JP2005525984A - 低パワーレンジにおいてガス状炭化水素から水素を生成するための高効率かつコンパクトなリフォーマ・ユニット - Google Patents
低パワーレンジにおいてガス状炭化水素から水素を生成するための高効率かつコンパクトなリフォーマ・ユニット Download PDFInfo
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Abstract
Description
(数1)
CH4 + H2O → CO + 3H2 △RH0 = 206 kJ/mol (1)
(数2)
CH4 + 2H2O → CO2 + 4H2 △RH0 = 165 kJ/mol (2)
熱は、前述の燃料ガスで作動されるバーナーを介して供給される。一酸化炭素濃度が容積で最大10%以上になるので、反応パラメータ圧力、温度、及び前記リフォーマステージの蒸気過剰ステージに応じて、更に2つの反応ステージが、一酸化炭素のレベルを低下させかつ更に水素を得る目的で、しばしば下流に接続される。これらの反応ステージはシフトコンバータとして知られている。コンバージョンは、2つの温度ステージ、即ち330℃と500℃の間の温度でFe/Cr触媒で高温シフト(HTシフト)および190℃と280℃の間の温度、Cu/Zn触媒で低温シフト(LTシフト)のステージで、発熱性の均等な水・ガス反応に従って起こる。
(数3)
CO + H2O → CO2 + H2 △RH0 = −45 kJ/mol (3)
その後、水素高含有ガス混合物は、未だ、約0.5〜1%の一酸化炭素を含んでいる。
反応器と、
出発材料を前記反応器に供給するフィードラインと、
前記出発材料フィードラインに接続されかつ該フィードラインに連結された第1チューブと、第2チューブとを備えた熱交換器と、
前記熱交換器の前記第1チューブに接続され、リフォーマスペースの回りに配置された別の熱交換器と、
前記熱交換器に接続され、かつ前記ガス状の出発材料を、触媒ユニットが内部に配列されてバーナーで加熱され得る前記リフォーマスペースに供給するための少なくとも1つの出側開口部を有するラインと、
前記リフォーマスペース内で形成された前記リフォーメイトを前記熱交換器の前記第2チューブに排出するための、他端がシフト反応器に接続された、少なくとも1つの排出ラインと、
前記シフト反応器から排出された製品ガスのための製品排出ラインと、前記反応器からの前記燃焼排ガスのための少なくとも1つの排出ラインとを備えている。
2 出発材料入口ライン
3 環状ギャップチューブ3aおよび内側チューブ3bを備えた同軸熱交換器3
4 シフト反応器
5 チューブコイル
6 リフォーミングスペース
7 バーナー
8 ガス拡散チューブ
9 パイプライン
10 自由体積
Claims (10)
- 炭化水素と水の混合物を含む出発材料から水素を生成するためのリフォーマユニットであって、
a.反応器1と、
b.出発材料を前記反応器1に供給するフィードライン2と、
c.前記出発材料フィードライン2に接続され、前記フィードライン2に連結された第1チューブ3aと、第2チューブとを備えた熱交換器3と、
d.前記熱交換器3の前記第1チューブ3aに接続され、リフォーマスペース6の回りに配置された、更に別の熱交換器5と、
e.前記熱交換器5に接続され、かつ前記ガス状の出発材料を、触媒ユニットが内部に配置されバーナー7で加熱されるようになされた前記リフォーマスペース6に供給するための少なくとも1つの出口開口部を有するライン8と、
f.前記リフォーマスペース6内で生成された前記リフォーメイトを前記熱交換器3の前記第2チューブ3bに排出する、他端がシフト反応器4に接続された、少なくとも1つの排出ライン9と、
g.前記シフト反応器4から排出された製品ガスのための製品排出ライン11と、前記反応器1からの前記燃焼排ガスのための少なくとも1つの排出ライン12と、
を備えている。 - 請求項1に記載のリフォーマユニットであって、前記出発材料フィードライン2に接続された前記熱交換器3が、第1の外側チューブ3aと第2の内側チューブ3bとを有する同軸熱交換器であることを特徴とする。
- 請求項2に記載のリフォーマユニットであって、前記出発材料フィードライン2に接続された前記同軸熱交換器3が、前記放熱流体と前記吸熱流体用のフィードとディスチャージとが加熱されるべき前記流体が前記2つの放熱流体に対して対向流となるように前記チューブ3b内を通過するように前記対応するチューブに接続された状態で、別の放熱流体を受け入れる外側チューブによって取り囲まれていることを特徴とする。
- 請求項1に記載のリフォーマユニットであって、前記出発材料フィードライン2が接続された前記熱交換器3が、対向流熱交換器であり、軸長さが同じで直径が異なり互いに嵌め合わされた2つの中空シリンダを有する中空シリンダブロックと、吸熱流体を受け入れる螺旋チューブとを備えており、前記螺旋チューブは、前記2つの中空シリンダ間の前記筒状の環状ギャップ内に配置されており、前記螺旋チューブは、前記中空シリンダの外壁または内壁にしっかりと密接しており、前記筒状シリンダ間の前記筒状環状ギャップは、環状閉塞プレートで両端部を閉鎖されており、前記螺旋チューブまたは筒状環状ギャップへ逆方向に流通する前記流体用の少なくとも1つのフィードまたはディスチャージが前記閉塞プレートに存在することを特徴とする。
