JP4890538B2 - 純水素発生用小型装置 - Google Patents
純水素発生用小型装置 Download PDFInfo
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- JP4890538B2 JP4890538B2 JP2008507791A JP2008507791A JP4890538B2 JP 4890538 B2 JP4890538 B2 JP 4890538B2 JP 2008507791 A JP2008507791 A JP 2008507791A JP 2008507791 A JP2008507791 A JP 2008507791A JP 4890538 B2 JP4890538 B2 JP 4890538B2
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- membrane
- hydrogen
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Description
国防総省により契約番号DAAD19-01-C-0002を受け、政府の支援で一部開示を行った。政府は、この開示において特定の権利を有する。
図2は、例示的な両面反応器サブアセンブリを説明する。
図3Aは、例示的な膜アセンブリの分解斜視図を説明する。
図3Bは、図3Aの膜アセンブリの小さくまとめた斜視図を説明する。
図4は、図3A及び3Bに示すように、二つの膜アセンブリを含む例示的な反応器サブアセンブリを説明する。
図5は、図1の反応器サブアセンブリの例示的なプレナムのない変異形を説明する。
図6は、図5の反応器サブアセンブリの例示的な支持体要素を説明する。
図7は、図5のプレナムのない反応器サブアセンブリの例示的な変異形を説明する。
図8は、図1の反応器サブアセンブリを燃焼室と統合する例示的な膜反応器を説明する。
図9は、図2の反応器サブアセンブリを燃焼室と統合する例示的な膜反応器を説明する。
図10は、図3A及び3Bに示す膜アセンブリを含む図9の膜反応器の例示的な変異形を説明する。
図11は、図3A及び3Bに示すように、幾つかの膜アセンブリを含む図8の膜反応器の例示的な変異形を説明する。
図12は、二つの室の間に内部コネクタを含む図9の膜反応器の例示的な「包まれた」変異形を説明する。
図13は、図5に示すように、二つの反応サブアセンブリを含む図12の膜反応器の例示的なプレナムのない変異形を説明する。
図14は、統合した原料ガス予熱器を具える図13のプレナムのない「包まれた」膜反応器を説明する。
図15Aは、図13の「包まれた」膜反応器の例示的なガスケットを施した変異形を説明する。
図15Bは、図15Aの例示的な「包まれた」ガスケットを施した膜反応器の小さくまとめた図を説明する。
図16は、図15A及び15Bのガスケットを施した膜反応器の断面図を説明する。
図17は、統合した水蒸発器及び原料前処理室を含む図8に示す膜反応器の例示的な変異形を説明する。
図18は、図17に示す膜反応器の断面図を説明する。
図19は、前処理室が反応室から分離していない図17及び18の膜反応器の変異形の断面図を説明する。
図20Aは、統合したガスケットを含む例示的な膜アセンブリの分解斜視図を説明する。
図20Bは、図20Aの膜アセンブリの小さくまとめた斜視図を説明する。
図21は、図20A及び図20Bに示す膜アセンブリの断面図を説明する。
図22は、管状膜要素からなる膜アセンブリを説明する。
図23は、図22の管状膜アセンブリからなる膜反応器を説明する。
図24は、アンモニア系水素発生器における図8の膜反応器の配置図を示す。
図25は、炭化水素系水素発生器における図8の膜反応器の配置図を示す。
図26は、例1に記載された図1の反応器サブアセンブリを通した水素流れ(sccm/cm2)の測定を報告する図表を示す。y軸上に水素流れを報告する。x軸上に測定の時間を報告する。
図27は、例2に記載された図1の反応器サブアセンブリの変異形を通した水素流れ(sccm/cm2)の測定を報告する図表を示す。y軸上に水素流れを報告する。x軸上に試験時間を報告する。
図28は、例3に記載された図5の反応器サブアセンブリを通した純水素生成速度(sccm)の測定を報告する図表を示す。y軸上に生成速度を報告する。x軸上に試験時間を報告する。
図29は、例5に記載された図13及び14の反応器サブアセンブリを通したアンモニアの流量の測定を報告する図表を示す。y軸上に流量を報告する。x軸上に試験時間を報告する。
図30は、例5に記載された膜リジェクト流れの熱含量を報告する図表を示す。y軸上に熱含量を報告する。x軸上に試験時間を報告する。
