JP5078165B2 - 水蒸気改質ユニット - Google Patents
水蒸気改質ユニット Download PDFInfo
- Publication number
- JP5078165B2 JP5078165B2 JP2008536817A JP2008536817A JP5078165B2 JP 5078165 B2 JP5078165 B2 JP 5078165B2 JP 2008536817 A JP2008536817 A JP 2008536817A JP 2008536817 A JP2008536817 A JP 2008536817A JP 5078165 B2 JP5078165 B2 JP 5078165B2
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- Prior art keywords
- combustion
- stages
- reactor
- catalyst
- reforming
- Prior art date
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- 238000000629 steam reforming Methods 0.000 title description 10
- 238000002485 combustion reaction Methods 0.000 claims description 57
- 239000003054 catalyst Substances 0.000 claims description 55
- 238000002407 reforming Methods 0.000 claims description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 239000001257 hydrogen Substances 0.000 claims description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 47
- 239000000446 fuel Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000567 combustion gas Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims 2
- 230000000149 penetrating effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 24
- 238000012546 transfer Methods 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 238000000746 purification Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000013461 design Methods 0.000 description 7
- 238000006057 reforming reaction Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 210000005069 ears Anatomy 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002303 thermal reforming Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- -1 fuel oils Chemical class 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Description
本開示は、水素生成システムに関するものであり、より具体的には、小型の水蒸気改質水素生成システムに組み込まれる小型の一体型水蒸気改質装置に関係する。
水素生成ユニット(HGU)又はシステムには、一般的に水蒸気改質方法が含まれ、その方法には、燃料−水蒸気混合物を、燃料原料の組成に応じて、主として水素(H2)、一酸化炭素(CO)、二酸化炭素(CO2)、メタン(CH4)、水蒸気(H2O)、水素(H)及びその他のガスからなる水素リッチガス混合物に転換する熱化学的プロセスの組み合わせが含まれる。製造されているこの混合物は、一般的にリフォーメート(reformate)として知られている。多くの用途において、このリフォーメートストリームは、次に水素精製ユニットに移され、該ユニットにおいて、水素の60%〜90%は、比較的純粋な水素ストリーム(99+% H2)と、リフォーメート混合物中の他の種類のオフガスストリームに分離される。
この開示は、水素生成システムに用いられる水蒸気改質システム及び方法に関する。従来の燃料オイルのような炭化水素化合物を利用する水素生成システムは、例えば、望ましくは水素を抽出するために改質システムを利用する。この改質プロセスにおいて、改質反応は吸熱性であって、反応を進めるには熱が必要であることを意味している。改質器供給物(reformer feed)は、間接的に過熱温度まで加熱され、これにより、改質器供給物が、後にリフォーメートから分離される放出水素を分解できるようにしている。燃焼熱交換器における燃料ガスの燃焼は、リフォーメート温度を要求される高温まで上げるために用いられる。その後、改質器供給物が加熱され、触媒床を通過し、よりシンプルな構成ガスに分解されるとき、改質反応が起こる。高速の熱伝達が可能である一般的な小型改質器は、マイクロチャネルと平板熱交換器に基づいており、一般的にデザインが矩形又は正方形であって、拡散接合又は溶接されたコーナー部での熱応力によって欠陥が生ずる。この開示は、新規な一体型の改質反応器に特に焦点を当てたものであり、該改質反応器は、円筒形の改質反応器モジュールを形成するように直列に積み重ねて配置された複数の改質ステージと燃焼ステージを含んでいる。各改質ステージは、リフォーメートが通過する円盤形の触媒パックに隣接する円盤形の燃焼部を有しており、リフォーメートは、ステージ間で軸線方向に方向付けられ、各ステージ内では半径方向に方向付けられ、燃焼混合物は、ステージのグループ間で半径方向に方向付けられ、各ステージ内では円周方向に方向付けられる。
