JP2004071312A - Heat self supporting solid oxide fuel cell system - Google Patents
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- JP2004071312A JP2004071312A JP2002228036A JP2002228036A JP2004071312A JP 2004071312 A JP2004071312 A JP 2004071312A JP 2002228036 A JP2002228036 A JP 2002228036A JP 2002228036 A JP2002228036 A JP 2002228036A JP 2004071312 A JP2004071312 A JP 2004071312A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、熱自立型固体酸化物形燃料電池システムに関し、より具体的には全負荷運転時に加え、部分負荷運転時においても熱自立させるようにしてなる熱自立型固体酸化物形燃料電池システムに関する。
【０００２】
【従来の技術】
固体酸化物形燃料電池（ＳＯＦＣ：Ｓｏｌｉｄ Ｏｘｉｄｅ Ｆｕｅｌ Ｃｅｌｌｓ）は８５０〜１０００℃程度という高温で運転されるが、最近ではそれより低温、例えば７５０℃程度というような温度で運転されるものも開発されつつある。従来、ＳＯＦＣを運転するに際しては、全負荷運転が基本であり、しかも常時運転することが想定されている。しかし、現実には、例えば昼間に全負荷運転をし、夜間には低負荷運転をすることが考えられる。
【０００３】
ＳＯＦＣにおいては、上記のように高温で運転され、全負荷運転時には熱余り状態である。しかし、低負荷運転時には、電池内部の発熱に比して外部への散熱が大きくり、この場合でも、熱自立、すなわちＳＯＦＣの運転時に、発電に関して発生する熱とは別に別途余分なエネルギーを無駄に消費することなく、運転温度が所定の温度に維持され、保温される状態とすることが必要である。
【０００４】
ここで、一般的には、ＳＯＦＣシステムにおいては、システムケールが大きい場合には内部発熱に対して外部への放熱量が小さくなるため、熱自立は容易となる。また、ＳＯＦＣスタックのエネルギー密度を増加させると、ＳＯＦＣ自体コンパクトにできるために熱自立しやすくなる。しかし一方で、発電効率が低下するため、一般的には、セル電位が例えば０．７Ｖ程度の条件で所定の出力となるように設計される。したがって、この条件を全負荷運転とし、全負荷運転時に熱自立することが要求される。
【０００５】
ところで、ＳＯＦＣスタックにおいては、その燃料利用率は高々８０〜８５％程度であるので、スタックで利用されない２０〜１５％の燃料は燃焼して利用される。このため、ＳＯＦＣシステムでは、通常、ＳＯＦＣスタックとオフガス燃焼部が断熱材を配した断熱容器に収容されている。すなわち、オフガス燃焼部では燃料極からのオフガスを空気極からのオフガスで燃焼させる。燃焼ガスは、ＳＯＦＣスタックに供給する燃料及び空気の加熱に利用した後、ＳＯＦＣシステム外へ排出される。この排出燃焼ガス（燃焼排ガス）は、例えばコジェネレーションシステムにおける水蒸気発生用や給湯用に利用されるが、水蒸気や給湯の需要量にも限度がある。
【０００６】
また、電力需要家の使用用途によっては、夜間には部分負荷運転という使用条件となることから、全負荷運転時はもちろん、部分負荷運転時にも熱自立することが望ましい。部分負荷運転時には通常熱不足となり、また断熱容器からの放熱は不可避であることから、部分負荷運転時に熱不足が生じた場合には熱不足を補い、ＳＯＦＣシステムを保温する必要がある。
【０００７】
【発明が解決しようとする課題】
本発明は、ＳＯＦＣシステムにおける上記のような事情に鑑み、それらの問題点を解決するためになされたものであり、ＳＯＦＣシステムにおいて、全負荷運転時はもちろん、部分負荷運転時にも熱自立を図るようにしてなる熱自立型固体酸化物形燃料電池システムを提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明は、（１）熱自立型固体酸化物形燃料電池システムであって、断熱容器内に、固体酸化物形燃料電池スタック及びオフガス燃焼部を配置するとともに、蓄熱材層を配置することにより、全負荷運転時の燃料電池内発熱を利用して自己保温するようにしてなることを特徴とする熱自立型固体酸化物形燃料電池システムを提供する。
【０００９】
