JP4267325B2 - アンモニアベース水素発生装置および同装置の使用方法 - Google Patents
アンモニアベース水素発生装置および同装置の使用方法 Download PDFInfo
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- JP4267325B2 JP4267325B2 JP2002570274A JP2002570274A JP4267325B2 JP 4267325 B2 JP4267325 B2 JP 4267325B2 JP 2002570274 A JP2002570274 A JP 2002570274A JP 2002570274 A JP2002570274 A JP 2002570274A JP 4267325 B2 JP4267325 B2 JP 4267325B2
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- ammonia
- reactor
- combustion
- hydrogen
- hydrogen generator
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims description 447
- 229910021529 ammonia Inorganic materials 0.000 title claims description 221
- 239000001257 hydrogen Substances 0.000 title claims description 168
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 168
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 164
- 238000000034 method Methods 0.000 title claims description 20
- 239000003463 adsorbent Substances 0.000 claims description 112
- 238000002485 combustion reaction Methods 0.000 claims description 112
- 238000006243 chemical reaction Methods 0.000 claims description 90
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- 239000000446 fuel Substances 0.000 claims description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 239000001273 butane Substances 0.000 claims description 47
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 47
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 47
- 239000012530 fluid Substances 0.000 claims description 43
- 239000007795 chemical reaction product Substances 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 20
- 238000000354 decomposition reaction Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
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- 238000013461 design Methods 0.000 description 8
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
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- 229910052719 titanium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- 229910001026 inconel Inorganic materials 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Description
本発明に基づき、燃料電池や他のアプリケーションに使用する小型のアンモニアベース水素発生装置が見出された。この水素発生装置は、比較的低温、好ましくは約550℃から650℃、より好ましくは約550℃から580℃で運転するが、それでいて残存アンモニアを除去するために使用する吸着剤は有意な量であることを必要としない。さらに、好適な実施形態では、水素発生装置は充填層反応装置を必要としない。
本発明の原理と運転を例証する目的で、以下に本発明の具体的な実施形態を詳細に説明する。しかしながら、多様な修正を加えることができ、本発明の範囲は、以下に説明する典型的な実施形態に限定されるものではない。
Claims (43)
- アンモニア供給装置と、
