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CN102639223A - 包括具有受控宏观孔隙和受控微观结构的多孔区域和具有标准微观结构的区域的催化反应器 - Google Patents

包括具有受控宏观孔隙和受控微观结构的多孔区域和具有标准微观结构的区域的催化反应器 Download PDF

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CN102639223A
CN102639223A CN2010800540809A CN201080054080A CN102639223A CN 102639223 A CN102639223 A CN 102639223A CN 2010800540809 A CN2010800540809 A CN 2010800540809A CN 201080054080 A CN201080054080 A CN 201080054080A CN 102639223 A CN102639223 A CN 102639223A
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P·戴-嘉罗
D·加里
M·科尼拉克
A·屈尼
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

本发明涉及一种催化反应器，该催化反应器包括：至少一个第一组织结构/微观结构（1），其包括：陶瓷和/或金属多孔组织结构，其具有2ppi至80ppi的孔隙大小和大于85%的宏观孔隙率，以及具有100nm至5μm的颗粒大小和超过95%的骨架密实度的微观结构，以及催化层；以及至少一个第二组织结构/微观结构（2），其包括具有0.1至100μm的孔隙大小和小于60%的宏观孔隙率的球形或圆柱形组织结构，以及具有20nm至10μm的颗粒尺寸和20%至90%的骨架密实度的微观结构，以及催化层；第一和第二组织结构/微观结构堆叠在所述反应器内部。

