201000201 六、發明說明： 【發明所屬之技術領域】 本發明係有關用以使氧傳導性陶瓷膜再生之方法，該 氧傳導性陶瓷膜可用於藉由氧陰離子-傳導性陶瓷膜自氣 體混合物除去氧之方法，且係有關用於自氣體混合物除去 氧或用於進行氧化反應之改良反應器。 【先前技術】 已知可用於自氣體混合物除去多種氣體的不可滲透的 無孔性膜。例如’ P d膜可用於選擇性地除去氫，或適合 的陶瓷膜以獲得氧。 無孔性膜的子群爲混合傳導性膜的子群，該混合傳導 性膜係由具有同時傳導氧陰離子和電子的能力之陶瓷材料 所組成。這些提供自氣體混合物（例如空氣）除去氧之方 法。 該基本槪念爲使用陶瓷膜以分離兩個具有不同氧分壓 的氣體空間之系統。操作時，氧係根據下式於較高氧分壓 側（供入側）上的陶瓷膜處離子化 〇2 + 4e· + 202- ( 1 ) 且經由該陶瓷材料晶體構造中的晶格缺陷位置轉移至 較低氧分壓側（滲透側）。在該滲透側上，氧接著再根據 下式釋放 -5- 201000201 202· 〇2 + 4e 有關於該滲透側釋放至該反應室中的各個〇2分子， 釋放出4 e·的電荷，該〇2分子係運送至與該氧陰離子流 動方向相反的供入側。在混合傳導性陶瓷膜的情況中，經 由該陶瓷膜材料本身內的電子傳導以平衡電荷。 不用混合傳導性材料，陰離子-傳導性和電子傳導性 材料所組成的複合材料亦爲習知，其中藉由具有能傳導氧 陰離子的陶瓷材料之緊密混合物中的電子傳導性第二相平 衡電荷。同樣習知爲純氧陰離子傳導體（例如經釔-安定 化的二氧化锆），其中於氧滲透時藉由外部電路平衡電荷 〇 根據本發明所用的陶瓷膜原則上爲無孔性，但是也可 能由於限制（例如製程中的）而有少許洩漏。然而，重要 的是該物質分離的主要作用源於待除去的氣體與該無孔性 膜材料之間的交互作用。 在此說明內文中，據瞭解無孔性膜意指不可滲透膜， 其中於1 b ar的壓差下流過該膜剩餘細孔構造的氣體量小 於3 0 %，較佳小於5 %藉由離子傳導在操作條件下滲透的 氣體量。 上述用於除去氧的膜爲陶瓷材料，其具有於提高溫度 下傳導氧陰離子的能力。工業相關的氧滲透率至今經常在 高於80(TC的溫度時才能達到。 此類型的材料可，例如，源於下列群組：鈣鈦礦（ -6- 201000201 A B〇3 )或鈣鈦礦-相關的構造、螢石構造（a〇2 )、奧里 維里斯（aurivillius)構造（[Βίιί^ΠΑηΒηΟχ]或錦鐵銘 石構造（A 2 B 2 Ο 5 )。文獻中所述的系統作爲氧傳導性材料 或材料種類之典型實例爲LauCCaJi^BahCch.yFeyOy、 Ba(Sr)Co 卜 xFex03-S、Sr(Ba)Ti(Zr)i-x-y、Co 卜 yFex03.s、 L a 1.x S rχG a I.y F e y Ο 3.δ ' L a 〇 . 5 S r〇. 5 Μ η Ο 3. g、L a F e (N i) Ο 3 - δ、 L a〇 . 9 S r 〇. 1 F e Ο 3 - δ 或 B aC o x F e y Zr 卜x-y Ο 3 - δ。 （ A. Thursfield, I. S. Metcalfe, Journal of Material Science 2004, 14，275- 2485 ; Y. Teraoka, H. Zhang, S. Furukawa, N. Yamazoe， Chemistry Letters 1 985, 1 743 - 1 746 ； Y. Teraoka, T.201000201 VI. Description of the Invention: [Technical Field] The present invention relates to a method for regenerating an oxygen conductive ceramic membrane which can be used for removal from a gas mixture by an oxyanion-conductive ceramic membrane The method of oxygen, and is directed to an improved reactor for removing oxygen from a gas mixture or for performing an oxidation reaction. [Prior Art] An impermeable, nonporous film which can be used to remove a plurality of gases from a gas mixture is known. For example, the 'Pd film can be used to selectively remove hydrogen, or a suitable ceramic film to obtain oxygen. The sub-group of non-porous membranes is a sub-group of mixed conductive membranes composed of ceramic materials having the ability to simultaneously conduct oxygen anions and electrons. These provide a means of removing oxygen from a gas mixture, such as air. The basic commemoration is the use of a ceramic membrane to separate two gas spaces having different oxygen partial pressures. In operation, the oxygen ionizes 〇2 + 4e· + 202- ( 1 ) at the ceramic film on the higher oxygen partial pressure side (supply side) according to the following formula and the lattice defect in the crystal structure of the ceramic material The position is shifted to the lower oxygen partial pressure side (permeate side). On the permeate side, oxygen then releases -5 - 201000201 202 · 〇 2 + 4e according to the following formula, and the respective 〇 2 molecules released into the reaction chamber on the permeate side release a charge of 4 e· The 2 molecular system is transported to the supply side opposite to the flow direction of the oxyanion. In the case of a mixed conductive ceramic film, electrons within the ceramic film material itself are conducted to balance the charge. It is also known to use a composite of an anion-conducting and an electron-conducting material without mixing a conductive material, wherein the charge is balanced by an electron-conducting second phase in an intimate mixture of ceramic materials capable of conducting oxygen anions. It is also known as a pure oxygen anion conductor (for example, yttrium-stabilized zirconium dioxide) in which the charge is balanced by an external circuit during oxygen permeation. The ceramic membrane used according to the invention is in principle non-porous, but also There may be a slight leak due to restrictions (such as in the process). However, it is important that the primary action of the separation of the material results from the interaction between the gas to be removed and the non-porous membrane material. In the description herein, it is understood that the non-porous film means an impermeable film in which the amount of gas flowing through the remaining pore structure of the film under a pressure difference of 1 b ar is less than 30%, preferably less than 5% by ion. Conducting the amount of gas that permeates under operating conditions. The above membrane for removing oxygen is a ceramic material having an ability to conduct oxygen anions at an elevated temperature. Industry-related oxygen permeability has so far been achieved at temperatures above 80 (TC). This type of material can, for example, originate from the following groups: perovskites (-6-201000201 AB〇3) or perovskites - related structures, fluorite structure (a〇2), orivilillius structure ([Βίιί^ΠΑηΒηΟχ] or Jintie Mingshi structure (A 2 B 2 Ο 5 ). The system described in the literature Typical examples of oxygen conductive materials or material types are LauCCaJi^BahCch.yFeyOy, Ba(Sr)Co BuxFex03-S, Sr(Ba)Ti(Zr)ixy, Co Bu yFex03.s, L a 1.x S rχG a Iy F ey Ο 3.δ ' L a 〇. 5 S r〇. 5 Μ η Ο 3. g, L a F e (N i) Ο 3 - δ, L a〇. 9 S r 〇. 1 F e Ο 3 - δ or B aC ox F ey Zr xy Ο 3 - δ. ( A. Thursfield, IS Metcalfe, Journal of Material Science 2004, 14,275-2485; Y. Teraoka, H. Zhang, S. Furukawa , N. Yamazoe, Chemistry Letters 1 985, 1 743 - 1 746 ; Y. Teraoka, T.
