JP2009507755A - 水素発生装置およびその使用方法 - Google Patents
水素発生装置およびその使用方法 Download PDFInfo
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Abstract
Description
本発明は、米国陸軍研究所との契約(契約番号:DAAD19−01−C0015)の下でなされたものであり、米国政府は本発明に一定の権利を有する。
(化1)
2NH3 → N2+2H2
(化2)
CnH(2n+2) → Cn(solid)+(n+1)H2
(化3)
CnH(2n+2)+nO2 → nCO2+(n+1)H2
水蒸気改質は、以下の化学式4で表すことができる。
(化4)
CnH(2n+2)+2nH2O → nCO2+(3n+1)H2
11 メタン化装置
12 水素膜反応器
13a 反応室
13b 燃焼室
14 燃料供給源
15 前改質室
16 酸素供給源
17 メタン化装置ライン
18 水素貯蔵容器
19 貯水槽
20 燃料供給ライン
21 第2燃料供給ライン
22 酸素供給ライン
23 排ガス供給ライン
24 燃焼副生成物ライン
26 反応生成物ライン
28 燃料熱交換器
29 予備燃料供給ライン
30 酸素熱交換器
31 燃料電池
32 頂板
34 底板
36 分離板
37a、37b 対向面
38 水素分離膜
39a、39b 対向面
40 水素排気領域
41 反応領域
42 断熱板
46 断熱板
48 断熱板
50 燃焼チャネル
52 シート
54 第2燃料供給源
55 水供給源
56 シート
58 反応チャネル
59 シート
55 予備燃料供給源
68 第1流体入口
70 第2流体入口
72 第2流体出口
76 中間チャネル
78 空気噴射ポンプ
80 吸着剤供給源
81 吸着剤供給源
82 蓄電池
100 水素発生装置
120 燃料供給ライン
124 燃焼副生成物ライン
125 前処理室
140 タンク
142 タンク
144 ポンプ
148 回収水ライン
149 回収水貯蔵容器
191 水供給ライン
200〜204 弁
210 酸素センサ
281 シェル
282 チャネル
283 チャネル
Claims (54)
- 燃焼室と反応室とを有し、前記燃焼室が前記反応室と流体接続すると共に熱交換関係にあり、前記反応室が反応領域と水素排気領域とを有する、水素膜反応器と、
少なくとも一つの燃料供給源と、
前記燃料供給源から前記反応室へと燃料を移送するための燃料供給ラインと、
酸素供給源と、
前記酸素供給源から前記燃焼室へと酸素を移送するための酸素供給ラインと、
前記燃料供給源から前記燃焼室へと燃料を移送するための第2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、
前記燃焼室が該燃焼室を通る流体通路を形成する複数の燃焼チャネルを備え、
前記反応領域が該反応領域を通る流体通路を形成する複数の反応チャネルを備え、
前記水素排気領域が該水素排気領域を通る流体通路を形成する複数の水素排気チャネルを備えることを特徴とする水素発生装置。 - 第1燃料供給源と、第2燃料供給源と、前記第1燃料供給源から前記反応室へと第1燃料を移送するための第1燃料供給ラインと、前記第2燃料供給源から前記燃焼室へと第2燃料を移送するための第2燃料供給ラインとを更に具える請求項1に記載の水素発生装置。
- 前記第1燃料と前記第2燃料とが同一である請求項2に記載の水素発生装置。
- 前記第2燃料供給ラインが前記酸素供給ラインと流体接続している請求項2に記載の水素発生装置。
- 前記排ガス供給ラインが前記反応室から前記燃焼室へと排ガスを移送し、前記第2燃料供給源が前記排ガス供給ラインと流体接続している請求項2に記載の水素発生装置。
- 前記水素膜反応器が頂板と、底板と、分離板とを具え、
前記分離板が第1対向面と第2対向面とを有し、
前記頂板と前記分離板の第1面とが一緒に前記反応室を画成し、
前記底板と前記分離板の第2面とが一緒に前記燃焼室を画成し、
第1対向面と第2対向面とを有する水素分離膜を前記頂板と前記底板との間に配置し、
前記頂板と前記水素分離膜の前記第1面とが一緒に水素排気領域を画成し、
前記分離板と前記水素分離膜の前記第2面とが一緒に反応領域を画成し、
前記第1燃料供給ラインが燃料を前記反応領域に移送し、前記第2燃料供給ラインが前記燃焼室と流体接続し、前記排ガス供給ラインが前記反応領域から前記燃焼室へと排ガスを移送する請求項1に記載の水素発生装置。 - 前記燃焼室の複数の燃焼チャネルが前記分離板の前記第2面又は前記底板から放射状に延在し、前記反応室の複数の反応チャネルが前記分離板の前記第1面から放射状に延在して前記反応領域を通る流体通路を形成し、および/または前記複数の水素排気チャネルが前記頂板から放射状に延在する請求項6に記載の水素発生装置。
