Instituto de Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia, Consejo Superior de Investigaciones Científicas, Avenida de los Naranjos s/n.46022 Valencia, Spain.
ChemSusChem. 2012 Aug;5(8):1587-96. doi: 10.1002/cssc.201100747. Epub 2012 Jul 12.
Process intensification by the integration of membranes and high-temperature reactors offers several advantages with regard to conventional process schemes, that is, energy saving, safe operation, reduced plant/unit size, and higher process performance, for example, higher productivity, catalytic activity, selectivity, or stability. We present the study of oxidative dehydrogenation of ethane at 850 °C on a catalytic membrane reactor based on a mixed ionic-electronic conducting membrane. The surface of the membrane made of Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) has been activated by using different porous catalytic layers based on perovskites. The layer was deposited by screen printing, and the porosity and thickness was studied for the catalyst composition. The different catalyst formulations are based on partial substitution of A- and B-site atoms of doped strontium ferrite/cobaltites (A(0.6)Sr(0.4)Co(0.5)Fe(0.5)O(3-δ) and Ba(0.6)Sr(0.4)BO(3-δ)) and were synthesized by an ethylenediaminetetraacetic acid-citrate complexation route. The use of a disk-shaped membrane in the reactor enabled the direct contact of gaseous oxygen and hydrocarbons to be avoided, and thus, the ethylene content increased. High ethylene yields (up to ≈81 %) were obtained by using a catalytic coating based on Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ), which included macropores produced by the addition of graphite platelets into the screen-printing ink. The promising catalytic results obtained with this catalytically modified membrane reactor are attributed to the combination of 1) the high activity, as a result of the high temperature and oxygen species diffusing through the membrane; 2) the control of oxygen dosing and the low concentration of molecules in the gas phase; and 3) suitable fluid dynamics, which enables appropriate feed contact with the membrane and the rapid removal of products.
通过膜与高温反应器的集成实现过程强化相对于传统工艺方案具有若干优势,例如节能、安全操作、减小工厂/单元尺寸以及提高工艺性能,例如提高生产率、催化活性、选择性或稳定性。我们研究了在基于混合离子-电子导体膜的催化膜反应器中,在 850°C 下乙烷的氧化脱氢反应。由 Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ)制成的膜的表面通过使用不同的基于钙钛矿的多孔催化层进行了活化。该层通过丝网印刷沉积,研究了催化剂组成的孔隙率和厚度。不同的催化剂配方基于掺杂锶铁氧体/钴酸盐的 A-和 B-位原子的部分取代(A(0.6)Sr(0.4)Co(0.5)Fe(0.5)O(3-δ)和 Ba(0.6)Sr(0.4)BO(3-δ)),并通过乙二胺四乙酸-柠檬酸络合路线合成。在反应器中使用盘形膜可避免气体氧气和碳氢化合物的直接接触,从而增加了乙烯的含量。通过使用基于 Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ)的催化涂层,获得了高达 ≈81%的高乙烯收率,该涂层包括通过在丝网印刷油墨中添加石墨薄片产生的大孔。这种催化改性膜反应器获得的有前景的催化结果归因于以下因素的结合:1)由于高温和氧物种通过膜扩散,因此具有高活性;2)控制氧气剂量和气相中分子的低浓度;3)适当的流体动力学,使适当的进料与膜接触并快速去除产物。