Nobunaga, K. Okamoto, N. Miura, N. Yasmazoe, Solid State Ionics 1991，48, 207-2 1 2 ； J. Tong, W. Yang, B.Nobunaga, K. Okamoto, N. Miura, N. Yasmazoe, Solid State Ionics 1991, 48, 207-2 1 2 ; J. Tong, W. Yang, B.
Zhu, R. Cai, Journal of Membrane Science 2002, 203, 1 75 -189)。 和該膜的組成一樣，氧滲透率顯然取決於操作條件（ T. Schiestel, M. Kilgus, S. Peter, K.J. Caspary, H. Wang, J. Caro, Journal of Membrane Science 2005，25 8，1-4)。 在本文中特別重要的是溫度，其對於氧的滲透率一般 具有線性至指數的影響。 此膜經常被述及的應用爲經由烴類的部分氧化獲得合 成氣，例如，如同WO 2007/068369 A1所述。 其他可能的應用在於，例如，獲得富含氧的空氣，例 如，如同DE 10 2005 006 571 A1中所述；烴類或烴衍生 物的氧化性脫氫；甲烷的氧化性耦合；或獲得供發電廠應 201000201 用用的氧（對此主題，參照H. Wang, Y. Cong, X. Zhu, W. Yang, React. Kinet. Catal. Lett. 2003, 79, 3 5 1 -3 5 6 ； X. Tan, K. Li, Ind. Eng. Chem. Res. 2006, 45，1 42- 1 49 ； R. Bredesen, K. Jordal，〇. Bolland，Chemical Engineering and Processing 2004, 43，1 1 2 9- 1 1 5 8 )。 當此用於獲得氧的膜係用於化學反應器時，習慣使用 藉由包含氧陰離子-傳導性陶瓷膜（1 )區分爲至少兩個室 的反應器。氧-供應氣體或氣體混合物（3 ) (例如空氣 )最初係塡在該陶瓷膜的供入側（=基材室） （2 )， 且可氧化介質（5 )係塡在該滲透側（=滲透室） （4 ) 。操作時，來自較高氧分壓該側的氧滲透穿過該陶瓷膜（ 1 )且與存在於相反側的可氧化介質（5 )反應而得到氧化 產物（6 )。自該供入側除去氧耗盡的氣體（7 )。第1圖 槪略顯示此本質上習知的程序。 因爲氧在該滲透側不斷消耗，所以滲透側的氧分壓比 供入側的氧分壓低。因此該供入側可使用具有相當低壓的 空氣，而明顯提高的溫度同時存在於滲透側。供入側的壓 力下限爲供入側的氧分壓必須比滲透側的氧分壓高。 此等陶瓷膜系統因此可作爲既定的低溫空氣分離之不 貴的替代物。 然而，由於經常需要的的陶瓷膜的高操作溫度，僅一 些化學結構非常簡單的化合物至今仍適合作爲可氧化的介 質。經常地，這些爲C,或c2烴類。 當更複雜的分子（如芳族、脂族、筒級脂族或不飽和 -8- 201000201 脂族化合物’例如苯、甲苯、二甲苯、乙苯、乙烷、乙烯 、乙炔、丙烷、丙烯、丁烷、丁烯或13-丁二烯）係用於 此具有慣用操作溫度800 °C或更高的陶瓷膜系統之反應器 中時，這些分子將有顯著的熱分解。結果爲可達到的產物 選擇性和可達到的產率降低相當多，及提高的焦炭形成量 ’結果商業上對此等應用經常不太感興趣。 在自氣體混合物除去氧以獲得氧的情況中，亦期盼在 低於目前慣用的溫度下進行。 因此極力要求往較低操作溫度方向擴張操作陶瓷膜的 溫度範圍。 從根本期盼降低操作溫度至今無法完成，因爲該陶瓷 膜的氧滲透性在較低溫下一定的時間之後將變差且操作將 不再能經濟地實施。 頃意外地發現氧陰離子-傳導性陶瓷膜可經由暫時提 高溫度而再生，且這使得該膜的初始氧滲透性能重新被建 立。 因此提供氧除去可藉由陶瓷膜在低於800°C相當多的 溫度，例如在400至600°C的範圍，下穩定操作之方法。 【發明內容】 本發明係有關用於使能傳導氧陰離子的陶瓷之膜的氧 滲透性再生之方法。此方法包含在操作階段之後對該膜進 行至少一個再生階段，其中該膜的溫度係提高至高於該操 作階段所選擇之溫度達到該膜的氧滲透性再度提高之程度 -9- 201000201 在此說明內文中，據瞭解陶瓷膜意指基本上非金屬之 結晶性爲主的膜，其係經由燒結法製造。 該膜的氧滲透性再生的結果爲操作時已經降低之膜的 氧滲透性再度提高。此方法較佳用以重建在操作和再生階 段的周期開始時存在之膜的氧滲透性之至少90%，且尤其 是至少9 5 %，且最佳爲1 0 0 %。 更佳地，此方法，在經過數個操作和再生階段的周期 之過程中，使該膜的氧滲透性維持在各個和每次周期開始 時存在原先存在的氧滲透性之至少9 5 %。 在根據本發明的方法之較佳變體中，該再生階段中的 膜溫度爲爲比該膜在操作階段中的溫度高至少50°C，較佳 高至少1 0 0 °C。 在根據本發明的方法之另一個較佳變體中，在該操作 階段中該膜的溫度爲在4 0 0與6 0 0 °C之間。 根據本發明的方法較佳爲用於分離設備中除去氧’該 分離設備具有藉由包含能傳導氧陰離子的陶瓷之膜區分爲 至少一個基材室和至少一個滲透室的內部，該分離方法包 含下列步驟： a ) 壓縮且加熱包含氧的氣體及/或至少一種釋放氧 的化合物以得到供入氣體， b ) 將該經壓縮且加熱的供入氣體加入該分離設備 的基材室， c ) 任意地將洗淨氣體加入該分離設備的滲透室， -10- 201000201 d ) 在該基材室及/或該滲透室中建立使該基材室及 該滲透室中的氧分壓能透過能傳導氧陰離子的陶瓷將氧運 送至該滲透室之壓力， e) 自該基材室除去氧耗盡的供入氣體， f ) 自該滲透室除去富含氧的洗淨氣體或氧， g ) 該分離設備的操作包含多個被至少一個再生階 段所中斷的分離階段， h ) 在該等分離階段時該膜的溫度爲低於8 00 °C，及 i ) 在該再生階段時該膜的溫度爲比在該操作階段時 該膜的溫度高至少5 (TC，較佳高至少1 0 0°C。 所述的氧除去可爲該基材室中的氧含量之消耗，在該 情況中氧可源於包含氧的氣體及/或釋放氧的化合物。這 使該滲透室中富含氧。 該分離方法可以數個變體操作。在一個變體中，該基 材室中使用供入氣體，且該滲透室中使用洗淨氣體，操作 時該滲透室中富含氧且自該滲透室除去。在另一個變體中 ，該基材室中使用供入氣體，而沒有洗淨氣體被供應至該 滲透室且在該滲透室中收集純氧，操作時自該滲透室除去 純氧。 根據本發明的方法較佳亦係用於膜反應器中進行氧化 反應的方法，該膜反應器具有藉由包含能傳導氧陰離子的 陶瓷之膜區分爲至少一個基材室和至少一個滲透室的內部 ，且該方法包含下列步驟： a) 壓縮且加熱包含氧及/或至少一種釋放氧的化合 -11 - 201000201 物的氣體以得到供入氣體， b ) 將該經壓縮且加熱的供入氣體加入該膜反應器 的基材室， c’） 將包含至少一種反應物的洗淨氣體加入該膜反 應器的滲透室， d') 在該基材室及/或該滲透室中建立使該基材室及 該滲透室中的氧分壓能透過能傳導氧陰離子的陶瓷將氧運 送至該滲透室及使該至少一種反應物至少部分氧化之壓力 e) 自該基材室除去氧耗盡的供入氣體， Γ ) 自該滲透室除去該包含至少一種經部分氧化的 反應物之洗淨氣體， g') 該膜反應器的操作包含數個被至少一個再生階 段所中斷的反應階段， h’） 在該等反應階段時該膜的溫度爲低於8 00°C，及 i ) 在該再生階段時該膜的溫度爲比在該反應階段時 該膜的溫度高至少5 0 °C，較佳高至少1 〇 〇 °C。 【實施方式】 在本說明內文中，據瞭解"使該至少一種反應物至少 部分氧化”意指使至少一部分加入該滲透室的反應物與氧 反應。 所用的供入氣體可爲任何包含氧的氣體及/或釋放氧 的化合物。這些較佳額外包含氮且更特別的是不包含任何 -12- 201000201 可氧化的成分。 釋放氧的成分之實例爲水蒸氣、氮氧化物（如N Ox 或N20、碳氧化物（如co2或CO )及硫氧化物（如S〇x )，其中 X = 1-3 。 特佳的是使用空氣作爲供入氣體。該供入氣體的氧含 量經常爲至少5體積％，較佳至少1 〇體積％，更佳1 〇_30 體積％。 所用的洗淨氣體可爲任何氣體，附帶條件爲彼等使該 膜中能維持氧分壓梯度。在根據本發明的方法之一個變體 中，使用包含氧和氮的氣體（例如空氣）。在根據本發明 的方法之另一個變體中，使用包含可氧化的成分（任意地 結合氧和氮）之氣體。 該洗淨氣體可包含惰性及/或可氧化的成分（如水蒸 氣或二氧化碳）’及飽和及/或不飽和的脂族及/或芳族及/ 或芳脂族烴類。特佳爲使用烴類作爲洗淨氣體。 在根據本發明的方法中，可使用任何能傳導氧陰離子 且對於氧具有選擇性的陶瓷膜。 膜的形態可如所願。彼等可，例如，以平坦形態或呈 陶瓷中空纖維的形態存在。 該膜較佳以陶瓷中空纖維的形態存在，其具有至少 1 〇的長對直徑比。這些中空纖維尤其係以複合材料的形 態使用，如w Ο 2 0 0 6 / 8 1 9 5 9 A 1所述。 能運送氧陰離子且依據本發明使用的陶瓷類本身爲習 知。 -13- 201000201 這些陶瓷類可由能同時傳導氧陰離子和電子的材料（ =混合傳導性材料）構成。然而’其也可使用不同陶瓷 類或陶瓷與非陶瓷材料的組合。其實例爲氧陰離子-傳導 性陶瓷類與電子-傳導性非陶瓷材料（如金屬）之組合， 或各自傳導氧陰離子和電子或所有成分並非均具有氧傳_ 作用的不同陶瓷類之組合。 多相膜系統的實例爲具有離子傳導性的陶瓷與具有β 子傳導性的另一種材料，尤其是金屬，之混合物。這些包 括尤其是具有螢石構造或螢石相關構造的材料與電子傳_ 性材料的組合，例如Zr02或Ce02 (其係任意地摻雜Ca〇 或Y2〇3 )與金屬（如鈀）的組合。 多相膜系統另外的實例爲具有部分鈣鈦礦構造的混合 構造（即，各種不同晶體結構均以固態存在的混合系統） ’且該等混合構造之至少一者爲鈣鈦礦構造或鈣鈦礦相關 構造。 所用的氧-運送材料較佳爲混合傳導性氧化物陶瓷類 ，其中特佳爲具有鈣鈦礦構造或具有鈣鐵鋁石構造或具有 奧里維里斯構造者。 依據本發明使用的鈣鈦礦經常具有AB03.s構造，其 中A代表二價陽離子且B代表三價或更高價陽離子，A 的離子半徑大於B的離子半徑，且δ爲在0.001與1.5之 間’較佳在0 _ 0 1與〇 _ 9之間，且更佳在〇 . 〇 1與〇 _ 5之間 的數字’以’以建立該材料的電中性。在依據本發明所用 的鈣欽礦中’也可存在不同陽離子Α及/或陽離子Β的混 -14- 201000201 合物。 依據本發明所用的鈣鐵鋁石經常具有a2b2〇5_s構造， 其中A、B和δ各自如上所述。在依據本發明所用的鈣鐵 鋁石中同樣地，可存在不同陽離子Α及/或陽離子Β的混 合物。 陽離子B較佳可分數種氧化態發生。然而，一些或甚 至所有B型陽離子也可爲具有固定氧化態的三價或更高價 陽離子。 特佳的氧化物陶瓷含有A型陽離子，其係選自第二 主族陽離子、第一過渡族陽離子、第二過渡族陽離子、鑭 系元素陽離子，或這些陽離子的混合物，較佳爲選自 Mg2+、Ca2+、Sr2+、Ba2+、Cu2+、Ag2+、Zn2+、Cd2 +及 / 或 鑭族陽離子。 特佳的氧化物陶瓷含有B型陽離子，其係選自週期表 ΙΙΙΒ至VIIIB族的陽離子及/或鑭族陽離子、第三至五主 族金屬的陽離子或這些陽離子的混合物，較佳爲選自Fe3 + 、Fe4+、Ti3+、Ti4+、Zr3+、Zr4+、Ce3+、Ce4+、Mn3+、 Mn4+、Co2+、Co3+ ' Nd3+、Nd4+、Gd3+、Gd4+、Sm3+、 Sm4+、Dy3+、Dy4+、Ga3+、Yb3+、Al3+ ' Bi4+或這些陽離 子的混合物。 又更佳的氧化物陶瓷含有B型陽離子，其係選自 Sn2+、Pb2+、Ni2+、Pd2+、鑭系元素或這些陽離子的混合 物。 依據本發明所用的奧里維里斯經常具有（Bi202 ) 24 -15- 201000201 (vo3.5[]Q.5) 2 —構造要素或相關的構造要素，其中□意指 氧缺陷位置。 特佳的膜由BaCoxFeyZrz〇3.s構成，其中X、y及z可 各自獨立地假設爲在〇_〇1至0·9，較佳爲0.1至0.8的範 圍內之數値，且X、y及z的總和爲丨，且δ爲在0.001與 1 · 5之間的數字’以建立該材料的電中性。極佳的膜爲此 型的膜，其中X爲0.1至0.6，y爲0.2至0.8且ζ爲0.】 至 0.4。 該基材室中的供入氣體之壓力可變化於廣大範圍內。 個別情況中的壓力係選擇使得該膜供入側的氧分壓係大於 該滲透室。