本発明は、（２）熱自立型固体酸化物形燃料電池システムであって、断熱容器内に、固体酸化物形燃料電池スタック及びオフガス燃焼部に加えて蓄熱材層を配置し、且つ、蓄熱材層に空気導入管及び空気導出管を配置するとともに、その流路に対してバイパス流路を設け、全負荷運転時には、余剰熱を蓄熱材層に蓄熱するとともに、空気をバイパス流路にバイパスさせてスタックに供給し、部分負荷運転時には、空気を蓄熱材に通して全負荷運転時に蓄熱した熱を回収してスタックに戻すようにしてなることを特徴とする熱自立型固体酸化物形燃料電池システムを提供する。
【００１０】
本発明は、（３）前記（２）の熱自立型固体酸化物形燃料電池システムにおいて、蓄熱材層の空気導出管からスタックに至る空気流路に電気ヒーターを配置し、部分負荷運転時に、空気を蓄熱材に通して全負荷運転時に蓄熱した熱を回収してスタックに戻すとともに、蓄熱材からの回収熱量だけでは熱量が不足する場合もしくは温度調節が困難である場合、電気ヒーターを付加的に利用して温度調節を行うようにしてなることを特徴とする熱自立型固体酸化物形燃料電池システムを提供する。
【００１１】
本発明は、（４）前記（２）の熱自立型固体酸化物形燃料電池システムにおいて、燃料極オフガスの一部を原燃料にリサイクルさせる流路を設け、燃料極オフガス中の水蒸気を内部改質に利用するとともに、燃料極オフガス中の未利用燃料を再利用するようにしてなることを特徴とする熱自立型固体酸化物形燃料電池システムを提供する。
【００１２】
本発明は、（５）断熱容器内に、固体酸化物形燃料電池スタック、オフガス燃焼部及び蓄熱材層を配置し、蓄熱材層に空気導入管及び導出管を配置するとともに、その流路に対してバイパス流路を設け、且つ、スタックからの燃料極オフガス導管を、順次、ＣＯ変成器及び水素吸蔵体容器に連結してなり、全負荷運転時には、余剰熱を蓄熱材層に蓄熱するとともに、空気をバイパス流路にバイパスさせてスタックに供給し、且つ、燃料極オフガスをＣＯ変成器を経て水素吸蔵体容器に通して水素を貯蔵し、部分負荷運転時には、空気を蓄熱材に通して全負荷運転時に蓄熱した熱を回収してスタックに戻すとともに、水素吸蔵体容器中の水素を燃料として発電するようにしてなることを特徴とする熱自立型固体酸化物形燃料電池システムを提供する。
【００１３】
【発明の実施の形態】
本発明は、断熱容器内に、ＳＯＦＣスタック及びオフガス燃焼部を配置してなるＳＯＦＣシステムにおいて、該断熱容器内に蓄熱材層を配置し、全負荷運転時に加え、部分負荷運転時においても電池内発熱の熱を利用して自己保温するようにしてなることを特徴とする。断熱容器に配置する断熱材としてはスラグウールやガラスウール、あるいは各種耐火物その他適宜の材料が用いられる。
【００１４】
ＳＯＦＣシステムにおける通常の全負荷運転では基本的に熱余りの状態である。そこで、本発明においては、ＳＯＦＣシステムにおいて、全負荷運転時の余剰熱を蓄熱材に吸収させて蓄熱しておき、部分負荷運転時に、蓄熱材の熱をＳＯＦＣスタックにフィードバックして利用する。
【００１５】
図１はＳＯＦＣシステムにおける全負荷運転時の熱バランスを説明する図である。図１のとおり、断熱材を配置した断熱容器内にＳＯＦＣスタックとオフガス燃焼部が収容されている。ここで、ＳＯＦＣスタックの出力が１０ｋＷのシステムの場合を例にすると、その仕様は表１のようになり、全負荷運転時の熱バランスは表２のとおりとなる。
【００１６】
熱回収後の排ガス温度は約２３０℃であり、熱バランスはＱ１＋Ｑ５＝Ｑ３＋Ｑ６＝２０ｋＷとなる。しかし、これはＱ１＋Ｑ５≦Ｑ３＋Ｑ６において、その≦のうち＝の場合であり、ＳＯＦＣスタックの全負荷運転時には、通常、熱余りの状態、すなわちＱ１＋Ｑ５＜Ｑ３＋Ｑ６となる。
【００１７】
【表１】
【表２】
一方、同じくＳＯＦＣスタックの出力が１０ｋＷのシステムを２０％の部分負荷で運転する場合、すなわち２ｋＷの発電時の熱収支は表３のとおりとなる。ここでの熱バランスはＱ１＋Ｑ５＝４．９ｋＷ＞Ｑ３＋Ｑ６＝４．４ｋＷとなる。すなわち放散熱の方が発熱量よりも大きくなり、熱バランスが崩れる。
【００２０】
【表３】
そこで、本発明においては、ＳＯＦＣシステムの全負荷運転時における余剰熱をシステム内に配置した蓄熱材層に蓄熱しておき、そして、その部分負荷運転時に当該全負荷運転時に蓄熱した熱をスタックにフィードバックするものである。システムの保温に必要な熱量の不足分は５００Ｗである。例えば昼間に１６時間全負荷運転をし、夜間に８時間程度部分負荷運転をする場合、８時間の保温で必要とされる熱量は５００×３６００×８＝１．１５×１０７Ｊとなる。
【００２２】
