JP2009519195A - 酸化反応器および酸化方法 - Google Patents
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Abstract
Description
H2O+CH4⇔CO+3H2 ΔRH0 298=206kJ/mol (1)
に由来する化合物の吸熱性蒸気リフォーミングならびに前記化合物と酸素との次式
CH+1/2O→CO+2H ΔRH0 298=−36kJ/mol (2)
による少なくとも形式的に部分的な酸化での直接的な反応で製造される。
以下、BCFZと呼称される(Journal of Membrane Science, 2005, 258, 1-4)、混合伝導性膜に適した材料Ba(Co,Fe,Zr)O3-δの試験体を850℃および1バールの圧力で次の組成の合成ガス雰囲気に晒した:
酸素または酸素含有ガスが入口管を介して酸化反応器の分配空間内に導入され、
反応空間内に酸化すべきガスまたはガス混合物が導入され、
この場合反応空間内の温度は、200〜1200℃、有利に500〜1000℃、理想的には700〜900℃であり、およびさらに
圧力は、1〜200バール、有利に10〜70バール、理想的には30〜60バールである。
合成ガスの製造のために、予想すべき条件下で熱力学的に不安定な材料BCFZから次の寸法を有する中空繊維を製造した(Journal of Membrane Science, 2005, 258, 1-4):
長さ30cm、
外径約1.5mm、
肉厚約200μm。
陰影を付けた線で示された個々の膜モジュール中への空気5または別のO2供給媒体の流入、
束からのO2含量が減少された空気7の流出および
ガス流5とガス流6との間の気密な遮断に使用される。
Claims (18)
- 分配空間内または分配要素内に導入される酸素含有ガスのための供給管、反応空間内に導入される、全部または部分的に酸化すべき粗製ガスのための供給管を含み、その際反応空間内には酸素輸送に対して外側表面として入口面および出口面を有する多数の気密な酸素伝導性膜要素が配置されており、その際この出口面は、反応空間の側に配置されており、この膜要素は、分配空間と酸素含有ガスが貫流しうる捕集空間および/または出口管との空間的結合を形成し、さらに反応空間が触媒で充填可能である酸化反応器において、
1つ以上のスペーサー要素により、膜要素の外側表面と充填可能な触媒との間の定義された最少距離が保証されていることを特徴とする、酸化反応器。 - 1つ以上のスペーサー要素により、膜要素の束または群の外側表面と充填可能な触媒との間の定義された最少距離が保証されている、請求項1記載の酸化反応器。
- スペーサー要素が膜要素を個別的にかまたは束または群として包囲するか或いは膜要素を反応空間に向かって予め支承し、その際に成形体は、堆積物として存在しおよび/または個別要素、例えば外被管として形成されている、請求項1または2記載の酸化反応器。
- スペーサー要素が直接に外側の膜表面上に付着する1つ以上の不活性材料である、請求項1または2記載の酸化反応器。
- スペーサー要素が膜の出口面に対向しておよび/または接触して配置されている範囲内で反応器の規定された運転で酸化され、それによって不活性化される触媒作用を有する成形体である、請求項1から4までのいずれか1項に記載の酸化反応器。
- スペーサー要素が規則的または不規則な構造を有する、請求項1から5までのいずれか1項に記載の酸化反応器。
- スペーサー要素が1つ以上の触媒作用を有する表面を有し、理想的には反応空間に対向する表面が触媒活性材料で被覆されているかまたは触媒活性材料から形成されている、請求項1から6までのいずれか1項に記載の酸化反応器。
- 不活性の材料が充填可能な触媒の微粒子含分より小さい細孔容積または穿孔を有する、請求項1から7までのいずれか1項に記載の酸化反応器。
- 分配空間内または分配要素内に導入される酸素含有ガスのための供給管、反応空間内に導入される、全部または部分的に酸化すべき粗製ガスのための供給管を含み、その際反応空間内には酸素輸送に対して外側表面として入口面および出口面を有する多数の気密な酸素伝導性膜要素が配置されており、その際この出口面は、反応空間の側に配置されており、この膜要素は、分配空間と酸素含有ガスが貫流しうる捕集空間および/または出口管との空間的結合を形成する酸化反応器において、
反応空間内に存在する触媒の成形により膜要素の外側表面、または膜要素の群または複合体の外側表面と触媒との間の定義された最少距離が保証されていることを特徴とする、酸化反応器。 - 触媒がストランドまたは平面状要素の形を有する、請求項9記載の酸化反応器。
- 触媒が板上で少なくとも片側で接着剤または焼結により固定されている、請求項9または10記載の酸化反応器。
- 膜要素が、ペロフスカイト(ABO3)、ペロフスカイトに使用される構造、フルオライト構造(AO3)、アウリビリウス構造([Bi2O2][An-1BnOx])またはブラウンミレライト構造(A2B2O5)の群に由来する1つ以上の材料から形成されている、請求項1から11までのいずれか1項に記載の酸化反応器。
- 膜表面が、次の一般構造式:La1-x(Ca、Sr、Ba)xCo1-yFeyO3-δ、Ba(Sr)CO1-xFexO3-δ、Sr(Ba)Ti(Zr)1-x-yCoyFexO3-δ、BaCOxFexZr1-x-yO3-δ、La1-xSrxGa1-yFeyO3-δ、La0.5Sr0.5MnO3-δ、La2NixFeyO4-δ、LaFe(Ni)O3-δまたはLa0.9Sr0.1FeO3-δによって記載されることができる1つ以上の材料から形成されている、請求項1から12までのいずれか1項に記載の酸化反応器。