該基材室中的典型壓力變化於1〇_2與1〇〇 bar 之間，較佳在1與80 bar之間且尤其是在2與10 bar之 間的範圍。該滲透室中的氣體壓力同樣可變化於廣大範圍 內且係依根據上文所指定的標準之個別情況建立。該滲透 室中的典型壓力變化於1(Γ3與100 bar之間，較佳在0.5 與80 bar之間且尤其是在0.8與20 bar之間的範圍。 根據本發明的方法之特徵爲將該設備的操作區分爲數 個分離或反應階段，該數個分離或反應階段被一或多個再 生階段所中斷。在該等分離或反應階段期間，該設備完成 其預期的目的，而該膜的分離能力係於再生階段時重建。 根據本發明的方法之額外的特徵爲比起該等分離或反 應階段該膜係於再生階段時加熱至提高的溫度。 經常地，該膜的溫度在該等再生階段時高於6 5 0 °C ’ 較佳高於7 5 (TC且更佳高於8 5 0 °C。 -16- 201000201 該分離設備或該膜反應器中的溫度係在各 熟於此藝之士選擇使得該分離或反應階段時可 物的最大分離效能及/或最大產量和選擇性， 膜之滲透能力係盡可能於再生階段時重建。個 選擇的溫度取決於膜的類型和各個情況中所進 應’且可經由慣用測試由熟於此藝之士測定。 在根據本發明的較佳分離方法中，使用自 去之富含氧的洗淨氣體以獲得合成氣或煙道氣 進工業熔爐（如玻璃熔爐、熔鐵爐或廢棄物焚 率。 在根據本發明的分離方法之另一個較佳具 用含氮和氧的供入氣體，且使用該氧耗盡的供 惰性氣體或作爲化學合成（例如在氨合成）中 除了習用的氧化方法之外，根據本發明的 包括氧化性脫氫、氧化性耦合或氧氯化，且可 以製備甲醇、甲酸、甲醛、乙醇、乙烯、醋酸 氧乙烷、丙醇、丙烯、甲乙酮、丙酮、丙醛、 二甲酸酐、順丁烯二酸酐、苯乙烯、對苯二甲 乙烯、二氯乙烯、硫氧化物、醋酸乙烯酯、丙 、氰化氫、1，4-丁二醇、環氧丙烷、蒽醌、丙 丙稀酸、稀丙基氯、甲基丙燒醛、焦苯六甲酸 烷及氯甲烷類。 根據特定的化學反應，可以用於想要反應 裝備該膜反應器。 個情況中由 達到氧化產 且用於氧的 別情況中所 行的化學反 該滲透室除 ，例如以增 化爐）的效 體例中，使 入氣體作爲 的氮來源。 氧化方法也 ，例如，用 、乙醛、環 丙烯醛、苯 酸、氯、氯 燦腈、丙酮 烯酸、甲基 酐、二氯乙 的觸媒額外 -17- 201000201 本發明亦係有關用於除去氧或進行氧化反應之特定構 造的設備。此設備的特徵爲存在下列元件： A ) 至少一個包含能傳導氧陰離子且將該設備區分 爲至少一個滲透室和至少一個基材室的陶瓷之膜， B ) 至少一個供入氣體的入口，該供入氣體包含氧 及/或至少一種釋放氧的化合物，該入口係連接至該基材 室， C ) 至少一個供入氣體的出口，該供入氣體已經耗 盡氧及/或至少一種釋放氧的化合物，該出口係連接至該 基材室， D ) 任意地至少一個洗淨氣體的入口，該洗淨氣體 任意地包含至少一種反應物，該入口係連接至該滲透室， E ) 至少一個洗淨氣體的出口，該洗淨氣體包含氧 、含氧的氣體混合物及/或經氧化的反應物，該出口係連 接至該滲透室，及 F ) 至少一個用於藉由直接或間接熱交換將該膜額 外加熱至高於操作溫度的組件。 本發明的設備可存在於數個變體中。在一個變體中， 至少一個洗淨氣體的入口係存在於該滲透室中，該洗淨氣 體任意地包含至少一種反應物。在另一個變體中，該滲透 室中沒有洗淨氣體的入口。 本發明的設備較佳包含至少一個洗淨氣體的入口 D ) ，該入口係連接至該滲透室。 本發明的設備係於提高的溫度下操作。這可藉由加熱 -18- 201000201 設備或經由加入氣體（即，熱供料的）及/或洗淨氣體， 或經由這些方法的組合引起。 本發明的設備之特徵爲存在一個組件，利用該組件能 將該膜控制加熱至高於該膜的操作溫度。 此加熱可間接加熱該膜，例如，經由使用與該膜熱接 觸的加熱元件。 此加熱元件可在該再生階段時以電力予以加熱或以超 熱介質塡充，其能使該膜的溫度升至高於操作溫度的想要 溫度，因此使該膜能再生。 此加熱也可爲直接加熱，例如經由以經加熱的氣體或 氣體混合物洗淨該膜的一或兩側。這可爲惰性氣體、空氣 或反應性氣體或氣體混合物，例如空氣和可氧化的化合物 。這些氣體較佳爲引導至接近該膜，且其熱能使該膜的溫 度能於該再生階段時升高至比該操作溫度高想要的程度， 因此使其能再生。這些方法的組合也可行。 在本發明的設備之較佳具體實施中，該設備包含，作 爲用於額外加熱該膜的組件，至少一個氣體入口，該至少 一個氣體入口開放至該基材室內或該滲透室內且熱惰性氣 體及/或空氣及/或可燃氣體可經過該至少一個氣體入口直 接通至該膜表面。 本發明的設備較佳額外包含G )至少一個溫度感測器 。這可存在於接近該膜或較佳在連接至該滲透室的出口中 〇 該溫度感測器G )能監測將該膜加熱至高於該操作溫 -19- 201000201 度，例如經由監測該滲透室的溫度。此測量可用作控制參 數以控制將該膜加熱至高於該操作溫度。 在上述設備的較佳具體實施例中，至該基材室及/或 該滲透室的入口係連接至壓縮器，經由該等壓縮器可獨立 建立該等室中的氣壓。 再生所需的溫度可在本發明的設備中達到，較佳經由 所獲得的廢氣（例如經由副產物的焚燒）之熱利用。選擇 地，可使用反應物氣體或其他可氧化的介質（例如天然氣 )當作加熱氣體。 在本發明的較佳變體中，以偏移時間操作數個分離設 備或膜反應器，在該情況中至少個別設備係在各個情況中 自生產操作暫時分離出來且予以再生。再生可，例如，經 由將熱氣供入所再生的設備且將熱氣全面氧化而引起，氧 化所需的氧係由該膜提供。加熱氣體可至少部分由實際目 標反應的副產物構成。選擇地，再生溫度可藉由外部燒製 和與所再生的反應器直接或間接熱交換而提供。 接下來的實施例和接下來的圖形將例證本發明而不會 限制彼。 組成BaCoxFeyZrz03.s (其中x + y + z = 1 )的陶瓷膜係 使用。這些係描述於文獻中且可用以獲得各種不同應用的 氧（T. Schiestel，M. Kilgus，S. Peter, K.J. Caspary，H. Wang, J. Caro, Journal of Membrane Science 2005, 25 8, 1 -4 ; DE 1 0 200 5 006 5 7 1 A1 或 DE 1 0 2005 060 1 7 1 A1 )。 當組成 BaCoQ.4Fe().4Zr〇.203-5 (BCFZ)的膜係在 400 -20- 201000201 與5 00 t之間的溫度下以相當高的氧滲透率操作。 第2圖顯示在此溫度範圍內的氧滲透實驗結果’使用 如先前所述的實驗裝置，例如’在 T_SchieStel，M· Kilgus, S. Peter, K.J. Caspary, H- Wang, J. Caro, Journal of Membrane Science 2005, 258, 1 -4 中 ° 在該膜的供入側，將1 50 ml/min的空氣當作供入氣 體添加，同時最初將30 ml/min的He (純度> 99.995% )塡在該膜的滲透側。 在該膜兩側上的壓力爲1.03 6 bar (絕對）；滲透的 氧量係藉由氣體層析法予以測定。 爲了預防實驗結果被烘箱的溫度分佈扭曲’該膜在該 烘箱的非等溫區中係覆以金糊。在等溫區中的有效膜表面 積爲 0.43 cm2。 在操作該BCFZ膜時，氧滲透作用持續降低（第3圖 ，操作溫度5 0 0 °C )。 此氧滲透作用的降低可能與局部組成的變化有關。 表1顯示新鮮膜的組成與所用的膜的組成（在5〇〇°C 下經過2 0小時的滲透實驗；藉由E D X S分析）的比較。 頃發現該氧滲透的重建可經由將該膜加熱至9 2 5 °C且 使此溫度維持1小時的時期。 第4圖顯示在500 °C下使用膜自空氣除去氧的實驗之 結果。在各個情況中經過2 0小時之後，在該滲透側藉由 空氣替代氦’且以i K/min的速率將該膜加熱至925 1。 將該膜留在此溫度下1小時，接著再冷卻至5 0 0 °C。據發 -21 - 201000201 現，經過此程序之後’將再達到原先的氧滲透作用。 表1 8&(原子％) c 0 (原子％ ) F e (原子％) 冗“原子％) 新鮮膜 54.2 18.4 17.6 9.8 滲透測量 之後的膜 供入側 (空氣側） 70.9 12.1 12.0 5.0 總體體積 56.1 17.1 16.3 10.5 滲透側 (He 側） 50.0 18.7 19.0 12.3 【圖式簡單說明】 第1圖顯示經由氧陰離子-傳導性陶瓷膜將反應器區 分爲兩個室的程序。 第 2圖顯示在400-500 °c的溫度範圍內使用組成 BaCoo.4Feo.4Zro.2O34 (BCFZ)的膜之氧滲透實驗的結果 〇 第3圖顯示在操作該BCFZ膜時氧滲透作用持續降低 (操作溫度5 0 0。(：）。 第4圖顯示在500°C下使用膜自空氣除去氧的實驗之 結果，其中在各個情況中經過2 0小時之後’在該滲透側 藉由空氣替代氨，且以1 K/min的速率將該膜加熱至 92 5 〇C。 【主要元件符號說明】 -22 - 201000201 (1 ):氧陰離子-傳導性陶瓷膜 (2 ):基材室 (3 ):氣體混合物 (4 ):滲透室 (5 ):可氧化介質 (6 ):氧化產物 (7 ):氧耗盡的氣體Zhu, R. Cai, Journal of Membrane Science 2002, 203, 1 75-189). As with the composition of the membrane, the oxygen permeability clearly depends on the operating conditions (T. Schiestel, M. Kilgus, S. Peter, KJ Caspary, H. Wang, J. Caro, Journal of Membrane Science 2005, 25 8, 1- 4). Of particular importance herein is temperature, which generally has a linear to exponential effect on oxygen permeability. The use of this film, which is often referred to, is to obtain a synthesis gas via partial oxidation of a hydrocarbon, for example as described in WO 2007/068369 A1. Other possible applications are, for example, obtaining oxygen-enriched air, for example as described in DE 10 2005 006 571 A1; oxidative dehydrogenation of hydrocarbons or hydrocarbon derivatives; oxidative coupling of methane; or obtaining electricity for generation The plant should use 201000201 oxygen (for this topic, see H. Wang, Y. Cong, X. Zhu, W. Yang, React. Kinet. Catal. Lett. 2003, 79, 3 5 1 -3 5 6 ; X Tan, K. Li, Ind. Eng. Chem. Res. 2006, 45,1 42- 1 49 ; R. Bredesen, K. Jordal, 〇. Bolland, Chemical Engineering and Processing 2004, 43,1 1 2 9- 1 1 5 8 ). When the membrane for obtaining oxygen is used in a chemical reactor, it is customary to use a reactor which is divided into at least two chambers by including an oxyanion-conductive ceramic membrane (1). The oxygen-supply gas or gas mixture (3) (for example, air) is initially tied to the supply side (=substrate chamber) (2) of the ceramic