- 前記燃料供給ラインおよび前記反応生成物ラインに操作可能に接続された燃料熱交換器と、前記酸素供給ラインおよび前記燃焼副生成物ラインに操作可能に接続された酸素熱交換器とを更に具える請求項1に記載の水素発生装置。
- 前記燃料がアンモニアであり、更に前記反応生成物ラインおよび前記燃焼副生成物ラインに流体接続したアンモニア吸着剤供給源を具える請求項1に記載の水素発生装置。
- 燃焼室と反応室とを有し、前記燃焼室が前記反応室と流体接続すると共に熱交換関係にある水素膜反応器を具え、
前記燃焼室は第1触媒の塗布基板を有し、
前記第1触媒の塗布基板が細孔を有し、金属の発泡体、モノリス若しくはメッシュ又はセラミックの発泡体またはモノリスの形状をしており、
前記反応室は第2触媒の塗布基板を有し、
前記第2触媒の塗布基板が細孔を有し、金属の発泡体、モノリス若しくはメッシュ又はセラミックの発泡体またはモノリスの形状をしていることを特徴とする水素発生装置。 - 前記第1触媒の塗布基板および前記第2触媒の塗布基板のうち少なくとも一つが、約0.2〜約3.0mmの範囲にある近似細孔直径または基板の流れ大きさを有する請求項10に記載の水素発生装置。
- 近似細孔直径または基板の流れ大きさが約0.5〜約2.0mmの範囲にある請求項10に記載の水素発生装置。
- 前記燃焼室内の触媒塗布基板が始動化合物を有し、該始動化合物が始動シーケンス中に燃料の着火を容易にする請求項10に記載の水素発生装置。
- 頂板と、底板と、分離板とを具え、前記分離板が第1対向面と第2対向面とを有する水素膜反応器であって、
前記頂板と前記分離板の第1面とが一緒に反応室を画成し、第1対向面と第2対向面とを有する水素分離膜を前記頂板と前記底板との間に配置し、前記頂板と前記水素分離膜の前記第1面とが一緒に水素排気領域を画成し、前記分離板と前記水素分離膜の前記第2面とが一緒に反応領域を画成し、
前記底板と前記分離板の第2面とが一緒に燃焼室および燃焼領域を画成し、
前記燃焼領域、前記反応領域、および前記排気領域のうち少なくとも一つが、該領域を通る流体通路を形成する燃焼触媒塗布の多孔質基板を内蔵することを特徴とする水素膜反応器。 - 前記基板が前記領域の表面と接触している請求項14に記載の水素膜反応器。
- 前記燃焼領域、前記反応領域および前記排気領域のうち少なくとも一つが複数のチャネルを具え、前記燃焼チャネルが該領域を通る流体通路を形成する請求項14に記載の水素膜反応器。
- 前記燃焼室内の燃焼領域が、前記分離板の前記第2面または前記底板から放射状に延在する複数の燃焼チャネルを備え、該燃焼チャネルが前記燃焼室を通る流体通路を形成する請求項14に記載の水素膜反応器。
- 前記反応領域が、前記分離板の前記第1面から放射状に延在して前記反応領域を通る流体通路を形成する複数の反応チャネルを備える請求項14に記載の水素膜反応器。
- 前記水素排気領域が、前記頂板から放射状に延在して前記水素排気領域を通る流体通路を形成する複数の水素排気チャネルを備える請求項14に記載の水素膜反応器。
- 燃焼室と反応室とを有し、前記燃焼室が前記反応室と流体接続すると共に熱交換関係にある水素膜反応器と、
燃料供給源と、
前記燃料供給源から前記水素膜反応器へと燃料を移送するための少なくとも一つの燃料供給ラインと、
前記水素膜反応器および前記燃料供給ラインと流体接続した前処理室とを具え、
前記燃料供給ラインからの燃料が、前記水素膜反応器に供給される前に前記前処理室で水素含有ガス混合物へと前改質されることを特徴とする水素発生装置。 - 前記前処理室が前記燃料供給ラインの高温領域により構成され、該高温領域に適当な触媒を組み込んで前記水素膜反応器へ供給すべき水素含有ガス混合物を生成する請求項20に記載の水素発生装置。
- 前記燃料供給ラインが前記燃料を前記水素膜反応器の前記反応室へ移送する請求項21に記載の水素発生装置。
- 前記燃料供給ラインが前記燃料を前記水素膜反応器の前記燃焼室へ移送する請求項21に記載の水素発生装置。
- 前記前処理室が、前記水素膜反応器と熱交換関係にあると共に流体接続した前改質室により構成され、該前改質室に適当な触媒を組み込んで前記水素膜反応器へ供給すべき水素含有ガス混合物を生成する請求項20に記載の水素発生装置。
- 前記前改質室が、前記水素膜反応器の反応室と熱交換関係にあると共に流体接続している請求項24に記載の水素発生装置。