水蒸気改質反応器は、改質反応を推進するために、熱エネルギーを改質触媒に添加することが必要である。改質器は、一般的に、操業温度が700℃〜900℃の範囲内であり、副産熱エネルギーが、改質反応によって要求される吸熱エネルギーに用いられると、最高の効率に達する。水素生成システムにおいて、水素精製システムからのオフガスは、この副産熱エネルギーに用いることができる。燃料電池システムでは、アノードオフガスは、この副産熱エネルギーの供給源として用いることもできる。
CH4+H2O←→CO+3H2
CH4+2H2O←→CO2+4H2
CO+H2O←→CO2+H2
(CH2)n+n(H2O)←→n(CO)+(2nH2)
(CH2)n+(2nH2O)←→n(CO2)+(3nH2)
CH4←→C+2H2
2CO←→C+CO2
(CH2)n←→(C)n+(nH2)
Claims (20)
- 水素生成システムであって:
炭化水素燃料供給部と;
水供給部と;
燃焼ガス混合部;及び
燃料供給の一部を受け入れてリフォーメートとして処理し、別途燃焼混合物を受け入れる一体型の改質反応器を含んでおり、該反応器は:
積み重ねられ連続する構成に配置された複数の改質ステージを含み、各改質ステージは、リフォーメートが通過する円盤形の触媒パックに隣接する円盤形の燃焼部を有しており、リフォーメートは、ステージ間で軸線方向に、各ステージ内では半径方向に方向付けられ、燃焼混合物は、ステージのグループ間で軸線方向に、各ステージ内では円周方向に方向付けられる水素生成システム。 - 各ステージの燃焼部は、一対の対向する円盤形のプレートを含んでおり、各プレートは、フラットな熱交換面と反対面とを有し、反対面は、反対面上に形成された複数の弓形の同心円状リブと、貫通する中心軸方向ボアとを有しており、一対の円盤形のプレートは、一対のプレートの第1側縁から一対のプレートの反対の側縁に延びて、弓形で同心円状の通路を形成するように交互に配置された同心円状のリブと嵌まり合う請求項1に記載のシステム。
- 燃焼ガスを受入及び排出するために、交互に配置されたリブの側縁と側端との間に形成されたテーパー状入口通路と、反対のテーパー状出口通路とをさらに含んでいる請求項2に記載のシステム。
- 各リブの横断面は、各弓形通路をシールするように、反対のプレート面に接触している請求項2に記載のシステム。
- 触媒パックは、2つの触媒スクリーンの間に挟まれたフラットな円盤形のダイバータプレートを含んでいる請求項1に記載のシステム。
- 各触媒パックは、ダイバータプレートを挟む一連の触媒スクリーンを有している請求項5に記載のシステム。
- 燃焼部は、燃焼部を貫通する中央ボアを有し、中央ボアを通ってリフォーメートが通過し、隣接する触媒パックに軸線方向に入る請求項5に記載のシステム。
- リフォーメートは、最初に半径方向に触媒を通って、ダイバータプレートの外縁の周囲で、中央ボアからダイバータプレートの外縁に方向付けられ、隣接するステージの別の燃焼部の中央ボアへ半径方向内側に方向付けられる請求項7に記載のシステム。
- 一体型の改質反応器は、3つのグループに配置された複数のステージを有しており、燃焼ガスは、平行なステージの各グループを通って、一続きに順に接続されたグループ間を流れる請求項1に記載のシステム。
- 一体型の改質反応器は、少なくとも12のステージを有しており、燃焼ガスをステージのグループ間に方向付けるために、ステージに取り付けられたマニホールドを含んでいる請求項9に記載のシステム。
- 水素生成システムに使用するための一体型の改質反応器であって、該反応器は、リフォーメートを受け入れ、別途燃焼混合物を受け入れるものであって、該反応器は:
積み重ねられ連続する構成に配置された複数の改質ステージを含み、各改質ステージは、円盤形の触媒パックに隣接する円盤形の燃焼部を有しており、燃焼部をリフォーメートが通過し、リフォーメートは、ステージ間で軸線方向に、各ステージ内では半径方向に方向付けられ、燃焼混合物は、ステージのグループ間で軸線方向に、各ステージ内では円周方向に方向付けられる水素生成システムに用いられる一体型改質反応器。 - 各ステージの燃焼部は、一対の対向する円盤形のプレートを含み、各プレートは、フラットな熱交換面と反対面とを有し、反対面は、反対面上に形成された複数の弓形で同心円状のリブと、貫通する中心軸方向ボアとを有しており、一対の円盤形のプレートは、一対のプレートの第1側縁から一対のプレートの反対の側縁に延び、弓形で同心円状の通路を形成するように交互に配置された同心円状のリブと嵌まり合う請求項11に記載の反応器。
- 燃焼ガスを受入及び排出するために、交互に配置されたリブの側縁と側端との間に形成されたテーパー状入口通路と、反対のテーパー状出口通路とをさらに含んでいる請求項12に記載の反応器。
- 各リブの横断面は、各弓形通路をシールするように、反対のプレート面に接触している請求項12に記載の反応器。
- 触媒パックは、2つの触媒スクリーンの間に挟まれたフラットな円盤形のダイバータプレートを含んでいる請求項11に記載の反応器。
- 各触媒パックは、ダイバータプレートを挟む一連の触媒スクリーンを有している請求項15に記載の反応器。
- 燃焼部は、燃焼部を貫通する中央ボアを有し、中央ボアをリフォーメートが通過して、隣接する触媒パックに軸線方向に入る請求項15に記載の反応器。
- リフォーメートは、最初に半径方向に触媒を通って、ダイバータプレートの外縁の周囲で、中央ボアからダイバータプレートの外縁に方向付けられ、隣接するステージの別の燃焼部の中央ボアへ半径方向内側に方向付けられる請求項17に記載の反応器。