membrane, and the oxidizable medium (5) is tied to the permeate side (= Penetration chamber) (4). In operation, oxygen from the side of the higher oxygen partial pressure permeates through the ceramic membrane (1) and reacts with the oxidizable medium (5) present on the opposite side to give an oxidized product (6). The oxygen-depleted gas (7) is removed from the feed side. Figure 1 shows a program that is essentially known in this way. Since oxygen is continuously consumed on the permeate side, the partial pressure of oxygen on the permeate side is lower than the partial pressure of oxygen on the supply side. Therefore, the supply side can use air having a relatively low pressure, and a significantly elevated temperature exists simultaneously on the permeate side. The lower pressure limit on the supply side is that the oxygen partial pressure on the supply side must be higher than the oxygen partial pressure on the permeate side. These ceramic membrane systems are therefore an inexpensive alternative to established cryogenic air separation. However, due to the high operating temperatures of ceramic membranes that are often required, only a few compounds with very simple chemical structures are still suitable as oxidizable media. Often these are C, or c2 hydrocarbons. When more complex molecules (such as aromatic, aliphatic, cartridge aliphatic or unsaturated-8- 201000201 aliphatic compounds such as benzene, toluene, xylene, ethylbenzene, ethane, ethylene, acetylene, propane, propylene, When butane, butene or 13-butadiene is used in the reactor of the ceramic membrane system having a conventional operating temperature of 800 ° C or higher, these molecules will have significant thermal decomposition. The result is a considerable reduction in the achievable product selectivity and achievable yield, and an increased amount of coke formation. The results are often of little commercial interest in such applications. In the case where oxygen is removed from the gas mixture to obtain oxygen, it is also expected to be carried out at a temperature lower than the conventional one. Therefore, it is strongly required to expand the temperature range in which the ceramic membrane is operated in the direction of lower operating temperature. It has been fundamentally expected to lower the operating temperature until now that the oxygen permeability of the ceramic membrane will deteriorate after a certain period of time at a lower temperature and the operation will no longer be economically carried out. It has been unexpectedly found that the oxyanion-conducting ceramic membrane can be regenerated by temporarily raising the temperature, and this allows the initial oxygen permeation performance of the membrane to be re-established. Therefore, it is possible to provide a method in which oxygen removal can be stably performed by a ceramic film at a temperature which is considerably lower than 800 ° C, for example, in the range of 400 to 600 ° C. SUMMARY OF THE INVENTION The present invention relates to a method for oxygen permeable regeneration of a ceramic membrane for conducting an oxyanion. The method comprises at least one regeneration stage of the membrane after the operating phase, wherein the temperature of the membrane is increased above the temperature selected for the operation phase to achieve a degree of increase in oxygen permeability of the membrane again - 9 - 201000201 In the text, it is understood that a ceramic film means a film mainly composed of a non-metallic crystal which is produced by a sintering method. As a result of the oxygen permeability regeneration of the membrane, the oxygen permeability of the membrane which has been lowered during the operation is again increased. Preferably, the method is used to reconstruct at least 90%, and especially at least 5%, and most preferably 100% of the oxygen permeability of the membrane present at the beginning of the cycle of the operating and regeneration stages. More preferably, the method maintains the oxygen permeability of the membrane at least 95% of the oxygen permeability originally present at each and every beginning of the cycle during a number of cycles of operation and regeneration. In a preferred variant of the process according to the invention, the film temperature in the regeneration stage is at least 50 ° C higher than the temperature of the film in the operating phase, preferably at least 100 ° C. In another preferred variant of the method according to the invention, the temperature of the membrane during this stage of operation is between 4,000 and 690 °C. The method according to the invention is preferably for the removal of oxygen in a separation apparatus having a separation of at least one substrate chamber and at least one permeation chamber by means of a membrane comprising a ceramic capable of conducting oxygen anions, the separation method comprising The following steps: a) compressing and heating a gas containing oxygen and/or at least one oxygen releasing compound to obtain a feed gas, b) adding the compressed and heated feed gas to a substrate chamber of the separation device, c) Optionally, adding a cleaning gas to the permeation chamber of the separation device, -10-201000201 d) establishing, in the substrate chamber and/or the permeation chamber, a partial pressure of oxygen permeation in the substrate chamber