が水素リッチガス流路の水素リッチガス冷却器と低温一酸化炭素変成器の中間に設置され、低温一酸化炭素変成器及び脱硫器が複合一体化されたことを特徴とする請求項１、２、３、４または５記載の固体高分子型燃料電池発電装置。The desulfurizer is installed between the hydrogen-rich gas cooler and the low-temperature carbon monoxide converter in the hydrogen-rich gas flow path, and the low-temperature carbon monoxide converter and the desulfurizer are combined and integrated. 3. The polymer electrolyte fuel cell power generator according to 3, 4, or 5. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する第１の合流点が形成され、
燃料混合ガス予熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、
分岐点の下流に燃焼ガスが合流する第２の合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器、水凝縮器の順に通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置されたことを特徴とする請求項１、２、３、４、５または６記載の固体高分子型燃料電池発電装置。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A first junction is formed between the exhaust gas burner and the steam superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
A branch point is formed between the fuel gas mixture preheater and the water evaporator to separate the combustion gas,
A second merge point where the combustion gas merges is formed downstream of the branch point,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the first junction. The combustion gas that has passed through the steam superheater and the fuel gas mixture preheater in this order and branched at the branch point is the fuel cell cooling medium heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide shift catalyst layer, and the selective oxidation. After passing through the order of the carbon monoxide removal catalyst layer, the combustion gas from the remaining startup burner is joined again at the second junction, and the startup burner combustion gas passes through the water evaporator and the water condenser in this order. Composed of
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. 7. The polymer electrolyte fuel cell power generator according to claim 1, 2, 3, 4, 5 or 6. 起動バーナーと第１の合流点の間に第１止め弁が設けられ、分岐点と燃料電池冷却媒体加熱器の間に第２止め弁が設けられ、選択酸化式一酸化炭素除去触媒層と第２の合流点の間に第３止め弁が設けられたことを特徴とする請求項７記載の固体高分子型燃料電池発電装置。A first stop valve is provided between the start burner and the first junction, and a second stop valve is provided between the branch point and the fuel cell coolant heater, and the selective oxidation carbon monoxide removal catalyst layer and the first stop valve are provided. 8. The polymer electrolyte fuel cell power generator according to claim 7, wherein a third stop valve is provided between the two junctions. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する第１の合流点が形成され、
燃料混合ガス予熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、
分岐点の下流に燃焼ガスが合流する第２の合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器、水凝縮器の順に通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置され、
起動バーナーと第１の合流点の間に第１止め弁が設けられ、分岐点と燃料電池冷却媒体加熱器の間に第２止め弁が設けられ、選択酸化式一酸化炭素除去触媒層と第２の合流点の間に第３止め弁が設けられた固体高分子型燃料電池発電装置の運転方法において、
装置起動時でかつ水蒸発器温度、燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁、第２止め弁及び第３止め弁が開き、
装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかの温度が予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第１止め弁が開いて第２止め弁及び第３止め弁が閉じ、
第２止め弁及び第３止め弁が開いた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、
第２止め弁及び第３止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて運転状態に移行し、
運転時には第１止め弁、第２止め弁及び第３止め弁が閉じ、
停止時には第１止め弁が閉じて第２止め弁及び第３止め弁が開くことを特徴とする固体高分子型燃料電池発電装置の運転方法。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A first junction is formed between the exhaust gas burner and the steam superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
A branch point is formed between the fuel gas mixture preheater and the water evaporator to separate the combustion gas,
A second merge point where the combustion gas merges is formed downstream of the branch point,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the first junction. The combustion gas that has passed through the steam superheater and the fuel gas mixture preheater in this order and branched at the branch point is the fuel cell cooling medium heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide shift catalyst layer, and the selective oxidation. After passing through the order of the carbon monoxide removal catalyst layer, the combustion gas from the remaining startup burner is joined again at the second junction, and the startup burner combustion gas passes through the water evaporator and the water condenser in this order. Composed of
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. Installed,
A first stop valve is provided between the start burner and the first junction, a second stop valve is provided between the branch point and the fuel cell coolant heater, and the selective oxidation carbon monoxide removal catalyst layer and the first stop valve are provided. In the operation method of the polymer electrolyte fuel cell power generator in which the third stop valve is provided between the two junctions,
Target at which at least one of water evaporator temperature, fuel cell cooling medium heater temperature, desulfurizer temperature, low temperature carbon monoxide shift catalyst layer temperature, selective oxidation carbon monoxide removal catalyst layer temperature is set in advance at the time of starting the apparatus The first stop valve, the second stop valve, and the third stop valve are opened when none of the temperatures reaches the preset maximum temperature limit,
Whether the fuel cell cooling medium heater temperature, desulfurizer temperature, low-temperature carbon monoxide shift catalyst layer temperature, and selective oxidation carbon monoxide removal catalyst layer temperature all exceeded the preset target temperature at the time of startup Alternatively, when one of the temperatures reaches a preset maximum limit temperature and the water evaporator temperature does not reach the preset target temperature, the first stop valve is opened and the second stop valve and the third stop valve are opened. Close,
When the water evaporator temperature reaches a preset maximum limit temperature with the second stop valve and the third stop valve open, only the first stop valve is closed,
When the water evaporator temperature reaches a preset target temperature with the second stop valve and the third stop valve closed, the first stop valve is closed and the operation state is shifted.