蓄熱材の比熱が１Ｊ／Ｋ／ｇである場合、蓄熱状態を９００℃とし、最終放熱温度を２００℃とすると、１７ｋｇの蓄熱材による蓄熱量は（９００−２００）×１７×１０３＝１．１９×１０７Ｊとなり、これにより部分負荷運転時の保温のために必要な熱量を確保することができる。蓄熱材としては、耐熱性で熱容量が大きい材料であれば特に限定はなく、その例としては、例えばセラミックス、れんが、石、コンクリート、塩化カルシウム６水塩などが挙げられる。
【００２３】
また、前述のとおり、ＳＯＦＣスタックにおいては、その燃料利用率は高々８０〜８５％程度であり、スタックで利用されない残余の燃料（２０〜１５％）は燃料極オフガスとして排出される。そこで、本発明（５）においては、蓄熱材を利用して、全負荷運転時だけでなく、部分負荷運転時においても電池内発熱（＝ＳＯＦＣシステム内発熱）の熱を利用して自己保温するのに加え、全負荷運転時に燃料極オフガス中の水素を水素吸蔵体に貯蔵しておき、この水素を部分負荷運転時の燃料として発電する。
【００２４】
水素吸蔵体としては、水素含有ガスから水素を選択的に吸蔵し、水素以外のガスは吸蔵しないか、実質上吸蔵しない材料であれば特に限定はないが、その例としては、例えば水素吸蔵合金（Ｈｙｄｒｏｇｅｎ Ｓｔｏｒａｇｅ Ａｌｌｏｙ）やカーボンナノチューブなどが挙げられる。これによって燃料極オフガス中の水素を選択的に貯蔵し、貯蔵された水素は加熱することにより放出される。水素吸蔵合金の例としては、例えばＴｉＦｅ０．９Ｍｎ０．１、Ｍｇ２Ｎｉ、ＣａＮｉＳ、ＬａＮｉ５、ＬａＮｉ４．７Ａｌ０．３、ＭｍＮｉ４．５Ａｌ０．５（Ｍｍ＝ミッシュメタル）、ＭｍＮｉ４．１５Ｆｅ０．８５（Ｍｍ＝ミッシュメタル）等を挙げることができる。
【００２５】
この態様では、断熱容器内に、ＳＯＦＣスタック、オフガス燃焼部及び蓄熱材層を配置し、蓄熱材層に空気導入管及び導出管を配置するとともに、該蓄熱材層を介する流路に対するバイパス流路を断熱容器外に設け、且つ、スタックからの燃料極オフガス導管を、順次、ＣＯ変成器及び水素吸蔵体容器に連結する。
【００２６】
そして、全負荷運転時に、余剰熱を蓄熱材層に蓄熱するとともに、空気をバイパス流路にバイパスさせてスタックに供給し、且つ、燃料極オフガスをＣＯ変成器を経て水素吸蔵体容器に通し、燃料極オフガス中の水素を貯蔵する。一方、部分負荷運転時には、空気を蓄熱材に通して全負荷運転時に蓄熱していた熱を回収してスタックに戻すとともに、水素吸蔵体容器中の水素を放出し、これを燃料として発電する。
【００２７】
【実施例】
以下、実施例を基に本発明をさらに詳しく説明するが、本発明がこれら実施例に限定されないことはもちろんである。
【００２８】
〈実施例１〉
図２は本実施例１を示す図である。断熱材を配した断熱容器内に、下部から上部へ順次ＳＯＦＣスタック、オフガス燃焼部及び蓄熱材層を配置する。そして、蓄熱材層に空気導入管及び空気導出管を配置するとともに、その空気流路に対してバイパス流路を設ける。バイパス流路は断熱容器外に配置する。また、オフガス燃焼部からの燃焼排ガスを熱源としてスタックへ導入する空気及び燃料を加熱する熱交換器を設ける。
【００２９】
オフガス燃焼部は、ＳＯＦＣスタックに連設するか、あるいはその近傍に配置する。オフガス燃焼部では燃料極オフガスを空気極オフガスで燃焼させ、その熱を蓄熱材層の蓄熱材に蓄熱する。燃焼ガスは、▲１▼蓄熱材層に直接通してもよく、▲２▼蓄熱材層に配置した管内に通してもよい。▲２▼の場合には間接熱交換になるが、間接熱交換の仕方として、管内を通すのに代えて、▲３▼オフガス燃焼部を囲むように蓄熱材層を配置して、燃焼熱をその壁面を通して蓄熱するようにしてよい。また、蓄熱材層は、ＳＯＦＣスタックとともに断熱容器に収容されているので、蓄熱材にはＳＯＦＣスタックでの発生熱も蓄熱される。
【００３０】
全負荷発電時には、上記余剰熱を蓄熱材に蓄熱し、且つ、空気をバイパス流路を経てスタックの空気極に供給する。空気は、蓄熱材層を通らず、断熱容器外に配置されたバイパス流路を通ってバイパスするので冷却効果が高められる。空気は、熱交換器で、オフガス燃焼部からの燃焼排ガスとの熱交換によってのみ予熱され、スタックの空気極に導入される。一方、部分負荷運転時には、空気を空気導入管を介して蓄熱材に供給する。空気は、蓄熱材との直接熱交換により全負荷発電時に蓄熱した熱を回収し、空気導出管を経て、さらに熱交換器で加熱され、スタックの空気極に導入される。
【００３１】
このように、断熱容器内に、ＳＯＦＣスタック及びオフガス燃焼部に加え、蓄熱材層を配置しておくことにより、全負荷運転時に余剰熱を蓄熱材に蓄熱する。そして、この熱を部分負荷運転時にシステム保温用の熱としてフィードバックする。この熱により部分負荷運転時の内部発熱不足を補うことにより、例えばその保温用に、別途、燃料を無駄に消費することなく、システムを保温することができる。