and the permeation chamber a ceramic conducting oxygen anion transporting oxygen to the pressure in the permeate chamber, e) removing oxygen depleted feed gas from the substrate chamber, f) removing oxygen enriched scrubbing gas or oxygen from the permeate chamber, g) The operation of the separation apparatus comprises a plurality of separation stages interrupted by at least one regeneration stage, h) the temperature of the membrane is less than 800 ° C during the separation stages, and i) the membrane during the regeneration stage Temperature ratio The temperature of the membrane at this stage of operation is at least 5 (TC, preferably at least 1000 ° C. The oxygen removal may be the consumption of oxygen in the substrate chamber, in which case oxygen may be derived from a gas containing oxygen and/or a compound that releases oxygen. This enriches the permeation chamber with oxygen. The separation method can be operated in several variants. In one variation, a feed gas is used in the substrate chamber, and A purge gas is used in the permeate chamber, and the permeate chamber is enriched in oxygen and removed from the permeate chamber during operation. In another variation, a feed gas is used in the substrate chamber, and no scrubbing gas is supplied to the chamber. The permeate chamber collects pure oxygen in the permeate chamber and removes pure oxygen from the permeate chamber during operation. The method according to the invention is preferably also used in a membrane reactor for carrying out an oxidation reaction, the membrane reactor having A membrane comprising a ceramic capable of conducting an oxyanion is divided into at least one substrate chamber and an interior of at least one permeate chamber, and the method comprises the steps of: a) compressing and heating a compound -11 comprising oxygen and/or at least one oxygen release. 201000201 The gas of the object to get Into the gas, b) adding the compressed and heated feed gas to the substrate chamber of the membrane reactor, c') adding a purge gas comprising at least one reactant to the permeate chamber of the membrane reactor, d') Establishing, in the substrate chamber and/or the permeation chamber, a partial pressure of oxygen in the substrate chamber and the permeation chamber to transmit oxygen to the permeation chamber through the ceramic capable of conducting oxygen anions and at least one of the at least one reactant a partial oxidation pressure e) removing an oxygen-depleted supply gas from the substrate chamber, Γ) removing the cleaning gas comprising at least one partially oxidized reactant from the permeate chamber, g') the membrane reactor The operation comprises a plurality of reaction stages interrupted by at least one regeneration stage, h') the temperature of the membrane is less than 800 ° C during the reaction stages, and i) the temperature of the membrane is proportional to the regeneration stage The temperature of the film during the reaction stage is at least 50 ° C, preferably at least 1 ° C. [Embodiment] In the context of the present description, it is understood that "at least partially oxidizing the at least one reactant means that at least a portion of the reactants fed to the permeate chamber react with oxygen. The feed gas used may be any oxygen-containing gas. a gas and/or an oxygen-releasing compound. These preferably additionally comprise nitrogen and more particularly do not comprise any oxidizable component of -12-201000201. Examples of oxygen-releasing components are water vapor, nitrogen oxides (such as N Ox or N20, carbon oxides (such as co2 or CO) and sulfur oxides (such as S〇x), where X = 1-3. It is particularly preferred to use air as the feed gas. The oxygen content of the feed gas is often at least 5 vol%, preferably at least 1 〇 vol%, more preferably 1 〇 _30 vol%. The cleaning gas used may be any gas, provided that they maintain the oxygen partial pressure gradient in the film. In a variant of the inventive method, a gas comprising oxygen and nitrogen, such as air, is used. In another variant of the method according to the invention, a gas comprising an oxidizable component (optionally combining oxygen and nitrogen) is used. . The purge gas may comprise inert and/or oxidizable components (such as water vapor or carbon dioxide) and saturated and/or unsaturated aliphatic and/or aromatic and/or araliphatic hydrocarbons. As a cleaning gas, in the method according to the present invention, any ceramic film capable of conducting an oxyanion and having selectivity to oxygen may be used. The morphology of the film may be as desired. They may, for example, be in a flat form or in a ceramic form. The form of the hollow fiber is present. The film preferably exists in the form of a ceramic hollow fiber having a long to diameter ratio of at least 1 。. These hollow fibers are especially used in the form of a composite material, such as w Ο 2 0 0 6 / 8 1 9 5 9 A 1. The ceramics which can transport oxygen anions and are used according to the invention are known per se. -13- 201000201 These ceramics can be made of materials capable of conducting both oxygen anions and electrons (=mixed conductive materials). Composition. However, it can also use different ceramics or a combination of ceramic and non-ceramic materials. Examples of this are combinations of oxyanion-conducting ceramics and electron-conducting