During operation, the first stop valve, the second stop valve and the third stop valve are closed,
A method of operating a polymer electrolyte fuel cell power generator, wherein the first stop valve is closed and the second stop valve and the third stop valve are opened when the engine is stopped. 第２止め弁と第３止め弁の間の流路のいずれかの箇所に第２の分岐点が形成され、
第２の分岐点には外気に開放される配管が接続され、
この配管に第４止め弁が設けられたことを特徴とする請求項８記載の固体高分子型燃料電池発電装置。A second branch point is formed at any point in the flow path between the second stop valve and the third stop valve;
A pipe that is open to the outside air is connected to the second branch point,
9. The polymer electrolyte fuel cell power generator according to claim 8, wherein a fourth stop valve is provided in the pipe. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する第１の合流点が形成され、
燃料混合ガス予熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、
分岐点の下流に燃焼ガスが合流する第２の合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器、水凝縮器の順に通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置され、
起動バーナーと第１の合流点の間に第１止め弁が設けられ、分岐点と燃料電池冷却媒体加熱器の間に第２止め弁が設けられ、選択酸化式一酸化炭素除去触媒層と第２の合流点の間に第３止め弁が設けられ、
さらに、第２止め弁と第３止め弁の間の流路のいずれかの箇所に第２の分岐点が形成され、
第２の分岐点には外気に開放される配管が接続され、
この配管に第４止め弁が設けられた固体高分子型燃料電池発電装置の運転方法において、
装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁、第２止め弁及び第３止め弁が開いて第４止め弁が閉じ、
装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかが予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第２止め弁及び第３止め弁が閉じて第１止め弁及び第４止め弁が開き、
第２止め弁及び第３止め弁が開いて第４止め弁が閉じた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、
第２止め弁及び第３止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて第４止め弁が開いて運転状態に移行し、
運転時には第１止め弁、第２止め弁及び第３止め弁が閉じて第４止め弁が開き、
装置停止時には第２止め弁または第３止め弁の少なくとも一方と第４止め弁が開くことを特徴とする固体高分子型燃料電池発電装置の運転方法。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A first junction is formed between the exhaust gas burner and the steam superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
A branch point is formed between the fuel gas mixture preheater and the water evaporator to separate the combustion gas,
A second merge point where the combustion gas merges is formed downstream of the branch point,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the first junction. The combustion gas that has passed through the steam superheater and the fuel gas mixture preheater in this order and branched at the branch point is the fuel cell cooling medium heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide shift catalyst layer, and the selective oxidation. After passing through the order of the carbon monoxide removal catalyst layer, the combustion gas from the remaining startup burner is joined again at the second junction, and the startup burner combustion gas passes through the water evaporator and the water condenser in this order. Composed of
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. Installed,
A first stop valve is provided between the start burner and the first junction, a second stop valve is provided between the branch point and the fuel cell coolant heater, and the selective oxidation carbon monoxide removal catalyst layer and the first stop valve are provided. A third stop valve is provided between the two junctions;
Furthermore, a second branch point is formed at any location in the flow path between the second stop valve and the third stop valve,
A pipe that is open to the outside air is connected to the second branch point,
In the operation method of the polymer electrolyte fuel cell power generator in which the fourth stop valve is provided in the pipe,
At the time of starting the apparatus, at least one of the fuel cell coolant heating temperature, the desulfurizer temperature, the low-temperature carbon monoxide conversion catalyst layer temperature, and the selective oxidation type carbon monoxide removal catalyst layer temperature does not reach a preset target temperature and If none of the temperatures reaches the preset maximum limit temperature, the first stop valve, the second stop valve and the third stop valve are opened and the fourth stop valve is closed,
Whether the fuel cell cooling medium heater temperature, desulfurizer temperature, low-temperature carbon monoxide shift catalyst layer temperature, and selective oxidation carbon monoxide removal catalyst layer temperature all exceeded the preset target temperature at the time of startup Alternatively, when either reaches the preset maximum limit temperature and the water evaporator temperature does not reach the preset target temperature, the second stop valve and the third stop valve are closed and the first stop valve and the fourth stop valve are closed. The stop valve opens,
When the water evaporator temperature reaches a preset maximum limit temperature with the second stop valve and the third stop valve open and the fourth stop valve closed, only the first stop valve is closed,
When the water evaporator temperature reaches a preset target temperature with the second stop valve and the third stop valve closed, the first stop valve is closed and the fourth stop valve is opened to shift to the operating state.