図31は、例6に記載された図15A、15B及び16の反応器サブアセンブリを通したアンモニア及び純水素の流量を報告する図表を示す。y軸上に流量を報告する。x軸上に試験時間を報告する。
図32は、例7に記載された図8の反応器サブアセンブリを通した水素生成速度(sccm)の測定を報告する図表を示す。y軸上に生成速度を報告する。x軸上に試験時間を報告する。
図33は、例8に記載された図8の反応器サブアセンブリを通した純水素生成速度(sccm)の測定を報告する図表である。y軸上に生成速度を報告する。x軸上に試験時間を報告する。
図34は、例9に記載された図17及び図18の反応器サブアセンブリを通した純水素生成速度(sccm)の測定を報告する図表を示す。y軸上に生成速度を報告する。x軸上に生成速度を報告する。
図35は、例10に記載された図17及び18の反応器サブアセンブリを通した純水素生成速度(sccm)の測定を報告する図表を示す。y軸上に生成速度を報告する。x軸上に生成速度を報告する。
図1に示す反応室を約450℃に加熱した後、75%H2及び25%N2の表示体積比の水素及び窒素からなる気体混合物を1500sccmの表示流量で該反応室に供給した。反応サブアセンブリは、SS304から作製された。その膜は、表示組成75%Pd/25%AgのPd/Ag箔からなり、23cm2の表面積を有した。
膜箔が、均等に間隔を開けた直径1/32"(0.079375cm)の小さな孔を含み、0.23in2 (1.483868cm 2 )の全露出表面積を有する固体SS304板上に支持されることを除けば、例1で用いたものと同一の反応器サブアセンブリを用い、例1に記載の試験を繰り返し行った。特に、水素流れ(sccm/cm2)は、600℃、5.8barの表示圧力にて、種々の温度サイクルで、同じものとみなされる二つのユニット1及び2を通り抜けた。各温度サイクルは、周囲温度と600℃の間であった。
基板は、装置の出口に水素を移送するための流路としても機能する。
反応器を約550℃に加熱した後の図13及び14に示す膜反応器に、3800sccmの表示流量で75%H2及び25%N2の表示体積比の水素及び窒素からなる気体混合物を供給した。膜反応器は、304Lステンレス鋼から作製され、相互に流体連通している二つの反応室間に挟まれた燃焼室を含んだ。各反応室は、表示組成75%Pd/25%AgのPd/Ag箔(JohnsonMatthey)からなり、55cm2の表面積を有する膜を含んだ。膜箔は、41%の表示多孔度を有する焼結多孔性SS 316基板(MottCorp)上に支持された。各反応器は、40ppiインコネル(登録商標)625金属フォーム基板を含んだ。該金属フォーム基板は、アンモニアから分解により水素を生成するのに有効である適当な触媒材料で被覆された。
例4に記載された原料を含むH2/N2からの純水素の生成を実証した後、H2/N2原料混合物を無水アンモニアに置換した。アンモニアからの純水素の生成の間、アンモニア原料、膜リジェクト及び純水素の流量は、試験時間に応じて測定された。結果を図29に報告する。
反応器を約575℃に加熱した後の図17に示す膜反応器に、500sccm〜1200sccmの流量で無水アンモニアを供給した。膜反応器は、304Lステンレス鋼から作製され、相互に流体連通している二つの反応室間に挟まれた燃焼室を含んだ。各反応室は、表示組成75%Pd/25%AgのPd/Ag箔(JohnsonMatthey)からなり、90cm2の表面積を有する膜を含んだ。膜の表示厚みは、25ミクロンであった。膜箔は、41%の表示多孔度を有する焼結多孔性316ステンレス鋼基板(MottCorp)上に支持された。各反応器は、適切な触媒で被覆した40ppiインコネル(登録商標)625金属フォーム基板を含んだ。該金属フォーム基板は、アンモニアから分解により水素を生成するのに有効である適当な触媒材料で被覆された。
0.16ml/minの表示供給速度で流れる合成灯油燃料を、0.55ml/minの表示供給速度で流れる蒸留水と接触させ、図8に示す膜反応器の前処理室に供給した。この例の前処理室は、適した触媒で被覆した40ppiFeCrAlY金属フォーム基板を含んだ。前処理室を電熱テープにより加熱し、550〜580℃、5.8barで前処理室を保持した。前処理室を用い、灯油燃料を、軽質炭化水素及び酸化炭素と共に水素を含む混合物に転化した。
例7に記載されたように、約1010hの灯油からの純水素の生成を実証した後、灯油燃料を遮断し、プロパンに置換した。行った測定の結果を図33に報告する。