【００３２】
〈実施例２〉
図３は本実施例２を示す図である。ＳＯＦＣスタックの空気極への空気流路に電気ヒーターを設ける。他の構成は実施例１（図２）の場合と同様である。これにより、部分負荷運転時に、蓄熱材層から回収する熱量だけでは熱量が不足する場合、もしくは蓄熱材層から回収する熱量だけではシステムの温度調節が困難である場合に、付加的に電気ヒーターを利用して温度調節を行う。電気ヒーターの電源としては深夜電力等の安価な電気を利用することができる。
【００３３】
〈実施例３〉
図４〜５は本実施例３を示す図で、図４は全負荷運転時、図５は部分負荷運転時を示している。図４〜５のとおり、ＳＯＦＣスタックの燃料極からのオフガスの一部をリサイクルさせて再利用するようにする。他の構成は実施例１（図２）の場合と同様である。ＳＯＦＣスタックにおいては、例えば都市ガスを原燃料とする場合、その主成分はメタンである。メタンは通常水蒸気を添加して予備改質するか、ＳＯＦＣスタックの燃料極において水蒸気で内部改質して水素と一酸化炭素に変え、これを燃料として発電する。
【００３４】
このため、原燃料には水の添加が不可欠であるが、本実施例においては、燃料極オフガスの一部をリサイクルさせて原燃料に添加し、該オフガス中の水蒸気を内部改質に利用し、併せて該オフガス中の未利用の燃料を再利用する。図５は、全負荷運転時にバイパスさせていた空気の流れを、部分負荷運転時に徐々に蓄熱材層の方に切り替えて、蓄熱材層から全負荷運転時に蓄熱した熱を回収している状態を示している。なお、図４〜５において、実線で示す配管は流体が矢印（→）の方向に流れていることを示し、点線で示す配管は流体が流れていないことを示し、この点図６〜７においても同様である。
【００３５】
〈実施例４〉
図６〜７は蓄熱材に加えて水素吸蔵体を用いた例を示す図で、図６は全負荷運転時、図７は部分負荷運転時を示している。断熱容器内にＳＯＦＣスタック、オフガス燃焼部及び蓄熱材層を配置したシステムに、ＣＯ変成器及び水素吸蔵体容器を併置し、ＳＯＦＣスタックからの燃料極オフガスを、順次、ＣＯ変成器及び水素吸蔵体容器に通すように構成されている。空気極オフガスは、全負荷運転時に、熱交換器１に通して導入燃料及び空気の加熱源として利用する。他の構成は実施例３（図４〜５）の場合と同様である。
【００３６】
図６のとおり、全負荷運転時には、余剰熱を蓄熱材に蓄熱し、且つ、空気をバイパス流路、熱交換器１を経てスタックの空気極に供給する。そして、オフガス燃焼部は作動させず、燃料極オフガスを熱交換器１、ＣＯ変成器、熱交換器２を経て水素吸蔵体容器に導入して水素を貯蔵する。熱交換器１及び熱交換器２の熱源としては燃料極オフガスを利用する。また、空気極オフガスは、オフガス燃焼部に通して蓄熱した後、熱交換器１に通して導入燃料及び空気の加熱源として利用する。空気極オフガスは、蓄熱材層に直接通して直接熱交換により蓄熱してもよく、蓄熱材層に配置した管内に通して間接熱交換により蓄熱してよい。
【００３７】
一方、図７のとおり、部分負荷発電時には、オフガス燃焼部を作動させ、また空気を空気導入管を介して蓄熱材に供給する。ここで蓄熱材との直接熱交換により熱を回収し、空気導出管、熱交換器１を経てスタックの空気極に導入する。加えて、水素吸蔵体容器中の水素を放出し、この水素をＳＯＦＣスタックでの燃料として利用して発電する。水素の放出には、オフガス燃焼部から熱交換器１を経た燃焼排ガスの熱を利用することができる。この場合、燃焼排ガスは水素吸蔵体を間接的に加熱した後、排出される。
【００３８】
【発明の効果】
本発明によれば、ＳＯＦＣシステムにおいて、全負荷運転時に加え、部分負荷運転時にも熱自立を図ることができる。
【図面の簡単な説明】
【図１】ＳＯＦＣシステムにおける全負荷運転時の熱バランスを説明する図
【図２】実施例１を示す図
【図３】実施例２を示す図
【図４】実施例３を示す図
【図５】実施例３を示す図
【図６】実施例４を示す図
【図７】実施例４を示す図[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a self-supporting solid oxide fuel cell system, and more specifically, to a self-supporting solid oxide fuel cell system which is made to be self-supporting even during partial load operation in addition to full load operation. About.