- 前記請求項のうちのいずれか1に記載のリフォーマユニットであって、前記出発材料フィードライン2に接続された前記熱交換器3は、前記シフト反応器4の周囲に配置されており、該シフト反応器は好ましくは低温シフト反応器として設計されたものであることを特徴とする。
- 前記請求項のうちのいずれか1に記載のリフォーマユニットであって、前記ライン8は、前記ガス状出発材料を前記リフォーマスペース6内に供給するための複数個の出口開口部あるいは1つのギャップを有することを特徴とする。
- 前記請求項のうちのいずれか1に記載のリフォーマユニットであって、前記製品出口ライン11は、前記製品ガスを精製するための、好ましくは前記製品ガス内の前記一酸化炭素を減少させるためのユニットに接続されていることを特徴とする。
- ガス状炭化水素から水素を生成する方法であって、
炭化水素と水との混合物を含む出発材料が、予備加熱領域内に配置された熱交換器に導くフィードラインを介して反応器に供給され、この熱交換器から排出された前記加熱された出発材料ガスは、内部に触媒ユニットが配置されると共に前記触媒ユニットを加熱するためのバーナーを有するリフォーマスペースに供給され、前記リフォーマスペースから排出ラインを介して排出されたリフォーメイトはシフト反応器に供給され、該シフト反応器から排出された製品ガスは前記反応器から排出される。 - 請求項8に記載の、ガス状炭化水素から水素を生成する方法であって、
a.炭化水素ガス/水の混合物を含む前記出発材料が、先ず、熱交換器に供給され、該熱交換器は、前記反応器内の予備加熱領域内に配置され、対向流熱交換器として設計されている、
b.前記熱交換器から出る前記予備加熱された出発材料ガス混合物は、更に加熱されるために前記リフォーマ領域内に配置された前記熱交換器に供給される、
c.更に加熱されかつ前記熱交換器から排出された出発材料ガスは、内部に触媒ユニットが配置されると共に前記触媒ユニットを加熱するためのバーナーを有するリフォーマスペースに供給され、
d.排出ラインを介して前記リフォーマスペースから排出された前記リフォーマが、前記予備加熱領域内に配置された前記対向流熱交換器に供給され、該対向流熱交換器内に前記出発材料と対向する方向に供給されてシフト反応器に供給され、該シフト反応器は好ましくは低温シフト反応器として設計され、
e.前記シフト反応器から排出された前記製品ガスが、前記反応器から排出される。 - 炭化水素ガス/水の混合物を含む出発材料を予備加熱する方法であって、
前記製品ガスおよび燃焼排ガスと対向流である前記出発材料が、前記反応器内の予備加熱領域内に配置され対向流熱交換器として設計された熱交換器内を通過し、該熱交換器から触媒コンバージョンのための前記リフォーマスペースに供給される。
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PCT/DE2002/003064 WO2003024867A1 (de) | 2001-09-03 | 2002-08-22 | Kompakte reformereinheit zur wasserstofferzeugung aus gasförmigen kohlenwasserstoffen im kleinen leistungsbereich |
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DE102006019407B4 (de) * | 2006-04-23 | 2009-10-22 | Zentrum für Brennstoffzellen-Technik GmbH | Temperaturgeführter Reaktor zur Kohlenmonoxidreinigung |
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DK1425244T3 (da) | 2007-08-27 |
ES2284923T3 (es) | 2007-11-16 |
DE10142999A1 (de) | 2003-03-27 |
KR100848047B1 (ko) | 2008-07-23 |
WO2003024867A1 (de) | 2003-03-27 |
US20060188434A1 (en) | 2006-08-24 |
NO20041404L (no) | 2004-04-05 |
EP1425244A1 (de) | 2004-06-09 |
EP1425244B1 (de) | 2007-04-11 |
CA2459429A1 (en) | 2003-03-27 |
CA2459429C (en) | 2010-10-19 |
ATE359232T1 (de) | 2007-05-15 |
DE10142999B4 (de) | 2006-07-06 |
PT1425244E (pt) | 2007-07-17 |
KR20040058180A (ko) | 2004-07-03 |
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