- 前記前改質室が、前記反応室の入口に位置した膜無し部分を構成する請求項25に記載の水素発生装置。
- 前記前改質室が、前記水素膜反応器の反応室を介して前記燃焼室と熱交換関係にあると共に流体接続している請求項24に記載の水素発生装置。
- 燃焼室と反応室とを有し、前記燃焼室が前記反応室と流体接続すると共に熱交換関係にあり、前記反応室が反応領域と水素排気領域とを有する水素膜反応器と、
燃料を有する少なくとも一つの燃料供給源と、
前記燃料供給源から前記反応室へと燃料を移送するための燃料供給ラインと、
酸素供給源と、
前記酸素供給源から前記燃焼室へと酸素を移送するための酸素供給ラインと、
前記燃料供給源から前記燃焼室へと燃料を移送するための第2燃料供給ラインと、
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、
前記燃料供給ラインおよび反応排ガスラインに操作可能に接続した燃料熱交換器と、
前記酸素供給ラインおよび燃焼副生成物ラインに操作可能に接続した酸素熱交換器とを具え、
前記燃料熱交換器および前記酸素熱交換器のうち少なくとも一つが該交換器を通る通路を形成する多孔質基板を備えることを特徴とする水素発生装置。 - 前記燃料熱交換器および前記酸素熱交換器のうち少なくとも一つが、向流式の、多管式または積層板式熱交換器である請求項28に記載の水素発生装置。
- 燃焼室と反応室とを有し、前記燃焼室が前記反応室と流体接続すると共に熱交換関係にある水素膜反応器と、
炭化水素燃料を有する燃料供給源と、
前記燃料供給源から前記反応室へと前記炭化水素燃料を移送するための燃料供給ラインと、
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、
水供給源と、
前記水素膜反応器へ水を移送するための水供給ラインとを具え、
前記水供給ラインが前記水素膜反応器と熱交換関係にあると共に流体接続していることを特徴とする水素発生装置。 - 前記炭化水素燃料および水を水素膜反応器へと供給するための少なくとも一つのポンプを更に備える請求項30に記載の水素発生装置。
- 前記水供給ラインが前記水素膜反応器の反応室と熱交換関係にあると共に流体接続している請求項30に記載の水素発生装置。
- 前記水供給ラインが前記水素膜反応器と熱交換関係にある請求項30に記載の水素発生装置。
- 前記水が、前記反応室に供給する前記炭化水素燃料と接触する前に蒸気に気化される請求項30に記載の水素発生装置。
- 前記水素発生装置は、前記反応室および/または前記燃焼室用の水素含有ガス混合物を生成するための適当な触媒を含有する前処理室を更に備え、
予熱した水蒸気を前記炭化水素燃料供給源からの前記炭化水素燃料と前記前処理室の内側で接触する請求項30に記載の水素発生装置。 - 燃焼副生成物が水を有し、該水を前記燃焼副生成物ラインで凝縮し、前記水供給源に再循環する請求項30に記載の水素発生装置。
- 前記排ガス供給源が水を有し、該水を前記排ガスが前記燃焼室に送られる前に前記排ガスライン内で凝縮し、該凝縮した水を前記水供給源に再循環する請求項30に記載の水素発生装置。
- 燃焼室と反応室とを有し、前記燃焼室が前記反応室と流体接続すると共に熱交換関係にある水素膜反応器と、
燃料供給源と、
前記燃料供給源から前記水素膜反応器へと燃料を移送するための少なくとも一つの燃料供給ラインと、
予備燃料供給源とを具え、
前記予備燃料供給源が、水素発生装置の始動シーケンス中に前記燃焼室と流体接続することを特徴とする水素発生装置。 - 前記予備燃料が水素である請求項38に記載の水素発生装置。
- 前記燃料供給ラインが燃料を前記燃焼室へ移送し、前記燃料供給ラインが前記予備燃料供給源と流体接続している請求項38に記載の水素発生装置。
- 前記予備燃料を前記予備燃料供給源から前記燃焼室へと移送するための予備燃料供給ラインを更に備える請求項38に記載の水素発生装置。
- 前記予備燃料が水素であり、該水素が金属水素化物に圧縮、貯蔵され、
前記圧縮が特に水素化物および前記水素発生装置からの熱を用いて行われる請求項38に記載の水素発生装置。 - 燃焼室と反応室とを有し、前記燃焼室が前記反応室と流体接続すると共に熱交換関係にある水素膜反応器と、
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、
前記反応生成物ラインと流体接続したメタン化装置とを具えることを特徴とする水素発生装置。 - 前記メタン化装置が約200℃の温度に曝されるように前記反応生成物ラインに配置される請求項43に記載の水素発生装置。