[0002]
[Prior art]
Solid oxide fuel cells (SOFC) are operated at a high temperature of about 850 to 1000 ° C., but recently, a fuel cell operated at a lower temperature, for example, about 750 ° C., has been developed. It is getting. Conventionally, when operating an SOFC, full load operation is fundamental, and it is assumed that the SOFC is always operated. However, in reality, it is conceivable, for example, to perform full-load operation during the day and low-load operation at night.
[0003]
The SOFC is operated at a high temperature as described above, and is in an excessive heat state at the time of full load operation. However, during low-load operation, the heat dissipated to the outside is greater than the heat generated inside the battery. Even in this case, the heat becomes independent, that is, extra energy is wasted separately from the heat generated during power generation during the operation of the SOFC. It is necessary to keep the operating temperature at a predetermined temperature and keep the temperature without consuming it.
[0004]
Here, in general, in the SOFC system, when the system kale is large, the amount of heat radiated to the outside becomes small with respect to internal heat generation, so that the heat independence becomes easy. In addition, when the energy density of the SOFC stack is increased, the SOFC itself can be made compact, so that it becomes easier to stand by itself. On the other hand, however, since the power generation efficiency is reduced, the power supply is generally designed to have a predetermined output under the condition that the cell potential is, for example, about 0.7 V. Therefore, it is required that this condition be a full-load operation and that the vehicle be self-sustaining during the full-load operation.
[0005]
By the way, in the SOFC stack, the fuel utilization rate is at most about 80 to 85%, so that 20 to 15% of the fuel not used in the stack is burned and used. For this reason, in the SOFC system, the SOFC stack and the off-gas combustion unit are usually housed in a heat insulating container provided with a heat insulating material. That is, the off-gas burning section burns off-gas from the fuel electrode with off-gas from the air electrode. After the combustion gas is used for heating fuel and air supplied to the SOFC stack, it is discharged outside the SOFC system. The exhaust combustion gas (combustion exhaust gas) is used, for example, for generating steam and supplying hot water in a cogeneration system, but the demand for steam and hot water is limited.
[0006]
In addition, depending on the usage of the electric power consumer, since the usage condition is a partial load operation at night, it is desirable that the heat independence be achieved not only during the full load operation but also during the partial load operation. Since heat is usually insufficient during the partial load operation and heat radiation from the heat insulating container is inevitable, it is necessary to compensate for the insufficient heat and maintain the temperature of the SOFC system when the heat shortage occurs during the partial load operation.
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances in an SOFC system, and has been made to solve those problems. In an SOFC system, heat independence is achieved not only at full load operation but also at partial load operation. It is an object of the present invention to provide a thermally independent solid oxide fuel cell system configured as described above.
[0008]
[Means for Solving the Problems]
The present invention provides (1) a self-supporting solid oxide fuel cell system, in which a solid oxide fuel cell stack and an off-gas combustion section are arranged in a heat insulating container, and a heat storage material layer is arranged. A self-sustaining solid oxide fuel cell system characterized by self-heating by utilizing heat generated in the fuel cell during full load operation.
[0009]
The present invention relates to (2) a heat-independent solid oxide fuel cell system, in which a heat storage material layer is disposed in a heat insulating container in addition to a solid oxide fuel cell stack and an off-gas combustion section, and heat storage is performed. In addition to arranging an air introduction pipe and an air outlet pipe in the material layer, a bypass flow path is provided for the flow path, and during full load operation, excess heat is stored in the heat storage material layer and air is bypassed to the bypass flow path. The fuel is supplied to the stack, and at the time of partial load operation, air is passed through the heat storage material to recover heat stored at the time of full load operation and returned to the stack. Provide a battery system.