0.68ml/minの表示流量で流れる水を前処理室の表皮に溶接された管材料中で蒸気に蒸発し、前処理室において0.22ml/minの表示流量で流れる合成灯油燃料と接触させた。この例の前処理室は、適当な触媒で被覆した40ppiFeCrAlY金属フォーム基板を含んだ。前処理室を燃焼室と統合し、燃焼室との熱交換により加熱した。555℃の平均温度及び5.8barで原料の予熱及び予備改質を実現した。その後、熱予備改質流れが、図17及び18に示されるような形状の膜反応器の反応室に供給された。反応器の水素膜は、25ミクロンの表示厚み及び45cm2の表面積を有する75%Pd/25%Ag箔(JohnsonMatthey)で構成された。膜箔は、41%の表示多孔度を有する焼結多孔性316ステンレス鋼基板(Mott Corp)上に支持された。反応室及び燃焼室は、それぞれ適当な触媒で被覆した40ppiFeCrAlY金属フォーム基板を含んだ。610℃の表示反応温度及び5.8barで作動しながら、図34に示されるように、460〜470sccmの表示流量で純水素を生成した。
例9の続きとして、試験中、約210hで、他の作動パラメータを変更することなく、灯油燃料をプロパンと置換した。即ち、「活性交換」時に燃料を置換したが、ここで、該活性交換とは、発生器が定常状態にあるときの水素発生燃料の置換である。目的は、燃料として灯油を用いたときに測定されたものと同じレベルで水素生成速度を維持することであった。0.8ml/minの表示流量で流す水を蒸発し、200sccmの表示流量で流すプロパンと接触させた。図35に示されるように、水素生成速度は燃料交換にもかかわらずほとんど維持されていたので、この目的は実現された。
1.0〜1.5ml/minの表示流量で流れるアルコール−水混合物(アルコール=エタノール、メタノール)を前処理室に供給した。この例の前処理室は、適当な触媒で被覆した40ppiFeCrAlY金属フォーム基板を含んだ。前処理室を燃焼室と統合し、燃焼室との熱交換により加熱した。555℃の平均温度及び5.8barで原料の予熱及び予備改質を実現した。その後、熱予備改質流れが、図17及び18に示されるような形状の膜反応器の反応室に供給された。反応器の水素膜は、25ミクロンの表示厚み及び45cm2の表面積を有する75%Pd/25%Ag箔(JohnsonMatthey)で構成された。膜箔は、41%の表示多孔度を有する焼結多孔性316ステンレス鋼基板(Mott Corp)上に支持された。反応室及び燃焼室は、それぞれ適当な触媒で被覆した40ppiFeCrAlY金属フォーム基板を含んだ。625℃の表示反応温度及び5.8barで作動しながら、表4に纏めらたように、約400sccmの表示流量で純水素を生成した。
3 膜アセンブリ
4 プレナム
6 支持体
7 穿孔
8 膜箔
10 反応器サブアセンブリ
12 フレーム
14 入口
15 分離板
16 リジェクト口
18 出口
20 反応器サブアセンブリ
22 膜
24 支持体
26 外被
28 出口
30 両面水素分離膜アセンブリ
34 プレナム
38 板
40 反応器サブアセンブリ
42 支持体
44 膜箔
46 チャンネル
48 出口
50 反応器サブアセンブリ
52 ヘッダー
55 膜アセンブリ
60 反応器サブアセンブリ
62 燃焼室
64 入口
66 出口
70 膜反応器
80 膜反応器
90 膜反応器
100 膜反応器
110 膜反応器
112 内部コネクタ
120 膜反応器
122 巻き金属管材料
130 膜反応器
132 ガスケット
140 膜反応器
142 前処理室
143 接続管材料
146 入口
147 入口
148 出口
150 プレナム
152 プレナム
154 支持体
156 膜箔
158 ガスケット
162 フレーム
164 出口
166 穿孔
180 膜アセンブリ
181 閉端空洞
182 管状膜部材
183 開口部
184 外被
186 収集区域
188 出口
190 膜反応器
192 プレナム
194 金属管材料
196 前処理部分,改質器室
198 口
200 反応器サブアセンブリ
202 反応室
203 空気供給
204 燃料供給
205 反応燃料供給ライン
206 空気供給ライン
207 燃焼燃料供給
208 燃焼副生成物ライン
209 排ガス供給ライン
211 燃焼供給ライン
213 水供給ライン
Claims (11)
- 水素分離膜を含む反応器であって、前記反応器は、分離板のそれぞれの側面に配置された、一方の室が反応室を画定し、他方の室が燃焼室を画定する二つの室をさらに有し、前記燃焼室は、前記反応室と流体連通し且つ熱交換関係にある、反応器と、
前記分離板と反対側の燃焼室を閉じるための末端板と、
前記分離板と反対側の反応室を閉じる膜アセンブリと、
前記膜アセンブリの他の側面に位置し、水素収集用プレナムを提供する水素排気室と、
前記燃焼室と熱交換関係にあり、前記反応室と流体連通する原料前処理室と、
燃料供給と、
前記燃料供給から前記原料前処理室に燃料を移送するための反応燃料供給ラインと、
前記前処理室から前記反応室に処理した燃料を移送するための原料供給ラインと、
空気供給と、
前記空気供給から前記燃焼室に酸素を移送するための空気供給ラインと、