- 水素膜反応器で水素を発生する方法であって、
前記水素膜反応器が燃焼室と反応室とを有し、前記燃焼室が前記反応室と流体接続すると共に熱交換関係にあり、
前記燃焼室が燃焼触媒着火温度を有する燃焼触媒を含有し、
前記反応室が該反応室内に反応領域および排気領域を画成する分離膜を備え、
前記反応領域が反応触媒を有し、該反応触媒は反応触媒着火温度を有し、
前記燃焼触媒着火温度が前記反応触媒着火温度より低く、
前記方法が、
a)予備燃料を前記燃焼室へ前記燃焼触媒着火温度で流し、前記予備燃料を燃焼して第一燃焼生成物ガスを発生する工程と、
b)前記燃焼触媒の温度が前記燃焼触媒着火温度にほぼ達した時点で、前記燃焼室に流した予備燃料を可燃性燃料と置き換え、そして前記反応触媒の温度が前記反応触媒着火温度に達するように燃焼を継続し、前記可燃性燃料の燃焼が第二燃焼副生成物ガスを発生する工程と、
c)水素生成燃料を前記反応領域に流して前記反応触媒と前記反応触媒着火温度で接触させ、水素ガスおよび反応排ガスを有する反応領域水素ガス混合物を生成する工程と、
d)前記水素ガスを前記反応領域水素ガス混合物から前記水素分離膜を介して分離し、該水素ガスを前記反応室の前記排気領域に蓄積する工程と、
e)前記水素ガスを前記反応室の前記排気領域から収集する工程と、
を備えることを特徴とする水素発生方法。 - 前記水素ガスがCOおよび/またはCO2を含有し、
前記反応室の前記排気領域から前記水素ガスを収集する工程が、
e1)前記水素ガスをメタン化触媒を有するメタン化装置に流してCOおよび/またはCO2をCH4へと変換する工程を備える請求項45に記載の方法。 - 前記水素生成燃料を前記反応領域に流す工程が、
c1)前記水素生成燃料を、適当な触媒を有する前処理室内で反応触媒と接触させて前処理室水素含有ガス混合物を生成する工程と、
c2)生成した前処理室水素含有ガス混合物を前記反応領域へ流す工程とを備える請求項45に記載の方法。 - 前記水素生成燃料が炭化水素燃料であり、
前記水素生成燃料を前記反応領域に流す工程が、前記炭化水素燃料を前記反応領域で水と接触させて水素ガスおよび排ガスを生成する工程を備え、
前記水素ガスおよび前記反応排ガスが水蒸気を含有する請求項45に記載の方法。 - 前記水素生成燃料が炭化水素燃料であり、
前記水素生成燃料を前記反応領域に流す工程が、
c3)前記炭化水素燃料を、適当な触媒を有する前処理室内で水と接触させて前処理室水素含有ガス混合物を生成する工程と、
c4)生成した前処理室水素含有ガス混合物を前記反応領域へ流す工程とを備え、
前記前処理室水素含有ガス混合物および前記反応排ガスが水蒸気を含有する請求項48に記載の方法。 - f)前記反応排ガス中の水蒸気を冷却および減圧により凝縮して凝縮水と排ガスとを得る工程と、
g)前記生成した排ガスを燃焼室へ送る工程と、
h)前記凝縮水を再循環する工程とを更に具える請求項48または請求項49に記載の方法。 - 前記水を前記炭化水素燃料のほぼ沸点まで予熱する請求項48または請求項49に記載の方法。
- 前記可燃性燃料が炭化水素燃料であり、前記燃焼反応を水の存在下で行い、前記第2燃焼副生成物ガスが水蒸気を含有する請求項45に記載の方法。
- j)前記燃焼副生成物ガスに存在する水を前記燃焼室への流入空気との熱交換により凝縮する工程と、
k)前記水を水供給源へ再循環する工程と、
l)冷却された燃焼室生成物ガスを大気中に放出する工程とを更に備える請求項52に記載の方法。 - 前記膜を介した水素分離が、真空ポンプまたは凝縮性不活性ガスを用いた前記水素排気領域中の水素分圧の減圧により改善される請求項45に記載の方法。
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Also Published As
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WO2008024089A2 (en) | 2008-02-28 |
EP1917329A2 (en) | 2008-05-07 |
JP4762314B2 (ja) | 2011-08-31 |
WO2008024089A3 (en) | 2009-03-12 |
EP1917329A4 (en) | 2011-08-03 |
US20050281735A1 (en) | 2005-12-22 |
US7922781B2 (en) | 2011-04-12 |
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