[0010]
According to the present invention, (3) in the thermally self-supporting solid oxide fuel cell system of the above (2), an electric heater is arranged in an air flow passage from the air outlet pipe of the heat storage material layer to the stack, and at the time of partial load operation, Pass the air through the heat storage material to recover the heat stored during full load operation and return it to the stack.If the amount of heat recovered from the heat storage material alone is insufficient or it is difficult to control the temperature, add an electric heater. The present invention provides a thermally independent solid oxide fuel cell system characterized in that temperature control is performed by utilizing the method.
[0011]
According to the present invention, (4) in the thermally self-supporting solid oxide fuel cell system of the above (2), a flow path for recycling a part of the anode off-gas into raw fuel is provided, and the steam in the anode off-gas is internally reformed. The present invention provides a thermally independent solid oxide fuel cell system characterized by utilizing unused fuel in fuel electrode off-gas while reusing the fuel.
[0012]
The present invention provides (5) arranging a solid oxide fuel cell stack, an off-gas combustion section, and a heat storage material layer in a heat insulating container, arranging an air introduction pipe and a discharge pipe in the heat storage material layer, and providing a flow path in the flow path thereof. On the other hand, a bypass flow path is provided, and the fuel electrode off-gas conduit from the stack is connected to the CO converter and the hydrogen storage vessel in order, so that during full load operation, excess heat is stored in the heat storage material layer. The air is supplied to the stack by bypassing the air to the bypass flow path, and the fuel electrode off-gas is passed through the CO converter to the hydrogen storage container to store hydrogen. During partial load operation, the air is passed through the heat storage material. A self-supporting solid oxide fuel cell system characterized in that heat stored during full load operation is recovered and returned to the stack, and power is generated using hydrogen in the hydrogen storage container as fuel. That.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to an SOFC system in which an SOFC stack and an off-gas combustion section are arranged in an insulated container, in which a heat storage material layer is arranged in the insulated container and added to the battery during full load operation and also during partial load operation. It is characterized by self-heating by utilizing the heat of heat generation. Slag wool, glass wool, various refractories, and other suitable materials are used as the heat insulating material disposed in the heat insulating container.
[0014]
In a normal full load operation in an SOFC system, basically, there is a surplus state. Therefore, in the present invention, in the SOFC system, excess heat during full load operation is absorbed by the heat storage material to store heat, and during partial load operation, the heat of the heat storage material is fed back to the SOFC stack and used.
[0015]
FIG. 1 is a diagram for explaining the heat balance at the time of full load operation in the SOFC system. As shown in FIG. 1, the SOFC stack and the off-gas combustion section are accommodated in a heat insulating container in which a heat insulating material is arranged. Here, as an example, in the case of a system in which the output of the SOFC stack is 10 kW, the specifications are as shown in Table 1, and the heat balance at the time of full load operation is as shown in Table 2.
[0016]
The exhaust gas temperature after heat recovery is about 230 ° C., and the heat balance is Q1 + Q5 = Q3 + Q6 = 20 kW. However, this is the case where Q in Q1 + Q5 ≦ Q3 + Q6, and during the full load operation of the SOFC stack, usually, the state of excess heat, ie, Q1 + Q5 <Q3 + Q6.
[0017]
[Table 1]
[Table 2]
On the other hand, when the system with the output of the SOFC stack of 10 kW is operated at the partial load of 20%, that is, the heat balance at the time of the power generation of 2 kW is as shown in Table 3. The heat balance here is Q1 + Q5 = 4.9 kW> Q3 + Q6 = 4.4 kW. That is, the dissipated heat is larger than the calorific value, and the heat balance is lost.
[0020]
[Table 3]
Therefore, in the present invention, the excess heat during the full load operation of the SOFC system is stored in the heat storage material layer arranged in the system, and the heat stored during the full load operation is stored in the stack during the partial load operation. Give feedback. The shortfall in the amount of heat required to keep the system warm is 500W. For example, when a full-load operation is performed for 16 hours in the daytime and a partial load operation is performed for about 8 hours at night, the amount of heat required for keeping heat for 8 hours is 500 × 3600 × 8 = 1.15 × 10 7 J.
[0022]
If the specific heat of the heat storage material is 1 J / K / g, the heat storage state is 900 ° C., and the final heat radiation temperature is 200 ° C., the heat storage amount of the 17 kg heat storage material is (900−200) × 17 × 10 3 = 1. .19 × 10 7 J, whereby it is possible to secure the amount of heat necessary for keeping the temperature during partial load operation. The heat storage material is not particularly limited as long as it is heat-resistant and has a large heat capacity. Examples thereof include ceramics, brick, stone, concrete, calcium chloride hexahydrate and the like.