During operation, the first stop valve, the second stop valve and the third stop valve are closed and the fourth stop valve is opened,
A method for operating a polymer electrolyte fuel cell power generator, wherein at least one of the second stop valve and the third stop valve and the fourth stop valve are opened when the apparatus is stopped. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、
燃料混合ガス予熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、大気中に出て、一方、分岐点にて分岐された残余の起動バーナーからの燃焼ガスは更に水蒸発器、水凝縮器の順に通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置されたことを特徴とする請求項１、２、３、４、５または６記載の固体高分子型燃料電池発電装置。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A junction is formed between the exhaust gas burner and the steam superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
A branch point is formed between the fuel gas mixture preheater and the water evaporator to separate the combustion gas,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the junction, The combustion gas that passes through the superheater and the fuel gas mixture preheater in this order and branches at the branch point is the fuel cell coolant heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide shift catalyst layer, and the selective oxidation type monoxide. After passing through the order of the carbon removal catalyst layer, it exits into the atmosphere, and on the other hand, the combustion gas from the remaining startup burner branched at the branch point is further passed through the water evaporator and water condenser in this order. ,
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. 7. The polymer electrolyte fuel cell power generator according to claim 1, 2, 3, 4, 5 or 6. 起動バーナーと合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられたことを特徴とする請求項１２記載の固体高分子型燃料電池発電装置。13. The polymer electrolyte fuel according to claim 12, wherein a first stop valve is provided between the start burner and the junction, and a second stop valve is provided between the branch point and the desulfurizer absorbent layer. Battery power generator. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、
燃料混合ガス予熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器の順に通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、大気中に出て、一方、分岐点にて分岐された残余の起動バーナーからの燃焼ガスは更に水蒸発器、水凝縮器の順に通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置され、
起動バーナーと合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられた固体高分子型燃料電池発電装置の運転方法において、
装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁及び第２止め弁が開き、
装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかが予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第１止め弁が開いて第２止め弁が閉じ、
第２止め弁が開いた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、
第２止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて運転状態に移行し、
運転時には第１止め弁及び第２止め弁が閉じることを特徴とする固体高分子型燃料電池発電装置の運転方法。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A junction is formed between the exhaust gas burner and the steam superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
A branch point is formed between the fuel gas mixture preheater and the water evaporator to separate the combustion gas,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the junction, The combustion gas that passes through the superheater and the fuel gas mixture preheater in this order and branches at the branch point is the fuel cell coolant heater, the absorber layer of the desulfurizer, the low-temperature carbon monoxide shift catalyst layer, and the selective oxidation type monoxide. After passing through the order of the carbon removal catalyst layer, it exits into the atmosphere, and on the other hand, the combustion gas from the remaining startup burner branched at the branch point is further passed through the water evaporator and water condenser in this order. ,
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. Installed,
In the operation method of the polymer electrolyte fuel cell power generator in which the first stop valve is provided between the start burner and the junction, and the second stop valve is provided between the branch point and the desulfurizer absorbent layer,
At the time of start-up of the apparatus, at least one of the fuel cell cooling medium heater temperature, the desulfurizer temperature, the low temperature carbon monoxide conversion catalyst layer temperature, and the selective oxidation type carbon monoxide removal catalyst layer temperature does not reach a preset target temperature and If neither temperature reaches the preset maximum temperature limit, the first stop valve and the second stop valve are opened,
The temperature of the fuel cell cooling medium heater, the temperature of the desulfurizer, the low temperature carbon monoxide shift catalyst layer temperature, and the selective oxidation carbon monoxide removal catalyst layer temperature all reached or exceeded the preset target temperature when the device was started. Or if either reaches a preset maximum temperature limit and the water evaporator temperature does not reach a preset target temperature, the first stop valve opens and the second stop valve closes,
If the water evaporator temperature reaches a preset maximum limit temperature with the second stop valve open, only the first stop valve is closed,
When the water evaporator temperature reaches a preset target temperature with the second stop valve closed, the first stop valve closes and the operation state shifts.
A method for operating a polymer electrolyte fuel cell power generator, wherein the first stop valve and the second stop valve are closed during operation. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器、水蒸発器、燃料電池冷却媒体加熱器、水凝縮器の順に通過するように構成されたことを特徴とする請求項１、２、３、４、５または６記載の固体高分子型燃料電池発電装置。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A junction is formed between the exhaust gas burner and the steam superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the junction, The superheater, the fuel gas mixture preheater, the water evaporator, the fuel cell cooling medium heater, and the water condenser are configured to pass through in this order. The polymer electrolyte fuel cell power generator described in the paragraph. 起動バーナーと合流点の間に止め弁が設けられたことを特徴とする請求項１５記載の固体高分子型燃料電池発電装置。16. The polymer electrolyte fuel cell power generator according to claim 15, wherein a stop valve is provided between the start burner and the junction. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと水蒸気過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、水蒸気過熱器、燃料混合ガス予熱器、水蒸発器、燃料電池冷却媒体加熱器、水凝縮器の順に通過するように構成され、
起動バーナーと合流点の間に止め弁が設けられた固体高分子型燃料電池発電装置の運転方法において、
装置起動時の水蒸発器温度が予め設定された目標温度に未達であれば止め弁が開き、
止め弁が開いた状態で燃料電池冷却媒体加熱器温度が予め設定された最高限界温度に達した場合には、燃料電池冷却媒体冷却器が運転されて温度制御を行い、
水蒸発器温度が予め設定された目標温度に達したら止め弁が閉じて運転状態に移行し、
運転時には止め弁が閉じ、
かつ装置起動時には脱硫器、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の温度がそれぞれ個別に電力によって加熱されることを特徴とする固体高分子型燃料電池発電装置の運転方法。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A junction is formed between the exhaust gas burner and the steam superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the junction, It is configured to pass through a superheater, a fuel gas mixture preheater, a water evaporator, a fuel cell cooling medium heater, and a water condenser in this order.