- 一体型の改質反応器は、3つのグループに配置された複数のステージを有しており、燃焼ガスは、平行なステージの各グループを通って、一続きに順に接続されたグループ間を流れる請求項11に記載の反応器。
- 一体型の改質反応器は、少なくとも12のステージを有しており、燃焼ガスをステージのグループ間に方向付けるために、ステージに取り付けられたマニホールドを含んでいる請求項19に記載の反応器。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72763605P | 2005-10-17 | 2005-10-17 | |
| US60/727,636 | 2005-10-17 | ||
| US82948306P | 2006-10-13 | 2006-10-13 | |
| US60/829,483 | 2006-10-13 | ||
| PCT/US2006/040997 WO2007047898A1 (en) | 2005-10-17 | 2006-10-17 | Steam reforming unit |
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| US9093681B2 (en) * | 2010-12-15 | 2015-07-28 | Intelligent Energy Inc. | Hydrogen generation having CO2 removal with steam reforming |
| DK178843B1 (en) | 2014-07-16 | 2017-03-20 | Serenergy As | A reformer for a fuel cell system |
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|---|---|---|---|---|
| SE504795C2 (sv) * | 1995-07-05 | 1997-04-28 | Katator Ab | Nätbaserad förbränningskatalysator och framställning av densamma |
| US5858314A (en) * | 1996-04-12 | 1999-01-12 | Ztek Corporation | Thermally enhanced compact reformer |
| US6238815B1 (en) * | 1998-07-29 | 2001-05-29 | General Motors Corporation | Thermally integrated staged methanol reformer and method |
| JP2000323162A (ja) * | 1999-05-06 | 2000-11-24 | Honda Motor Co Ltd | 燃料改質装置 |
| US6969506B2 (en) * | 1999-08-17 | 2005-11-29 | Battelle Memorial Institute | Methods of conducting simultaneous exothermic and endothermic reactions |
| US6835354B2 (en) * | 2000-04-05 | 2004-12-28 | Hyradix, Inc. | Integrated reactor |
| AU2001267002A1 (en) * | 2000-06-19 | 2002-01-08 | Uop Llc | Apparatus for producing hydrogen |
| JP4759837B2 (ja) * | 2000-11-10 | 2011-08-31 | 株式会社デンソー | 水素供給装置 |
| JP2002201004A (ja) * | 2000-11-02 | 2002-07-16 | Toyota Motor Corp | 水素抽出装置 |
| JP2003160301A (ja) * | 2001-11-22 | 2003-06-03 | Mitsubishi Electric Corp | 改質器 |
| US6989134B2 (en) * | 2002-11-27 | 2006-01-24 | Velocys Inc. | Microchannel apparatus, methods of making microchannel apparatus, and processes of conducting unit operations |
-
2006
- 2006-10-17 US US12/090,325 patent/US8551197B2/en not_active Expired - Fee Related
- 2006-10-17 EP EP06826333.4A patent/EP1941008B1/en not_active Not-in-force
- 2006-10-17 JP JP2008536817A patent/JP5078165B2/ja not_active Expired - Fee Related
- 2006-10-17 WO PCT/US2006/040997 patent/WO2007047898A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP1941008A4 (en) | 2012-06-13 |
| EP1941008B1 (en) | 2018-05-02 |
| US20090220394A1 (en) | 2009-09-03 |
| JP2009511421A (ja) | 2009-03-19 |
| EP1941008A1 (en) | 2008-07-09 |
| US8551197B2 (en) | 2013-10-08 |
| WO2007047898A1 (en) | 2007-04-26 |
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