Description

包括具有受控宏观孔隙和受控微观结构的多孔区域和具有标准微观结构的区域的催化反应器
技术领域
本发明的主题是一种催化反应器，该催化反应器包括至少一个组织结构和至少一个标准组织结构的催化反应器，所述至少一个组织结构包括具有受控宏观孔隙和受控微观结构的催化陶瓷或金属泡沫。标准组织结构应理解为指催化剂——即鼓状物、棒条、珠子、片状物等——的制造商通常采用的组织结构。
背景技术
固定床反应器——特别是蒸汽重整反应器——的性能与催化床的结构直接相关。催化床的结构应理解为指相关的工业反应器中相同或不同的组织结构（鼓状物、球体、棒条等）的催化剂堆。目前还没有以工业水平开发多孔结构。将举例说明各种水-气转化反应器堆（水-气反应中包括的反应器）（组织结构相同但微观结构不同的连续催化床）。在这些情形中，工业反应器中存在的催化床结构可以是体积为A的催化剂、体积为B的催化剂和体积为C的催化剂组成的连续催化剂堆叠。A、B和C因催化剂的组织结构（几何形式、堆叠孔隙率等）或微观结构（化学成分、微观孔隙的大小、活性相的大小和分布等）或组织结构/微观结构而异。通常，催化床的标准结构由包括一个或多个孔的鼓状物、珠体、板条、球体等组成。
高性能催化床结构必须同时：
-具备最大的表面积/体积比（m2/m3），以便增大用于交换反应的几何表面积并因此间接提高催化效率，
-与由常规结构（球体、珠体、圆柱体、鼓等）造成的随机填充相比提高了管的填充密度，
-使沿催化床（在催化反应器的入口与出口之间）的压降最小，
-提供最大轴向和/或径向效率改善的热传递。轴向应理解为指沿催化反应器的轴线，径向应理解为指从催化反应器的内壁或外壁到催化床的中心，
-满足催化床所承受的热机械应力和/或热化学应力。
固定床催化反应器的整体结构是多级“现象”：
-材料（催化剂）本身的微观结构，即其化学成分、微观孔隙和/或中孔隙；活性相的大小和分散；沉积层的厚度等，
-催化剂的组织结构，也就是催化剂的几何形式（颗粒、鼓状、蜂窝状整料、泡沫型多孔结构、球体、珠体、棒条等），
-反应器内的床的结构（在微观结构方面、组织结构方面或两方面不同的催化材料的若干个体积的连续堆叠），也就是催化反应器内的受控组织结构和/或受控微观结构的催化材料的布局。例如，作为催化床的结构，可以设想包括或不包括不同功能的非催化元素的连续堆叠。
因此，问题在于提供一种具备改善的性能的催化反应器。
发明内容
本发明的一种方案是催化反应器，该催化反应器包括：
-至少一个第一组织结构/微观结构（1），其包括：
陶瓷和/或金属多孔组织结构，其具有在平均直径下介于0.3175mm与12.7mm之间的以mm表示的孔隙大小[介于2ppi与80ppi（每英寸孔数）之间]和大于85%的宏观孔隙率，以及具有介于100nm与5μm之间、优选地介于200nm与3μm之间的颗粒大小和大于95%的骨架密实度的微观结构；以及
催化层，
-至少一个第二组织结构/微观结构（2），其包括：
球形或圆柱形几何形式的组织结构，其具有介于0.1μm与100μm之间的孔隙大小和小于60%的宏观孔隙率，以及具有介于20nm与10μm之间、优选地介于0.5μm与5μm之间的颗粒大小和介于20%与90%之间、优选地50%与80%之间的骨架密实度的微观结构；以及
催化层，
第一组织结构/微观结构和第二组织结构/微观结构堆叠在所述反应器内。
具体实施方式
图1中示出了两个组织结构的堆叠。应注意，不同组织结构的相对高度仅为指示性的。
陶瓷和/或金属骨架的密实度优选通过扫描电子显微镜检查法（SEM）或通过阿基米德原理测量。
孔隙大小应理解为由陶瓷和/或金属骨架形成的多微孔的容积。通常，在陶瓷和/或金属多孔组织结构的情况下，该多微孔容积很低（未形成特定微观孔隙或中孔隙）并且小于0.1g/cm3。这使得不存在微观孔隙和中孔隙。已有的孔隙是与形成多孔组织结构的陶瓷颗粒堆叠有关的宏观孔隙。在陶瓷和/或金属骨架的情形中，与鼓状物、珠体或棒条型等催化支承物的标准组织结构/微观结构相比较，当密实度大于95%时，残余宏观孔隙基本上被封闭。
颗粒大小应理解为特别是指具有介于100nm与5μm之间、优选200nm与3μm之间的大小的个别的陶瓷颗粒，所述大小对应于颗粒的直径。
多孔催化组织结构优选是催化陶瓷或金属泡沫。催化应理解为指在多孔组织结构的表面存在催化剂。
公知由陶瓷甚至金属合金制成的泡沫被用作用于化学反应、更具体地用作多相催化反应中的催化剂支承物。这些泡沫特别有益于高放热或吸热反应（例如，放热费托（Fischer-Tropsch）反应、水-气转化反应、部分氧化反应、甲烷化反应等），和/或需要获得高空间速度的催化反应器（用于天然气、石脑油、LPG等的蒸汽重整的反应）。
根据本发明的催化反应器内的组织结构堆可以将催化泡沫在高表面积/体积比、高效热传递、限制压降和满足热机械应力和/或热化学应力方面的性能与具有降低的性能但具有潜在地较低的成本的“标准”催化剂相结合。
根据情况而定，根据本发明的反应器能够具备以下特征中的一个或多个：
-第一组织结构/微观结构1介于两个第二组织结构/微观结构2之间。这种堆叠可以避免反应器的壁与第一组织结构-微观结构之间可能的优先流动。图2中示出了3个组织结构的堆叠；
-第二组织结构/微观结构2介于两个第一组织结构-微观结构1之间；优选地，这两个第一组织结构/微观结构中的一个位于用于待处理的气体的入口侧且另一个位于用于所生产的气体的出口侧。这是因为用于所生产的气体的出口侧的区域承受较高温度，如果陶瓷和/或金属多孔组织结构具备优于球形或圆柱形几何形式的热机械特性，则这种组织结构堆可以使组织结构堆的总体强度最优。图3中示出了三个组织结构的堆叠；
-每个组织结构均可分为具有不同宏观孔隙和/或微孔隙的至少两个子组织结构；
-陶瓷和/或金属多孔组织结构包括至少一个孔隙率梯度，所述梯度在整个所述组织结构上在径向和/或轴向上是连续的和/或不连续的；
-所述反应器包括用于待处理的气体的入口和用于所生产的气体的出口，并且第一组织结构/微观结构1被置于用于待处理的气体的入口侧。这是因为，在此希望单位体积的催化活性最高并且希望最大的径向热传递，以便减小在用于待处理的气体的入口侧更明显的径向温度梯度；
-第二组织结构/微观结构由鼓状物、颗粒、粉末、球体、棒条、珠体或它们的组合构成。
应注意，在图2和3中，不同组织结构的相对高度仅为指示性的。
多孔组织结构由从聚氨酯（PU）、聚氯乙烯（PVC）、聚苯乙烯（PS）、纤维素和胶乳中选择的聚合材料制成的基质制成，但泡沫的理想选择受严格的要求限制。
聚合材料必需不释放有毒混合物，例如避免使用PVC，因为其可导致氯化氢的释放。
当具有陶瓷性质时，多孔催化组织结构通常包括从氧化铝（Al2O3）和/或掺杂氧化铝（La（按重量计算1%至20%）-Al2O3、Ce（按重量计算1%至20%）-Al2O3、Zr（按重量计算1%至20）-Al2O3）、氧化镁（MgO）、尖晶石（MgAl2O4）、水滑石、CaO、硅钙氧化物、硅铝氧化物、氧化锌、堇青石、多铝红柱石、钛酸铝和锆石（ZrSiO4）中选取的无机颗粒；或从以下选择的陶瓷颗粒：铈土（CeO2）、氧化锆（ZrO2）、稳定铈土（铈土中的Gd2O3介于3mol%与10mol%之间）和稳定氧化锆（氧化锆中的Y2O3介于3与10mol%之间），以及配方（I）的混合氧化物：
Ce(1-x)Zrx O(2-δ)    （I），
其中0＜x＜1且δ提供氧化物的电中性，
或配方（II）的掺杂混合氧化物：
Ce(1-x)Zrx O(2-δ)    （II），
其中D选自镁（Mg）、钇（Y）、锶（Sr）、镧（La）、镨（Pr）、钐（Sm）、钆（Gd）、铒（Er）或镱（Yb）；其中0＜x＜1，0＜y＜0.5，且δ提供氧化物的电中性。
根据本发明的催化反应器可用于产生气态产品，特别是合成气。
优选地，供给气体包含与甲烷混合的氧气、二氧化碳或蒸汽。然而，这些催化床结构可配置在用于通过蒸汽重整生产氢气的工艺的所有催化反应器上，即，特别是预重整床、重整床和水-气转化（水-气反应）床。
所用的反应温度高且在200℃与1000℃之间、优选在400℃与1000℃之间。
反应物（CO、H2、CH4、H2O、CO2等）的压力可在10bar与50bar之间，优选地在15bar与35bar之间。