In the operation method of the polymer electrolyte fuel cell power generator in which a stop valve is provided between the start burner and the junction,
If the water evaporator temperature at the time of starting the device does not reach the preset target temperature, the stop valve opens,
When the fuel cell coolant heating device temperature reaches a preset maximum limit temperature with the stop valve open, the fuel cell coolant cooling device is operated to control the temperature,
When the water evaporator temperature reaches the preset target temperature, the stop valve is closed and the operation state is shifted.
During operation, the stop valve closes,
The operation of the solid polymer fuel cell power generator is characterized in that the temperature of the desulfurizer, the low-temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer is individually heated by electric power when the apparatus is started. Method. 水素を含むガスを燃料とし固体高分子を電解質として酸化剤極と燃料極を有する燃料電池と、燃料電池を経由して冷却媒体を循環させる燃料電池冷却媒体径路と、燃料電池冷却媒体径路の燃料電池上流から燃料電池冷却媒体を分岐しこれを燃料電池冷却媒体径路に燃料電池下流にて合流させる燃料処理系冷却媒体径路と、燃料電池冷却媒体径路で冷却媒体を循環させる冷却媒体循環ポンプと、これら冷却媒体から熱量を除去し冷却媒体の温度を調整する燃料電池冷却媒体冷却器と、燃料電池燃料極上流に設置され改質触媒層を有しこの改質触媒層において炭素原子と水素原子を分子中に少なくとも各々一個以上含む燃料及び酸素を含む気体及び水蒸気の混合気を水素リッチガスに改質する改質器と、水素リッチガス流路の改質器下流に設置され水素リッチガスと燃料処理系冷却媒体径路を流通する燃料電池冷却媒体との熱交換を行う水素リッチガス冷却器と、水素リッチガス冷却器下流に設置され低温一酸化炭素変成触媒層を有する低温一酸化炭素変成器と、低温一酸化炭素変成器上流に設置され吸収材層を有しこの吸収材層により燃料もしくは水素リッチガス中の硫黄分を吸収する脱硫器と、低温一酸化炭素変成器下流に設置され選択酸化式一酸化炭素除去触媒層を有する単数もしくは複数の選択酸化式一酸化炭素除去器と、燃料電池の燃料極からの排気ガスの全量と酸化剤極からの排気ガスの全量もしくは一部を混合して燃焼する排気ガスバーナーと、排気ガスバーナーの燃焼ガス及び酸化剤極の排気ガスの混合ガスから水を凝縮させる水凝縮器とが備えられた固体高分子型燃料電池発電装置において、
改質器に供給する水蒸気を発生させる水蒸発器と、
酸素を含むガスと燃料と水蒸発器で発生した水蒸気との混合ガスを過熱する燃料混合ガス過熱器とが設けられ、
排気ガスバーナーからの燃焼ガスが、燃料混合ガス過熱器、水蒸発器、水凝縮器の順に通過するように燃焼ガス流路が形成されたことを特徴とする固体高分子型燃料電池発電装置。A fuel cell having a gas containing hydrogen and a solid polymer as an electrolyte and having an oxidant electrode and a fuel electrode, a fuel cell cooling medium path for circulating a cooling medium via the fuel cell, and a fuel in the fuel cell cooling medium path A fuel processing system cooling medium path that branches the fuel cell cooling medium from the upstream side of the battery and joins it to the fuel cell cooling medium path downstream of the fuel cell; a cooling medium circulation pump that circulates the cooling medium in the fuel cell cooling medium path; A fuel cell cooling medium cooler that removes heat from these cooling media and adjusts the temperature of the cooling medium, and a reforming catalyst layer installed upstream of the fuel cell fuel electrode, in which carbon atoms and hydrogen atoms are removed. Installed in the downstream of the reformer of the hydrogen rich gas flow path, and the reformer for reforming the gas mixture containing at least one fuel in the molecule and the gas containing oxygen and water vapor to hydrogen rich gas Low-temperature carbon monoxide conversion having a low-temperature carbon monoxide conversion catalyst layer installed downstream of the hydrogen-rich gas cooler and a hydrogen-rich gas cooler that exchanges heat between the hydrogen-rich gas and the fuel cell coolant flowing through the fuel treatment system coolant path A desulfurizer that is installed upstream of the low-temperature carbon monoxide converter and has an absorbent layer that absorbs sulfur in fuel or hydrogen-rich gas, and is installed downstream of the low-temperature carbon monoxide converter. Mix one or more selective oxidation carbon monoxide removers with an oxidized carbon monoxide removal catalyst layer and all or part of the exhaust gas from the fuel electrode of the fuel cell and all or part of the exhaust gas from the oxidizer electrode A solid polymer type fuel comprising an exhaust gas burner that burns and a water condenser that condenses water from a mixed gas of the exhaust gas of the exhaust gas burner and the exhaust gas of the oxidizer electrode In cell power plant,
A water evaporator for generating water vapor to be supplied to the reformer;
A fuel mixed gas superheater for superheating a mixed gas of oxygen-containing gas, fuel, and water vapor generated in the water evaporator;
A solid polymer fuel cell power generator characterized in that a combustion gas passage is formed so that combustion gas from an exhaust gas burner passes through a fuel gas mixture superheater, a water evaporator, and a water condenser in this order. 改質器の外筒部に水素リッチガス冷却器が設置され、改質器及び水素リッチガス冷却器が複合一体化されたことを特徴とする請求項１８記載の固体高分子型燃料電池発電装置。19. The polymer electrolyte fuel cell power generator according to claim 18, wherein a hydrogen rich gas cooler is installed in an outer cylinder portion of the reformer, and the reformer and the hydrogen rich gas cooler are combined and integrated. 排気ガスバーナーの外筒部に燃料混合ガス過熱器が設置され、排気ガスバーナー及び燃料混合ガス過熱器が複合一体化されたことを特徴とする請求項１８または１９記載の固体高分子型燃料電池発電装置。20. The polymer electrolyte fuel cell according to claim 18, wherein a fuel mixed gas superheater is installed in an outer cylinder portion of the exhaust gas burner, and the exhaust gas burner and the fuel mixed gas superheater are combined and integrated. Power generation device. 改質器外筒部に水素リッチガス冷却器と共に水蒸発器が設置され、改質器と水素リッチガス冷却器と水蒸発器とが複合一体化されたことを特徴とする請求項１９または２０記載の固体高分子型燃料電池発電装置。21. The water evaporator as well as the hydrogen rich gas cooler is installed in the reformer outer cylinder, and the reformer, the hydrogen rich gas cooler, and the water evaporator are combined and integrated. Solid polymer fuel cell power generator. 脱硫器が水素リッチガス流路の水素リッチガス冷却器と低温一酸化炭素変成器の中間に設置され、低温一酸化炭素変成器及び脱硫器が複合一体化されたことを特徴とする請求項１８、１９、２０または２１記載の固体高分子型燃料電池発電装置。The desulfurizer is installed between the hydrogen-rich gas cooler and the low-temperature carbon monoxide converter in the hydrogen-rich gas flow path, and the low-temperature carbon monoxide converter and the desulfurizer are combined and integrated. 20. A polymer electrolyte fuel cell power generator according to claim 20 or 21. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する第１の合流点が形成され、