non-ceramic materials (such as metals). Or a combination of different ceramics each having an oxygen anion and an electron or all of the components not having an oxygen transmission effect. Examples of the polyphase membrane system are ceramics having ion conductivity and another material having beta conductivity, especially a mixture of metals, including, in particular, a combination of a material having a fluorite structure or a fluorite-related structure and an electron-transporting material, such as Zr02 or Ce02 (which is optionally doped with Ca〇 or Y2〇3) and a metal ( A combination of, for example, palladium. Another example of a multiphase membrane system is a hybrid structure having a partial perovskite structure (ie, a hybrid system in which various crystal structures are present in a solid state)' and at least one of the mixed structures is calcium Titanium ore structure or perovskite related structure. The oxygen-transporting material to be used is preferably a mixed conductive oxide ceramic type, particularly preferably having a perovskite structure or having a perovskite structure or having an orivilis structure. Perovskites used in accordance with the present invention often have an AB03.s configuration in which A represents a divalent cation and B represents a trivalent or higher cation, the ionic radius of A is greater than the ionic radius of B, and δ is between 0.001 and 1.5. 'It is preferably between 0 _ 0 1 and 〇 _ 9, and more preferably 〇. The number ' between 〇 1 and 〇 _ 5' is used to establish the electrical neutrality of the material. Mixtures of different cationic cerium and/or cationic cerium may also be present in the calcium minerals used in accordance with the invention. The mayenite used in accordance with the present invention often has an a2b2〇5_s configuration, wherein A, B and δ are each as described above. Similarly, in the mayenite used in accordance with the present invention, a mixture of different cationic cerium and/or cationic cerium may be present. Cationic B preferably occurs in a fractional oxidation state. However, some or even all of the B-type cations may also be trivalent or higher cations having a fixed oxidation state. Particularly preferred oxide ceramics contain a type A cation selected from the group consisting of a second main group cation, a first transition cation, a second transition cation, a lanthanide cation, or a mixture of such cations, preferably selected from the group consisting of Mg2+. , Ca2+, Sr2+, Ba2+, Cu2+, Ag2+, Zn2+, Cd2+, and/or steroidal cations. Particularly preferred oxide ceramics contain a B-type cation selected from the group consisting of a cation of the Periodic Table to Group VIIIB and/or a cation of a steroid, a cation of a third to fifth main group metal or a mixture of these cations, preferably selected from the group consisting of Fe3 + , Fe4+, Ti3+, Ti4+, Zr3+, Zr4+, Ce3+, Ce4+, Mn3+, Mn4+, Co2+, Co3+ 'Nd3+, Nd4+, Gd3+, Gd4+, Sm3+, Sm4+, Dy3+, Dy4+, Ga3+, Yb3+, Al3+ 'Bi4+ or these a mixture of cations. Still more preferred oxide ceramics contain a Type B cation selected from the group consisting of Sn2+, Pb2+, Ni2+, Pd2+, a lanthanide or a mixture of such cations. The orivilis used in accordance with the present invention often has (Bi202) 24 -15- 201000201 (vo3.5 [] Q.5) 2 - structural elements or related structural elements, wherein □ means the position of the oxygen defect. A particularly preferred film consists of BaCoxFeyZrz〇3.s, wherein X, y and z can each independently be assumed to be in the range of 〇_〇1 to 0·9, preferably 0.1 to 0.8, and X, The sum of y and z is 丨, and δ is a number between 0.001 and 1-5 to establish electrical neutrality of the material. An excellent film is a film of this type, wherein X is from 0.1 to 0.6, y is from 0.2 to 0.8 and ζ is from 0.] to 0.4. The pressure of the supplied gas in the substrate chamber can be varied over a wide range. The pressure in the individual case is selected such that the oxygen partial pressure system on the feed side of the membrane is larger than the permeate chamber. Typical pressure variations in the substrate chamber are between 1 〇 2 and 1 〇〇 bar, preferably between 1 and 80 bar and especially between 2 and 10 bar. The gas pressure in the permeate chamber can likewise vary over a wide range and is established in accordance with the individual conditions of the criteria specified above. The typical pressure in the permeate chamber varies from 1 (between 3 and 100 bar, preferably between 0.5 and 80 bar and especially between 0.8 and 20 bar. The method according to the invention is characterized in that The operation of the apparatus is divided into a plurality of separation or reaction stages interrupted by one or more regeneration stages. During the separation or reaction stage, the apparatus performs its intended purpose while the membrane is The separation capability is reconstituted during the regeneration phase. An additional feature of the method according to the invention is that the membrane is heated to an elevated temperature when it is in the regeneration stage compared to the separation or reaction stages. Frequently, the temperature of the membrane is such In the regeneration stage, it is higher than 65 ° C. It is preferably higher than 7 5 (TC and more preferably higher than 8 5 0 ° C. -16- 201000201 The temperature