前記燃料供給から前記燃焼室に燃料を移送するための燃焼燃料供給ラインと、
前記反応室から排ガスを移送するための排ガス供給ラインと、
前記燃焼室から燃焼副生成物を移送するための燃焼副生成物ラインと、
前記反応室から水素を移送するための反応生成物ラインと、
を具え、
前記原料前処理室が、前記分離板と反対側にある燃焼室の側面に配置され、前記燃焼室の末端板と接触し、
前記原料前処理室が底板を具え、前記底板の外面が蒸気発生器として機能する巻き金属管材料を含む、水素発生器。 - 前記原料前処理室が前記燃焼室と反対側の前記底板を用いて閉じられ、
前記反応燃料供給ラインが前記原料前処理室に燃料を移送するためのものであり、前記原料供給ラインが前記原料前処理室から前記反応室に燃料を移送するためのものであり、前記燃焼燃料ラインが前記燃焼室に燃料を移送するためのものであり、前記排ガス供給ラインが前記反応室から排ガスを移送するためのものであり、前記反応生成物ラインが前記水素排気室から水素を移送するためのものである請求項1に記載の水素発生器。 - 前記原料前処理室が、オーステナイト鋼及びインコネル600シリーズよりなる群から選択される材料で構成される請求項1に記載の水素発生器。
- 前記原料前処理室が、触媒被覆多孔性金属基板を含む請求項1に記載の水素発生器。
- 前記原料前処理室に位置する触媒被覆基板が、前記反応室に位置する触媒と同一である請求項4に記載の水素発生器。
- 前記原料前処理室に位置する触媒被覆基板が、前記反応室に位置する触媒と異なる請求項4に記載の水素発生器。
- 前記巻き金属管材料が前記底板に直接溶接される請求項1に記載の水素発生器。
- 前記巻き金属管材料が、第一に、該管材料を受容するため前記底板に用意されたくぼみに配置され、次いで該底板に溶接される請求項1に記載の水素発生器。
- 水素分離膜を含む反応器であって、分離板及び該分離板のそれぞれの側面に配置された二つの室を具え、一方の室が多孔性金属基板に被覆した反応触媒を含む反応室を画定し、他方の室が多孔性金属基板に被覆した燃焼触媒を含む燃焼室を画定する反応器と、
前記分離板と反対側の燃焼室を閉じるための末端板と、
一方の側の前記燃焼室と他方の側の底板とにより括られ、多孔性金属基板に被覆した反応触媒を含み、該底板が水蒸気への水の蒸発を促進するために外面に巻き金属管材料を含む前処理室と、
膜及び膜支持体サブアセンブリを含み、前記分離板と反対側の反応室を閉じるための膜アセンブリであって、前記支持体サブアセンブリと接触していない膜表面が前記触媒基板に近い位置にあるが、該触媒基板から分離している膜アセンブリと、
前記膜アセンブリの他の側面に位置し、水素収集用プレナムを提供する水素プレナムと、
を具える水素発生器。 - 前記膜支持体サブアセンブリが、孔あき金属板に連接された焼結多孔性金属を具え、
前記支持体サブアセンブリの第一表面が、前記膜の第一表面と接触し、
前記支持体サブアセンブリの第二表面が、前記水素プレナムに連接され、
前記膜の第二表面が、ガスケットと接触して前記反応室と前記膜との間にシールを形成し、該ガスケットが圧縮され、前記膜アセンブリと前記反応室との間に漏れ止めシールを形成して反応サブアセンブリを形成し、前記燃焼室が該反応サブアセンブリに連接される請求項9に記載の水素発生器。 - 前記支持体サブアセンブリと接触していない膜表面が、セラミックマット及び保持フレームを用い、前記触媒基板から分離している請求項9に記載の水素発生器。
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Also Published As
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WO2006113680A3 (en) | 2007-11-29 |
KR20080012876A (ko) | 2008-02-12 |
US20060233700A1 (en) | 2006-10-19 |
KR100929351B1 (ko) | 2009-12-03 |
JP2008536796A (ja) | 2008-09-11 |
EP1877335A4 (en) | 2011-06-29 |
EP2578532A1 (en) | 2013-04-10 |
EP1877335A2 (en) | 2008-01-16 |
WO2006113680A2 (en) | 2006-10-26 |
US7527661B2 (en) | 2009-05-05 |
JP2011168488A (ja) | 2011-09-01 |
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LAPS | Cancellation because of no payment of annual fees |