燃料混合ガス過熱器の下流に燃焼ガスが分れる分岐点が形成され、
分岐点の下流に燃焼ガスが合流する第２の合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、次いで燃料混合ガス過熱器を通過した後、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過し、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器を通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置されたことを特徴とする請求項１８、１９、２０、２１、または２２記載の固体高分子型燃料電池発電装置。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A first junction is formed between the exhaust gas burner and the fuel gas mixture superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
A branch point where combustion gas is divided is formed downstream of the fuel gas mixture superheater,
A second merge point where the combustion gas merges is formed downstream of the branch point,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the first junction. Then, after passing through the fuel gas mixture superheater, the combustion gas branched at the branch point is the fuel cell cooling medium heater, the absorber layer of the desulfurizer, the low temperature carbon monoxide shift catalyst layer, the selective oxidation type monoxide It passes through the order of the carbon removal catalyst layer, is joined again to the combustion gas from the remaining startup burner at the second junction, and further configured to pass the startup burner combustion gas through the water evaporator,
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. 23. The polymer electrolyte fuel cell power generator according to claim 18, 19, 20, 21, or 22. 改質器の改質触媒層と第１の合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられ、選択酸化式一酸化炭素除去触媒層と第２の合流点の間に第３止め弁が設けられたことを特徴とする請求項２３記載の固体高分子型燃料電池発電装置。A first stop valve is provided between the reforming catalyst layer of the reformer and the first merging point, and a second stop valve is provided between the branch point and the desulfurizer absorbent layer, and selectively oxidized carbon monoxide. The solid polymer fuel cell power generator according to claim 23, wherein a third stop valve is provided between the removed catalyst layer and the second junction. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する第１の合流点が形成され、
燃料混合ガス過熱器の下流に燃焼ガスが分れる分岐点が形成され、
分岐点の下流に燃焼ガスが合流する第２の合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、次いで燃料混合ガス過熱器を通過した後、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過し、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器を通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置され、
改質器の改質触媒層と第１の合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられ、選択酸化式一酸化炭素除去触媒層と第２の合流点の間に第３止め弁が設けられた固体高分子型燃料電池発電装置の運転方法において、
装置起動時でかつ水蒸発器温度、燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁、第２止め弁及び第３止め弁が開き、
装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかの温度が予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第１止め弁が開いて第２止め弁及び第３止め弁が閉じ、
第２止め弁及び第３止め弁が開いた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、
第２止め弁及び第３止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて運転状態に移行し、
運転時には第１止め弁、第２止め弁及び第３止め弁が閉じ、
停止時には第１止め弁が閉じて第２止め弁及び第３止め弁が開くことを特徴とする固体高分子型燃料電池発電装置の運転方法。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A first junction is formed between the exhaust gas burner and the fuel gas mixture superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
A branch point where combustion gas is divided is formed downstream of the fuel gas mixture superheater,
A second merge point where the combustion gas merges is formed downstream of the branch point,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the first junction. Then, after passing through the fuel gas mixture superheater, the combustion gas branched at the branch point is the fuel cell cooling medium heater, the absorber layer of the desulfurizer, the low temperature carbon monoxide shift catalyst layer, the selective oxidation type monoxide It passes through the order of the carbon removal catalyst layer, is joined again to the combustion gas from the remaining startup burner at the second junction, and further configured to pass the startup burner combustion gas through the water evaporator,
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. Installed,
A first stop valve is provided between the reforming catalyst layer of the reformer and the first merging point, and a second stop valve is provided between the branch point and the desulfurizer absorbent material layer, and selectively oxidized carbon monoxide. In the operation method of the polymer electrolyte fuel cell power generator in which the third stop valve is provided between the removal catalyst layer and the second junction,
Target at which at least one of water evaporator temperature, fuel cell cooling medium heater temperature, desulfurizer temperature, low temperature carbon monoxide shift catalyst layer temperature, selective oxidation carbon monoxide removal catalyst layer temperature is set in advance at the time of starting the apparatus The first stop valve, the second stop valve, and the third stop valve are opened when none of the temperatures reaches the preset maximum temperature limit,
Whether the fuel cell cooling medium heater temperature, desulfurizer temperature, low-temperature carbon monoxide shift catalyst layer temperature, and selective oxidation carbon monoxide removal catalyst layer temperature all exceeded the preset target temperature at the time of startup Alternatively, when one of the temperatures reaches a preset maximum limit temperature and the water evaporator temperature does not reach the preset target temperature, the first stop valve is opened and the second stop valve and the third stop valve are opened. Close,
When the water evaporator temperature reaches a preset maximum limit temperature with the second stop valve and the third stop valve open, only the first stop valve is closed,
When the water evaporator temperature reaches a preset target temperature with the second stop valve and the third stop valve closed, the first stop valve is closed and the operation state is shifted.