[0023]
Further, as described above, in the SOFC stack, the fuel utilization rate is at most about 80 to 85%, and the remaining fuel (20 to 15%) not used in the stack is discharged as fuel electrode off-gas. Accordingly, in the present invention (5), the heat storage material is used to self-maintain the heat by using the heat generated in the battery (= the heat generated in the SOFC system) not only during the full load operation but also during the partial load operation. In addition, hydrogen in the fuel electrode off-gas is stored in the hydrogen storage during full load operation, and this hydrogen is used as fuel during partial load operation.
[0024]
The hydrogen storage material is not particularly limited as long as it is a material that selectively stores hydrogen from a hydrogen-containing gas and does not store or substantially does not store a gas other than hydrogen. Examples of the hydrogen storage body include a hydrogen storage alloy. (Hydrogen Storage Alloy) and carbon nanotubes. As a result, hydrogen in the anode offgas is selectively stored, and the stored hydrogen is released by heating. Examples of the hydrogen storage alloy include, for example, TiFe 0.9 Mn 0.1 , Mg 2 Ni, CaNiS, LaNi 5 , LaNi 4.7 Al 0.3 , MmNi 4.5 Al 0.5 (Mm = Misch metal) , MmNi 4.15 Fe 0.85 (Mm = Misch metal).
[0025]
In this aspect, the SOFC stack, the off-gas combustion section, and the heat storage material layer are arranged in the heat insulating container, the air introduction pipe and the discharge pipe are arranged in the heat storage material layer, and the bypass flow path to the flow path through the heat storage material layer is provided. Is provided outside the heat insulating container, and the anode off-gas conduit from the stack is sequentially connected to the CO converter and the hydrogen storage container.
[0026]
And, at the time of full load operation, while storing excess heat in the heat storage material layer, supplying air to the stack by bypassing air to the bypass flow path, and passing fuel electrode off-gas through the CO converter to the hydrogen storage container, Stores hydrogen in anode offgas. On the other hand, at the time of the partial load operation, air is passed through the heat storage material to recover the heat stored at the time of the full load operation and returned to the stack. At the same time, the hydrogen in the hydrogen storage container is released, and the hydrogen is used as fuel to generate power.
[0027]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.
[0028]
<Example 1>
FIG. 2 is a diagram illustrating the first embodiment. The SOFC stack, the off-gas combustion unit, and the heat storage material layer are sequentially arranged from the lower part to the upper part in the heat insulating container provided with the heat insulating material. Then, the air inlet pipe and the air outlet pipe are arranged in the heat storage material layer, and a bypass flow path is provided for the air flow path. The bypass flow path is arranged outside the heat insulating container. Further, a heat exchanger is provided for heating air and fuel introduced into the stack using the combustion exhaust gas from the off-gas combustion section as a heat source.
[0029]
The off-gas combustion section is connected to the SOFC stack or is disposed in the vicinity thereof. The off-gas combustion unit burns the fuel electrode off-gas with the air electrode off-gas and stores the heat in the heat storage material of the heat storage material layer. The combustion gas may be passed directly through (1) the heat storage material layer, or (2) through a pipe arranged in the heat storage material layer. In the case of (2), indirect heat exchange is performed. As a method of indirect heat exchange, instead of passing through the pipe, (3) a heat storage material layer is arranged so as to surround the off-gas combustion section, and the combustion heat is reduced. Heat may be stored through the wall. Further, since the heat storage material layer is housed in the heat insulating container together with the SOFC stack, the heat storage material also stores heat generated in the SOFC stack.
[0030]
At the time of full load power generation, the surplus heat is stored in the heat storage material, and air is supplied to the air electrode of the stack via the bypass flow path. Air does not pass through the heat storage material layer but bypasses through the bypass flow path arranged outside the heat insulating container, so that the cooling effect is enhanced. The air is preheated in the heat exchanger only by heat exchange with the flue gas from the off-gas combustion section and is introduced into the cathode of the stack. On the other hand, during the partial load operation, air is supplied to the heat storage material via the air introduction pipe. The air recovers the heat stored during full load power generation by direct heat exchange with the heat storage material, passes through the air outlet pipe, is further heated by the heat exchanger, and is introduced into the air electrode of the stack.
[0031]
In this way, by arranging the heat storage material layer in addition to the SOFC stack and the off-gas combustion section in the heat insulating container, excess heat is stored in the heat storage material during full load operation. Then, this heat is fed back as heat for keeping the system warm during the partial load operation. By supplementing the shortage of internal heat generation during the partial load operation by this heat, the system can be kept warm without wasting fuel separately, for example, for keeping the heat.