燃焼室と熱交換関係にある反応室を含む熱触媒式水素発生反応装置と、
アンモニアをアンモニア供給装置から反応室に送るアンモニア供給ラインと、
反応室から水素を送り出す反応生成物供給ラインと、
燃焼室に可燃流動体を送る燃焼流動体供給ラインと、
燃焼室から燃焼副生成物を送り出す燃焼副生成物排気ラインと、
反応装置に運転可能に接続された熱源と、を含む、
アンモニアベース水素発生装置であって、
水素発生反応装置が、上板、底板、および上板と底板との間に配置された反応装置中心部を含み、
反応装置中心部が反応面と燃焼面とを有し、各面が対向する端部と対向する側部とを画定する一段高くなった外縁を有し、そして反応装置中心部が、反応面から外側に延びて離隔した第1のセットのフィンと、燃焼面から外側に延びて離隔した第2のセットのフィンとを有し、第1のセットのフィンは第1の複数の燃焼導管を画定し、第2のセットのフィンは第2の複数の反応導管を画定し、各セットの導管が、一つの対向する側部からもう一つの対向する側部に向かい、且つ対向する端部から離隔したガス流路を形成し、
反応面と上板とが一緒になって反応室を画定し、燃焼面と底板とが一緒になって燃焼室を画定する水素発生装置。 - 少なくとも一つのセットのフィンが、厚さ0.5mm、高さ2mm、および長さ50mmであり、隣接するフィンの間隔が1mmである、請求項1記載の水素発生装置。
- 少なくとも一つのセットの導管で形成される流路が一直線である、請求項1記載の水素発生装置。
- 少なくとも一つのセットの導管で形成される流路がジグザグである、請求項1記載の水素発生装置。
- 反応装置が非耐熱金属で製造される、請求項1記載の水素発生装置。
- 非耐熱金属がチタンまたはステンレス鋼である、請求項5記載の水素発生装置。
- 反応室を着火温度600℃未満のアンモニア分解触媒で装填する、請求項1記載の水素発生装置。
- 触媒を反応導管に充填する、請求項7記載の水素発生装置。
- 触媒を反応室の流通導管の内部表面に被覆する、請求項7記載の水素発生装置。
- アンモニア分解触媒がルテニウムを含む、請求項7記載の水素発生装置。
- アンモニア分解触媒がニッケルを含む、請求項7記載の水素発生装置。
- アンモニア供給ラインおよび反応生成物供給ラインの少なくとも一つが、第1の対向する端部から反応装置中心部に入り、第2のセットのフィンと平行に、反応装置の対向する端部の直前にある反応装置中心部の末端にまで伸び、他のラインが第1の対向する端部で末端となる、請求項1記載の水素発生装置。
- 反応生成物ラインの外側に位置する反応生成物ラインの少なくとも一部をアンモニア供給ラインの外側に同軸上に配置する、請求項1記載の水素発生装置。
- 第1のセットのフィンの第2の端部と燃焼流動体ラインの末端との間にある燃焼室に配置された燃焼触媒をさらに含む、請求項1記載の水素発生装置。
- 燃焼触媒がプラチナ燃焼触媒である、請求項14記載の水素発生装置。
- 熱源がアンモニア供給装置に流動的に接続されたアンモニア燃焼器である、請求項1記載の水素発生装置。
- アンモニア供給装置がアンモニアをアンモニア燃焼室に供給する、請求項1記載の水素発生装置。
- 熱源が炭化水素燃焼器である、請求項1記載の水素発生装置。
- 燃焼流動体ラインが第1の対向する端部から反応装置中心部に入り、第1のセットのフィンと平行に、反応装置の対向する端部の直前にある反応装置中心部の末端にまで伸びる、請求項1記載の水素発生装置。
- 炭化水素供給装置がブタン供給装置である、請求項1記載の水素発生装置。
- 水素から残存アンモニアを除去するために反応生成物供給ラインに接続された第1の吸着剤供給装置をさらに含む、請求項1記載の水素発生装置。
- アンモニア供給ラインが熱伝導性金属で製造され、吸着剤供給装置を通る、請求項1記載の水素発生装置。
- 吸着剤が酸含浸炭素吸着剤である、請求項1記載の水素発生装置。
- 吸着剤が炭素1グラムあたり2ミリモルから5ミリモルの強酸性吸着サイトを有する、請求項23記載の水素発生装置。
- 水素から残存アンモニアを除去するために反応生成物供給ラインに接続された第2の吸着剤供給装置と、アンモニアを選択的に、アンモニア供給装置から第1または第2のいずれかの吸着剤供給装置に導入する第1のバルブと、反応生成物を選択的に、第1または第2のいずれかの吸着剤供給装置に導入する第2のバルブと、をさらに含む、請求項21記載の水素発生装置。
- 燃焼副生物排気ラインおよびアンモニア供給ラインに運転可能に接続された熱交換器をさらに含む、請求項1記載の水素発生装置。
- 熱交換器を、反応装置と吸着剤供給装置との間の燃焼副生成物排気ラインに配置する、請求項26記載の水素発生装置。
- 反応生成物供給ラインに流動的に接続された燃料電池をさらに含む、請求項1記載の水素発生装置。
- アンモニアベース水素発生装置であって、
アンモニア供給装置と、
上板、底板、および上板と底板との間に配置された反応装置中心部を含む熱触媒式水素発生反応装置と、を含み、
反応装置中心部は反応面と燃焼面とを有し、各面が対向する端部と対向する側部とを画定する一段高くなった外縁を有し、そして反応装置中心部が、反応面から外側に延びて離隔した第1のセットのフィンと、燃焼面から外側に延びて離隔した第2のセットのフィンとを有し、第1のセットのフィンは第1の複数の燃焼導管を画定し、第2のセットのフィンは第2の複数の反応導管を画定し、各セットの導管が、一つの対向する側部からもう一つの対向する側部に向かい、且つ対向する端部から離隔したガス流路を形成し、
反応面と上板とが一緒になって反応室を画定し、燃焼面と底板とが一緒になって燃焼室を画定し、