During operation, the first stop valve, the second stop valve and the third stop valve are closed,
A method of operating a polymer electrolyte fuel cell power generator, wherein the first stop valve is closed and the second stop valve and the third stop valve are opened when the engine is stopped. 第２止め弁と第３止め弁の間の流路のいずれかの箇所に第２の分岐点が形成され、
第２の分岐点には外気に開放される配管が接続され、
この配管に第４止め弁が設けられたことを特徴とする請求項２４記載の固体高分子型燃料電池発電装置。A second branch point is formed at any point in the flow path between the second stop valve and the third stop valve;
A pipe that is open to the outside air is connected to the second branch point,
25. The polymer electrolyte fuel cell power generator according to claim 24, wherein a fourth stop valve is provided in the pipe. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する第１の合流点が形成され、
燃料混合ガス過熱器の下流に燃焼ガスが分れる分岐点が形成され、
分岐点の下流に燃焼ガスが合流する第２の合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、第１の合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、次いで燃料混合ガス過熱器を通過した後、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過し、第２の合流点で再び残余の起動バーナーからの燃焼ガスに合流し、更に起動バーナー燃焼ガスが水蒸発器を通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置され、
改質器の改質触媒層と第１の合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられ、選択酸化式一酸化炭素除去触媒層と第２の合流点の間に第３止め弁が設けられ、
第２止め弁と第３止め弁の間の流路のいずれかの箇所に第２の分岐点が形成され、
第２の分岐点には外気に開放される配管が接続され、
この配管に第４止め弁が設けられた固体高分子型燃料電池発電装置の運転方法において、
装置起動時でかつ燃料電池冷却媒体加熱器、脱硫器温度、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達せずかついずれの温度も予め設定された最高限界温度に達しない場合には第１止め弁、第２止め弁及び第３止め弁が開いて第４止め弁が閉じ、
装置起動時でかつ燃料電池冷却媒体加熱器温度、脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達したかもしくはいずれかが予め設定された最高限界温度に達し、かつ水蒸発器温度が予め設定した目標温度に達しない場合には第２止め弁及び第３止め弁が閉じて第１止め弁及び第４止め弁が開き、
第２止め弁及び第３止め弁が開いて第４止め弁が閉じた状態で水蒸発器温度が予め設定された最高限界温度に達した場合には第１止め弁のみが閉じ、
第２止め弁及び第３止め弁が閉じた状態で水蒸発器温度が予め設定した目標温度に達した場合には第１止め弁が閉じて第４止め弁が開いて運転状態に移行し、
運転時には第１止め弁、第２止め弁及び第３止め弁が閉じて第４止め弁が開き、
装置停止時には第２止め弁または第３止め弁の少なくとも一方と第４止め弁が開くことを特徴とする固体高分子型燃料電池発電装置の運転方法。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A first junction is formed between the exhaust gas burner and the fuel gas mixture superheater, where the combustion gas from the startup burner joins the combustion gas flow path from the exhaust gas burner,
A branch point where combustion gas is divided is formed downstream of the fuel gas mixture superheater,
A second merge point where the combustion gas merges is formed downstream of the branch point,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the first junction. Then, after passing through the fuel gas mixture superheater, the combustion gas branched at the branch point is the fuel cell cooling medium heater, the absorber layer of the desulfurizer, the low temperature carbon monoxide shift catalyst layer, the selective oxidation type monoxide It passes through the order of the carbon removal catalyst layer, is joined again to the combustion gas from the remaining startup burner at the second junction, and further configured to pass the startup burner combustion gas through the water evaporator,
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. Installed,
A first stop valve is provided between the reforming catalyst layer of the reformer and the first merging point, and a second stop valve is provided between the branch point and the desulfurizer absorbent layer, and selectively oxidized carbon monoxide. A third stop valve is provided between the removal catalyst layer and the second junction,
A second branch point is formed at any point in the flow path between the second stop valve and the third stop valve;
A pipe that is open to the outside air is connected to the second branch point,
In the operation method of the polymer electrolyte fuel cell power generator in which the fourth stop valve is provided in the pipe,
At the time of starting the apparatus, at least one of the fuel cell cooling medium heater, the desulfurizer temperature, the low temperature carbon monoxide conversion catalyst layer, the selective oxidation carbon monoxide removal catalyst layer temperature does not reach the preset target temperature, and If the temperature does not reach the preset maximum temperature limit, the first stop valve, the second stop valve and the third stop valve are opened and the fourth stop valve is closed,
Whether the fuel cell cooling medium heater temperature, desulfurizer temperature, low-temperature carbon monoxide shift catalyst layer temperature, and selective oxidation carbon monoxide removal catalyst layer temperature all exceeded the preset target temperature at the time of startup Alternatively, when either reaches the preset maximum limit temperature and the water evaporator temperature does not reach the preset target temperature, the second stop valve and the third stop valve are closed and the first stop valve and the fourth stop valve are closed. The stop valve opens,
When the water evaporator temperature reaches a preset maximum limit temperature with the second stop valve and the third stop valve open and the fourth stop valve closed, only the first stop valve is closed,
When the water evaporator temperature reaches a preset target temperature with the second stop valve and the third stop valve closed, the first stop valve is closed and the fourth stop valve is opened to shift to the operating state.