in the separation equipment or the membrane reactor is familiar in each The artist chooses the maximum separation efficiency and/or maximum yield and selectivity of the material in the separation or reaction stage, and the membrane permeability is rebuilt as much as possible during the regeneration stage. The selected temperature depends on the type of membrane and In each case It should be 'and can be determined by a person skilled in the art through customary tests. In a preferred separation method according to the present invention, a self-depleted oxygen-rich cleaning gas is used to obtain a syngas or flue gas into an industrial furnace ( For example, a glass furnace, a molten iron furnace or a waste incineration rate. Another method of separating according to the present invention preferably uses a feed gas containing nitrogen and oxygen, and uses the oxygen-depleted inert gas or as a chemical synthesis. In addition to conventional oxidation methods (for example in ammonia synthesis), oxidative dehydrogenation, oxidative coupling or oxychlorination according to the invention may be employed, and methanol, formic acid, formaldehyde, ethanol, ethylene, ethylene oxide acetate may be prepared. , propanol, propylene, methyl ethyl ketone, acetone, propionaldehyde, dicarboxylic anhydride, maleic anhydride, styrene, terephthalic acid, dichloroethylene, sulfur oxides, vinyl acetate, propane, hydrogen cyanide, 1,4-butanediol, propylene oxide, hydrazine, propylene glycol, propyl propyl chloride, propyl propyl aldehyde, pyromellitate and methyl chloride. According to specific chemical reactions, can be used Want to react to the membrane reaction In one case, the chemical which is used for the oxidation production and is used for oxygen, in addition to the osmosis chamber, for example, in the effect of the furnace, the gas is used as the nitrogen source. The oxidation method is also, for example, Catalyst with acetaldehyde, cyclopropenal, benzoic acid, chlorine, chlorocanonitrile, acetic acid, methyl anhydride, dichloroethane -17-201000201 The invention is also related to the removal of oxygen or oxidation A device of the specific construction of the reaction. The device is characterized by the presence of the following elements: A) at least one ceramic film comprising an oxygen-conducting anion and distinguishing the device into at least one permeate chamber and at least one substrate chamber, B) at least one An inlet for supplying a gas comprising oxygen and/or at least one oxygen releasing compound, the inlet being connected to the substrate chamber, C) at least one outlet for supplying a gas, the supplied gas having been depleted of oxygen And/or at least one oxygen-releasing compound, the outlet being connected to the substrate chamber, D) optionally at least one purge gas inlet, the purge gas optionally comprising at least one reactant The inlet is connected to the permeate chamber, E) at least one outlet for the purge gas, the purge gas comprising oxygen, an oxygen-containing gas mixture, and/or an oxidized reactant, the outlet being connected to the permeate chamber, And F) at least one component for additionally heating the membrane to a temperature above the operating temperature by direct or indirect heat exchange. The device of the invention may be present in several variants. In a variant, at least one inlet for the purge gas is present in the permeate chamber, the purge gas optionally comprising at least one reactant. In another variation, there is no inlet for the purge gas in the permeate chamber. The apparatus of the present invention preferably includes at least one purge gas inlet D) that is connected to the permeate chamber. The apparatus of the present invention operates at elevated temperatures. This can be caused by heating the -18-201000201 device or via adding a gas (i.e., hot feed) and/or a purge gas, or via a combination of these methods. The apparatus of the present invention is characterized by the presence of an assembly with which the membrane can be controlled to be heated above the operating temperature of the membrane. This heating can indirectly heat the film, for example, via the use of a heating element in thermal contact with the film. The heating element can be electrically heated or superheated during the regeneration phase, which raises the temperature of the membrane to a desired temperature above the operating temperature, thereby enabling the membrane to be regenerated. This heating can also be direct heating, for example by washing one or both sides of the film with a heated gas or gas mixture. This can be an inert gas, air or a reactive gas or a mixture of gases such as air and oxidizable compounds. These gases are preferably directed to the membrane and their heat enables the temperature of the membrane to rise to a desired level above the operating temperature during the regeneration phase, thereby enabling regeneration. Combinations of these methods are also possible. In a preferred embodiment of the apparatus of the present invention, the apparatus includes, as an assembly for additionally heating the membrane, at least one gas inlet, the at least one gas inlet being open to the interior of the substrate or the permeate chamber and the hot inert gas And/or air and/or flammable gas may pass directly to the surface of the membrane through the at