反応室に装填される着火点が600℃未満のアンモニア分解触媒と、
第1のセットのフィンの第2の端部と燃焼流動体ラインの末端の間の燃焼室に配置されたプラチナ燃焼触媒と、
アンモニアをアンモニア供給装置から反応室に送るアンモニア供給ラインと、
反応室から水素を送り出す反応生成物供給ラインと、
燃焼室へ可燃流動体を送る燃焼流動体ラインと、
燃焼室から燃焼副生成物を送り出す燃焼副生成物排気ラインと、
反応装置に接続された炭化水素燃焼器と、
水素から残存アンモニアを除去するために反応生成物供給ラインに接続され、熱伝導性材料で製造されたアンモニア供給ラインが吸着剤供給装置を通過する、炭素1グラムあたり2ミリモルから5ミリモルの強酸性吸着サイトを有する酸含浸炭素吸着剤供給装置と、
反応装置と吸着剤供給装置との間に配置されて、アンモニア供給ラインに接続される燃焼副生成物排気ラインに運転可能に接続された熱交換器と、
反応生成物供給ラインに流動的に接続された燃料電池と、
を含む水素発生装置。 - 少なくとも一つのセットの導管で形成された流路が一直線である、請求項29記載の水素発生装置。
- 少なくとも一つのセットの導管で形成された流路がジグザグである、請求項29記載の水素発生装置。
- 触媒を反応導管に充填する、請求項29記載の水素発生装置。
- 触媒を反応室の流通導管の内部表面に被覆する、請求項29記載の水素発生装置。
- アンモニア分解触媒がルテニウムを含む、請求項29記載の水素発生装置。
- アンモニア分解触媒がニッケルを含む、請求項29記載の水素発生装置。
- アンモニア供給ラインおよび反応生物物ラインの少なくとも一つが、第1の対向する端部から反応装置中心部に入り、第2のセットのフィンと平行に、反応装置の対向する端部の直前にある反応装置中心部の末端にまで伸び、他のラインが第1の対向する端部で末端となる、請求項29記載の水素発生装置。
- 燃焼流動体ラインが、第1の対向する端部から反応装置中心部に入り、第1のセットのフィンと平行に、反応装置の対向する端部の直前にある反応装置中心部の末端にまで伸びる、請求項29記載の水素発生装置。
- 水素発生方法であって、
上板、底板、および上板と底板との間に配置された反応装置中心部を含む、熱触媒式水素発生反応装置の反応室にアンモニアを導入することを含み、
反応装置中心部は反応面と燃焼面とを有し、各面が対向する端部と対向する側部とを画定する一段高くなった外縁を有し、そして反応装置中心部が、反応面から外側に延びて離隔した第1のセットのフィンと、燃焼面から外側に延びて離隔した第2のセットのフィンとを有し、第1のセットのフィンは第1の複数の燃焼導管を画定し、第2のセットのフィンは第2の複数の反応導管を画定し、各セットの導管が、一つの対向する側部からもう一つの対向する側部に向かい、且つ対向する端部から離隔したガス流路を形成し、
反応面と上板とが一緒になって反応室を画定し、燃焼面と底板とが一緒になって燃焼室を形成し、
反応装置に熱を与えることと、
アンモニアが水素と窒素を含む反応生成物に分解されるまでの十分な時間に渡って、反応装置のアンモニアを550℃から650℃まで加熱することと、
反応装置から反応生成物を取り出すことと、
を含む方法。 - さらに、アンモニアを反応装置に導入する前に、アンモニアを予熱する、請求項38記載の方法。
- 反応装置に熱を供給するためにアンモニアを燃焼する、請求項38記載の方法。
- 反応装置に熱を供給するために炭化水素を燃焼する、請求項38記載の方法。
- 反応装置に熱を供給するためにブタンを燃焼する、請求項38記載の方法。
- 反応生成物が残存アンモニアを含み、残存アンモニアを反応生成物を吸着剤供給装置に通すことによって除去する、請求項38記載の方法。
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Publication number | Publication date |
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WO2002071451A2 (en) | 2002-09-12 |
KR100868392B1 (ko) | 2008-11-11 |
EP1372839A2 (en) | 2004-01-02 |
KR20040012729A (ko) | 2004-02-11 |
CN1239244C (zh) | 2006-02-01 |
WO2002071451A3 (en) | 2002-10-24 |
CN1507369A (zh) | 2004-06-23 |
US7875089B2 (en) | 2011-01-25 |
JP2009007245A (ja) | 2009-01-15 |
JP2004525058A (ja) | 2004-08-19 |
EP1372839A4 (en) | 2006-11-29 |
US20040154223A1 (en) | 2004-08-12 |
JP5068707B2 (ja) | 2012-11-07 |
CA2439586A1 (en) | 2002-09-12 |
JP2012162457A (ja) | 2012-08-30 |
MXPA03007886A (es) | 2004-10-15 |
CA2439586C (en) | 2012-02-28 |
AU2002335499A1 (en) | 2002-09-19 |
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