During operation, the first stop valve, the second stop valve and the third stop valve are closed and the fourth stop valve is opened,
A method for operating a polymer electrolyte fuel cell power generator, wherein at least one of the second stop valve and the third stop valve and the fourth stop valve are opened when the apparatus is stopped. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、
燃料混合ガス過熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入した後、燃料混合ガス過熱器を通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、大気中に出て、一方、分岐点にて分岐された残余の起動バーナーからの燃焼ガスは更に水蒸発器、水凝縮器の順に通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置されたことを特徴とする請求項１８、１９、２０、２１、または２２記載の固体高分子型燃料電池発電装置。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A junction is formed between the exhaust gas burner and the fuel gas mixture superheater where the combustion gas from the start burner joins the combustion gas flow path from the exhaust gas burner,
A branch point is formed between the fuel gas mixture superheater and the water evaporator, where the combustion gas is divided,
After the starter burner operates to generate combustion gas, the combustion gas passes through the reforming catalyst layer of the reformer, and then flows into the combustion gas flow path from the exhaust gas burner at the junction. Combustion gas that has passed through the fuel gas mixture superheater and branched at the branch point is a fuel cell coolant heater, a desulfurizer absorber layer, a low-temperature carbon monoxide shift catalyst layer, and a selective oxidation carbon monoxide removal catalyst layer. After passing in the order of, the combustion gas from the remaining start burner branched into the atmosphere at the branch point, further configured to pass in the order of the water evaporator, water condenser,
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. 23. The polymer electrolyte fuel cell power generator according to claim 18, 19, 20, 21, or 22. 改質触媒層と合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられたことを特徴とする請求項２８記載の固体高分子型燃料電池発電装置。29. The solid polymer according to claim 28, wherein a first stop valve is provided between the reforming catalyst layer and the junction, and a second stop valve is provided between the branch point and the desulfurizer absorbent layer. Type fuel cell power generator. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、
燃料混合ガス過熱器と水蒸発器の間に燃焼ガスが分れる分岐点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入した後、燃料混合ガス過熱器を通過し、分岐点にて分岐された燃焼ガスが燃料電池冷却媒体加熱器、脱硫器の吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の順に通過した後、大気中に出て、一方、分岐点にて分岐された残余の起動バーナーからの燃焼ガスは更に水蒸発器、水凝縮器の順に通過するように構成され、
かつ改質触媒層、脱硫器吸収材層、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層には起動バーナー燃焼ガスを流通する経路が、水素リッチガスが流通する経路とは独立して設置され、
改質触媒層と合流点の間に第１止め弁が設けられ、分岐点と脱硫器吸収材層の間に第２止め弁が設けられた固体高分子型燃料電池発電装置の運転方法において、
装置起動時でかつ脱硫器温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度の少なくとも一つが予め設定された目標温度に達しない場合には第１止め弁及び第２止め弁が開き、
装置起動時でかつ脱硫器温度温度、低温一酸化炭素変成触媒層温度、選択酸化式一酸化炭素除去触媒層温度のすべてが予め設定された目標温度以上に達した場合には第１止め弁が開いて第２止め弁が閉じ、
運転時には第１止め弁及び第２止め弁が閉じることを特徴とする固体高分子型燃料電池発電装置の運転方法。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A junction is formed between the exhaust gas burner and the fuel gas mixture superheater where the combustion gas from the start burner joins the combustion gas flow path from the exhaust gas burner,
A branch point is formed between the fuel gas mixture superheater and the water evaporator, where the combustion gas is divided,
After the starter burner operates to generate combustion gas, the combustion gas passes through the reforming catalyst layer of the reformer, and then flows into the combustion gas flow path from the exhaust gas burner at the junction. Combustion gas that has passed through the fuel gas mixture superheater and branched at the branch point is a fuel cell coolant heater, a desulfurizer absorber layer, a low-temperature carbon monoxide shift catalyst layer, and a selective oxidation carbon monoxide removal catalyst layer. After passing in the order of, the combustion gas from the remaining start burner branched into the atmosphere at the branch point, further configured to pass in the order of the water evaporator, water condenser,
In addition, in the reforming catalyst layer, the desulfurizer absorber layer, the low temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer, the path through which the startup burner combustion gas flows is independent of the path through which the hydrogen rich gas flows. Installed,
In the operation method of the polymer electrolyte fuel cell power generator in which the first stop valve is provided between the reforming catalyst layer and the junction, and the second stop valve is provided between the branch point and the desulfurizer absorber layer,