least one gas inlet. The apparatus of the present invention preferably additionally comprises G) at least one temperature sensor. This may be present in proximity to the membrane or preferably in the outlet connected to the permeate chamber. The temperature sensor G) can monitor the membrane to be heated above the operating temperature -19-201000201 degrees, for example by monitoring the permeation chamber temperature. This measurement can be used as a control parameter to control heating of the membrane above the operating temperature. In a preferred embodiment of the apparatus described above, the inlet to the substrate chamber and/or the permeate chamber is connected to a compressor via which the gas pressure in the chambers can be independently established. The temperature required for regeneration can be achieved in the apparatus of the present invention, preferably via the heat of the obtained off-gas (e.g., by incineration of by-products). Alternatively, a reactant gas or other oxidizable medium (e.g., natural gas) can be used as the heating gas. In a preferred variant of the invention, several separation devices or membrane reactors are operated at offset times, in which case at least individual equipment is temporarily separated from the production operation and regenerated in each case. The regeneration can be caused, for example, by supplying hot gas to the regenerated equipment and oxidizing the hot gas in a comprehensive manner, and the oxygen required for the oxidation is supplied from the membrane. The heated gas can be at least partially composed of by-products of the actual target reaction. Alternatively, the regeneration temperature can be provided by external firing and direct or indirect heat exchange with the regenerated reactor. The following embodiments and the following figures will illustrate the invention without limiting it. A ceramic film system composed of BaCoxFeyZrz03.s (where x + y + z = 1) is used. These lines are described in the literature and can be used to obtain oxygen for a variety of different applications (T. Schiestel, M. Kilgus, S. Peter, KJ Caspary, H. Wang, J. Caro, Journal of Membrane Science 2005, 25 8, 1 - 4 ; DE 1 0 200 5 006 5 7 1 A1 or DE 1 0 2005 060 1 7 1 A1 ). When the film system constituting BaCoQ.4Fe().4Zr〇.203-5 (BCFZ) is operated at a relatively high oxygen permeability at a temperature between 400 -20 - 201000201 and 5000 t. Figure 2 shows the results of oxygen permeation experiments in this temperature range 'using experimental setups as previously described, eg 'in T_SchieStel, M. Kilgus, S. Peter, KJ Caspary, H-Wang, J. Caro, Journal of Membrane Science 2005, 258, 1 -4 Medium ° On the feed side of the membrane, 1 50 ml/min of air is added as feed gas, while initially 30 ml/min of He (purity > 99.995%) The crucible is on the permeate side of the membrane. The pressure on both sides of the membrane was 1.03 6 bar (absolute); the amount of oxygen permeated was determined by gas chromatography. In order to prevent the experimental results from being distorted by the temperature distribution of the oven, the film was covered with a gold paste in the non-isothermal region of the oven. The effective membrane surface area in the isothermal zone was 0.43 cm2. Oxygen permeation continued to decrease during operation of the BCFZ membrane (Fig. 3, operating temperature 50,000 °C). This reduction in oxygen permeation may be related to changes in local composition. Table 1 shows the composition of the fresh film and the composition of the film used (permeation test at 20 ° C for 20 hours; analysis by ED X S). It was found that the reconstitution of oxygen permeation can be carried out by heating the membrane to 9 25 ° C and maintaining this temperature for a period of 1 hour. Figure 4 shows the results of an experiment in which oxygen was removed from air using a membrane at 500 °C. After 20 hours in each case, the film was heated to 92 1 at a rate of i K/min by replacing 氦' with air on the permeate side. The film was left at this temperature for 1 hour and then cooled to 500 °C. According to the report -21 - 201000201, after this procedure, the original oxygen permeation will be achieved. Table 1 8 & (atomic %) c 0 (atomic %) F e (atomic %) redundant "atomic %" fresh film 54.2 18.4 17.6 9.8 film supply side (air side) after permeation measurement 70.9 12.1 12.0 5.0 total volume 56.1 17.1 16.3 10.5 Permeate side (He side) 50.0 18.7 19.0 12.3 [Simple description of the diagram] Figure 1 shows the procedure for dividing the reactor into two chambers via an oxyanion-conducting ceramic membrane. Figure 2 shows at 400-500 The results of the oxygen permeation test using a membrane constituting BaCoo.4Feo.4Zro.2O34 (BCFZ) in the temperature range of °c, Fig. 3 shows that the oxygen permeation continues to decrease when the BCFZ membrane is operated (operating temperature 5000). :). Figure 4 shows the results of an experiment using a membrane to remove oxygen from air at 500 ° C, where in each case after 20 hours, 'on the permeate side, the air was replaced by air, and at 1 K/min. Rate the film to 92 5 〇 C. [Key component symbol description] -22 - 201000201 (1): Oxygen anion-conducting ceramic film (2): Substrate chamber (3): Gas mixture (4): Osmosis chamber (5): oxidizable medium (6): oxidation product (7): oxygen depleted Body
-23--twenty three-