Claims (9)

1.一种催化反应器，包括：
-至少一个第一组织结构-微观结构（1），其包括：
○陶瓷和/或金属多孔组织结构，其具有在平均直径下介于0.3175mm与12.7mm之间的以mm表示的孔隙尺寸[介于2ppi与80ppi（每英寸孔数）之间]和大于85%的宏观孔隙率，以及具有介于100nm与5μm之间的颗粒尺寸和大于95%的骨架密实度的微观结构；以及
○催化层，
-至少一个第二组织结构/微观结构（2），其包括：
○球形或圆柱形几何形式的组织结构，其具有介于0.1μm与100μm之间的孔隙尺寸和小于60%的宏观孔隙率，以及具有介于20nm与10μm之间的颗粒尺寸和介于20%与90%之间的骨架密实度的微观结构；以及
○催化层，
所述第一和第二组织结构-微观结构堆叠在所述反应器内。
2.根据权利要求1所述的催化反应器，其特征在于，所述第一组织结构-微观结构（1）介于2个第二组织结构-微观结构（2）之间。
3.根据权利要求1所述的催化反应器，其特征在于，所述第二组织结构-微观结构（2）介于2个第一组织结构-微观结构（1）之间。
4.根据权利要求1至3中任一项所述的催化反应器，其特征在于，每个组织结构均能够被分为具有不同宏观孔隙率和/或微观孔隙率的至少2个子组织结构。
5.根据权利要求1至4中任一项所述的催化反应器，其特征在于，所述陶瓷和/或金属多孔组织结构包括至少一个孔隙率梯度，所述梯度在整个所述组织结构上在径向和/或轴向上是连续的和/或不连续的。
6.根据权利要求1至5中任一项所述的催化反应器，其特征在于，所述反应器包括用于待处理的气体的入口和用于所生产的气体的出口，并且所述第一组织结构-微观结构（1）被置于用于待处理的气体的入口侧。
7.根据权利要求1至6中任一项所述的催化反应器，其特征在于，所述第二组织结构-微观结构由鼓状物、颗粒、粉末、球体、棒条、珠体或它们的混合物组成。
8.利用根据权利要求1至7中任一项所述的催化反应器来生产气体的用途。
9.根据权利要求8所述的用途，其特征在于，所述气体为合成气。
CN201080054080.9A 2009-12-01 2010-11-24 包括具有受控宏观孔隙和受控微观结构的多孔区域和具有标准微观结构的区域的催化反应器 Expired - Fee Related CN102639223B (zh)

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CN104948865A (zh) * 2015-06-23 2015-09-30 长兴县长安造型耐火材料厂 一种浇注用四通管道
CN112714686A (zh) * 2017-08-31 2021-04-27 康宁股份有限公司 具有织构的陶瓷壳体

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FR2961415A1 (fr) * 2010-06-18 2011-12-23 Air Liquide Reacteur catalytique comprenant une structure catalytique offrant une distribution amelioree du flux gazeux
EP2602024A1 (en) * 2011-12-08 2013-06-12 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Catalytic architecture with high S/V ratio, low DP and high void fraction for industrial applications
JP6540260B2 (ja) * 2015-06-18 2019-07-10 株式会社デンソー ハニカム構造体及び自動車用触媒コンバータ

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US6921516B2 (en) * 2001-10-15 2005-07-26 General Motors Corporation Reactor system including auto ignition and carbon suppression foam
GB2423489A (en) * 2005-02-25 2006-08-30 Johnson Matthey Plc Water gas shift reactor
US20070238610A1 (en) * 2006-04-05 2007-10-11 Laiyuan Chen Fuel reformer catalyst
EP2123618A1 (en) * 2008-05-13 2009-11-25 L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Ceramic foam with gradient of porosity in heterogeneous catalysis

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CN112714686A (zh) * 2017-08-31 2021-04-27 康宁股份有限公司 具有织构的陶瓷壳体

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