When at least one of the desulfurizer temperature, the low-temperature carbon monoxide shift catalyst layer temperature, and the selective oxidation carbon monoxide removal catalyst layer temperature does not reach the preset target temperature at the time of starting the apparatus, the first stop valve and the second 2 Stop valve opens,
When the apparatus is started up and all of the desulfurizer temperature, low temperature carbon monoxide conversion catalyst layer temperature, and selective oxidation carbon monoxide removal catalyst layer temperature have reached or exceeded the preset target temperature, the first stop valve is Open and the second stop valve closes,
A method for operating a polymer electrolyte fuel cell power generator, wherein the first stop valve and the second stop valve are closed during operation. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、燃料混合ガス過熱器、水蒸発器、燃料電池冷却媒体加熱器、水凝縮器の順に通過するように構成されたことを特徴とする請求項１８、１９、２０、２１、または２２記載の固体高分子型燃料電池発電装置。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A junction is formed between the exhaust gas burner and the fuel gas mixture superheater where the combustion gas from the start burner joins the combustion gas flow path from the exhaust gas burner,
When the device starts up, the start burner operates to generate combustion gas, which passes through the reforming catalyst layer of the reformer and flows into the combustion gas flow path from the exhaust gas burner at the junction. The solid polymer according to claim 18, 19, 20, 21, or 22, wherein the polymer gas is configured to pass through a mixed gas superheater, a water evaporator, a fuel cell cooling medium heater, and a water condenser in this order. Type fuel cell power generator. 改質器の改質触媒層と合流点の間に止め弁が設けられたことを特徴とする請求項３１記載の固体高分子型燃料電池発電装置。32. The polymer electrolyte fuel cell power generator according to claim 31, wherein a stop valve is provided between the reforming catalyst layer of the reformer and the junction. 燃料と酸素を含むガスを反応させて燃焼ガスを発生させる起動バーナーと、燃料電池の冷却媒体とガス体との熱交換を行う燃料電池冷却媒体加熱器とが設けられ、
排気ガスバーナーと燃料混合ガス過熱器の間に起動バーナーからの燃焼ガスが排気ガスバーナーからの燃焼ガス流路に合流する合流点が形成され、
装置起動時に起動バーナーが動作して燃焼ガスが発生し、この燃焼ガスが改質器の改質触媒層を通過した後、合流点にて排気ガスバーナーからの燃焼ガス流路に流入し、燃料混合ガス過熱器、水蒸発器、燃料電池冷却媒体加熱器、水凝縮器の順に通過するように構成され、
改質器の改質触媒層と合流点の間に止め弁が設けられた固体高分子型燃料電池発電装置の運転方法において、
装置起動時の水蒸発器温度が予め設定された目標温度に未達であれば止め弁が開き、
止め弁が開いた状態で燃料電池冷却媒体加熱器温度が予め設定された最高限界温度に達した場合には、燃料電池冷却媒体冷却器が運転されて温度制御を行い、
水蒸発器温度が予め設定された目標温度に達したら止め弁が閉じて運転状態に移行し、
運転時には止め弁が閉じ、
かつ装置起動時には脱硫器、低温一酸化炭素変成触媒層、選択酸化式一酸化炭素除去触媒層の温度がそれぞれ個別に電力によって加熱されることを特徴とする固体高分子型燃料電池発電装置の運転方法。A starting burner that reacts a gas containing fuel and oxygen to generate combustion gas, and a fuel cell cooling medium heater that performs heat exchange between the cooling medium of the fuel cell and the gas body,
A junction is formed between the exhaust gas burner and the fuel gas mixture superheater where the combustion gas from the start burner joins the combustion gas flow path from the exhaust gas burner,
When the device is started, the start burner operates to generate combustion gas. After this combustion gas passes through the reforming catalyst layer of the reformer, it flows into the combustion gas flow path from the exhaust gas burner at the junction, and fuel It is configured to pass in the order of mixed gas superheater, water evaporator, fuel cell coolant heater, water condenser,
In the operation method of the polymer electrolyte fuel cell power generator in which a stop valve is provided between the reforming catalyst layer of the reformer and the junction,
If the water evaporator temperature at the time of starting the device does not reach the preset target temperature, the stop valve opens,
When the fuel cell coolant heating device temperature reaches a preset maximum limit temperature with the stop valve open, the fuel cell coolant cooling device is operated to control the temperature,
When the water evaporator temperature reaches the preset target temperature, the stop valve is closed and the operation state is shifted.
During operation, the stop valve closes,
The operation of the solid polymer fuel cell power generator is characterized in that the temperature of the desulfurizer, the low-temperature carbon monoxide conversion catalyst layer, and the selective oxidation carbon monoxide removal catalyst layer is individually heated by electric power when the apparatus is started. Method.
JP27319999A 1999-09-27 1999-09-27 Solid polymer fuel cell power generator and method of operating the same Expired - Fee Related JP3813391B2 (en)

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