- 膜要素が、950℃および膜の両側上に存在する気相間の0.1バールを上廻る酸素分圧差で平均で0.1Nm3/(m2h)以上である酸素浸透率を有する、請求項1から13までのいずれか1項に記載の酸化反応器。
- 物質を酸化する方法において、
反応空間が触媒で充填されている、請求項1から14までのいずれか1項に記載の反応を使用し、
酸素または酸素含有ガスが入口管を介して酸化反応器の分配空間内に導入され、
反応空間内に酸化すべきガスまたはガス混合物が導入され、
この場合反応空間内の温度は、200〜1200℃、有利に500〜1000℃、理想的には700〜900℃であり、圧力は、1〜200バール、有利に10〜70バール、理想的には30〜60バールであることを特徴とする、物質を酸化する方法。 - 酸化すべきガスは、酸化不可能な成分も含有し、好ましくは、メタンまたは高いメタン含量を有する天然ガスである、請求項15記載の物質を酸化する方法。
- 請求項15または16記載の方法の使用において、それによって主要成分H2およびCOを有する合成ガスが製造されることを特徴とする、請求項15または16記載の方法の使用。
- 請求項15または16記載の方法の使用において、この方法を、アルカンの酸化脱水、酸化によるメタンカップリング、高級炭化水素および/または炭化水素誘導体の部分酸化またはガス混合物の個々の成分の選択的な酸化に使用することを特徴とする、請求項15または16記載の方法の使用。
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JP2012091984A (ja) * | 2010-10-28 | 2012-05-17 | Mitsubishi Heavy Ind Ltd | 高温シール材料、高温シール体、及び高温シール体を含む酸素透過モジュール |
JP2014515693A (ja) * | 2011-02-18 | 2014-07-03 | シュティヒティン・エネルギーオンデルツォイク・セントラム・ネーデルランド | 膜反応器及びこのような反応器によるガス状物体の製造の為のプロセス |
JP2019011220A (ja) * | 2017-06-30 | 2019-01-24 | 日本特殊陶業株式会社 | 改質構造体および改質装置 |
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WO2009071463A2 (de) * | 2007-12-03 | 2009-06-11 | Basf Se | Oxidative methankopplung via membranreaktor |
DE102008013292A1 (de) | 2008-03-07 | 2009-09-10 | Borsig Process Heat Exchanger Gmbh | Verfahren zum Regenerieren von Sauerstoff-leitenden keramischen Membranen sowie Reaktor |
DE102009039920A1 (de) | 2009-09-03 | 2011-03-10 | Karl-Heinz Tetzlaff | Verfahren und Vorrichtung zur Nutzung von Sauerstoff bei der Dampfreformierung von Biomasse |
DE102009060489A1 (de) | 2009-12-29 | 2011-06-30 | Uhde GmbH, 44141 | Vorrichtung und Verfahren zur Regelung der Sauerstoffpermeation durch nicht-poröse Sauerstoffanionen leitende keramische Membranen und deren Verwendung |
JP2014514073A (ja) | 2011-04-13 | 2014-06-19 | マイケル,クライン | 気体送出方法及び装置 |
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Also Published As
Publication number | Publication date |
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DK1968738T3 (da) | 2013-01-28 |
ZA200805086B (en) | 2009-03-25 |
DE102005060171A1 (de) | 2007-06-21 |
CN101394924B (zh) | 2012-07-04 |
US20090018373A1 (en) | 2009-01-15 |
ES2397966T3 (es) | 2013-03-12 |
WO2007068369A1 (de) | 2007-06-21 |
EG26485A (en) | 2013-12-10 |
CN101394924A (zh) | 2009-03-25 |
KR101376082B1 (ko) | 2014-03-19 |
EP1968738B1 (de) | 2012-10-31 |
EA200870037A1 (ru) | 2009-12-30 |
EP1968738A1 (de) | 2008-09-17 |
KR20080077667A (ko) | 2008-08-25 |
JP5366556B2 (ja) | 2013-12-11 |
CA2634263A1 (en) | 2007-06-21 |
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