[0032]
<Example 2>
FIG. 3 is a diagram showing the second embodiment. An electric heater is provided in the air flow path to the air electrode of the SOFC stack. Other configurations are the same as those of the first embodiment (FIG. 2). In this way, during partial load operation, if the amount of heat recovered from the heat storage material layer alone is insufficient, or if it is difficult to control the temperature of the system only by the amount of heat recovered from the heat storage material layer, the electric heater can be additionally provided. Use to control the temperature. Inexpensive electricity such as midnight electricity can be used as a power source for the electric heater.
[0033]
<Example 3>
4 and 5 show the third embodiment. FIG. 4 shows a full load operation, and FIG. 5 shows a partial load operation. As shown in FIGS. 4 and 5, a part of the offgas from the fuel electrode of the SOFC stack is recycled and reused. Other configurations are the same as those of the first embodiment (FIG. 2). In a SOFC stack, for example, when city gas is used as a raw fuel, the main component is methane. Methane is usually pre-reformed by adding steam, or internally reformed with steam at the fuel electrode of the SOFC stack to convert it into hydrogen and carbon monoxide, which is used as fuel for power generation.
[0034]
For this reason, the addition of water is indispensable to the raw fuel, but in this embodiment, part of the fuel electrode off-gas is recycled and added to the raw fuel, and the steam in the off-gas is used for internal reforming. In addition, unused fuel in the off-gas is reused. FIG. 5 shows a state in which the air flow bypassed during full load operation is gradually switched to the heat storage material layer during partial load operation, and the heat stored during full load operation is recovered from the heat storage material layer. Is shown. 4 and 5, pipes shown by solid lines indicate that fluid is flowing in the direction of the arrow (→), and pipes shown by dotted lines indicate that fluid is not flowing. The same is true for
[0035]
<Example 4>
6 and 7 show examples in which a hydrogen storage material is used in addition to the heat storage material. FIG. 6 shows a full load operation, and FIG. 7 shows a partial load operation. A CO converter and a hydrogen storage container are provided in a system in which an SOFC stack, an off-gas combustion section, and a heat storage material layer are arranged in an insulated container. It is configured to pass through a container. The air electrode off-gas is used as a heating source for the introduced fuel and air through the heat exchanger 1 during full load operation. Other configurations are the same as those of the third embodiment (FIGS. 4 and 5).
[0036]
As shown in FIG. 6, during full load operation, surplus heat is stored in the heat storage material, and air is supplied to the air electrode of the stack via the bypass passage and the heat exchanger 1. Then, the off-gas combustion unit is not operated, and the fuel electrode off-gas is introduced into the hydrogen storage container via the heat exchanger 1, the CO converter, and the heat exchanger 2 to store hydrogen. A fuel electrode off-gas is used as a heat source for the heat exchangers 1 and 2. The air electrode off-gas passes through the off-gas combustion unit to store heat, and then passes through the heat exchanger 1 to be used as a heating source for the introduced fuel and air. The air electrode off-gas may pass directly through the heat storage material layer to store heat by direct heat exchange, or may pass through a tube arranged in the heat storage material layer to store heat by indirect heat exchange.
[0037]
On the other hand, as shown in FIG. 7, at the time of partial load power generation, the off-gas combustion unit is operated, and air is supplied to the heat storage material via the air introduction pipe. Here, heat is recovered by direct heat exchange with the heat storage material, and introduced into the air electrode of the stack via the air outlet pipe and the heat exchanger 1. In addition, hydrogen in the hydrogen storage container is released, and the hydrogen is used as fuel in the SOFC stack to generate power. For the release of hydrogen, the heat of the combustion exhaust gas from the off-gas combustion section through the heat exchanger 1 can be used. In this case, the combustion exhaust gas is discharged after indirectly heating the hydrogen storage body.
[0038]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, in a SOFC system, the heat independence can be aimed at at the time of partial load driving | operation in addition to the full load driving | operation.
[Brief description of the drawings]
FIG. 1 is a diagram for explaining a heat balance at the time of full load operation in an SOFC system. FIG. 2 is a diagram showing a first embodiment. FIG. 3 is a diagram showing a second embodiment. FIG. 4 is a diagram showing a third embodiment. 5 is a diagram showing a third embodiment. FIG. 6 is a diagram showing a fourth embodiment. FIG. 7 is a diagram showing a fourth embodiment.
Claims (6)
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| JP2002228036A JP4008305B2 (en) | 2002-08-05 | 2002-08-05 | Thermal self-supporting solid oxide fuel cell system |
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| JP2002228036A JP4008305B2 (en) | 2002-08-05 | 2002-08-05 | Thermal self-supporting solid oxide fuel cell system |
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| JP2004071312A true JP2004071312A (en) | 2004-03-04 |
| JP4008305B2 JP4008305B2 (en) | 2007-11-14 |
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