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丙烯在三种典型 Fe-沸石上对 NH₃-SCR 中 NOχ 的中毒:从机理研究到涂层改性结构。

Propene poisoning on three typical Fe-zeolites for SCR of NOχ with NH₃: from mechanism study to coating modified architecture.

机构信息

State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China.

出版信息

Environ Sci Technol. 2012 Feb 7;46(3):1747-54. doi: 10.1021/es203070g. Epub 2012 Jan 20.

Abstract

Application of Fe-zeolites for urea-SCR of NO(x) in diesel engine is limited by catalyst deactivation with hydrocarbons (HCs). In this work, a series of Fe-zeolite catalysts (Fe-MOR, Fe-ZSM-5, and Fe-BEA) was prepared by ion exchange method, and their catalytic activity with or without propene for selective catalytic reduction of NO(x) with ammonia (NH(3)-SCR) was investigated. Results showed that these Fe-zeolites were relatively active without propene in the test temperature range (150-550 °C); however, all of the catalytic activity was suppressed in the presence of propene. Fe-MOR kept relatively higher activity with almost 80% NO(x) conversion even after propene coking at 350 °C, and 38% for Fe-BEA and 24% for Fe-ZSM-5 at 350 °C, respectively. It was found that the pore structures of Fe-zeolite catalysts were one of the main factors for coke formation. As compared to ZSM-5 and HBEA, MOR zeolite has a one-dimensional structure for propene diffusion, relatively lower acidity, and is not susceptible to deactivation. Nitrogenated organic compounds (e.g., isocyanate) were observed on the Fe-zeolite catalyst surface. The site blockage was mainly on Fe(3+) sites, on which NO was activated and oxidized. Furthermore, a novel fully formulated Fe-BEA monolith catalyst coating modified with MOR was designed and tested, the deactivation due to propene poisoning was clearly reduced, and the NO(x) conversion reached 90% after 700 ppm C(3)H(6) exposure at 500 °C.

摘要

用于柴油机尿素 SCR 的 Fe-沸石受烃(HC)影响催化剂失活的限制。在这项工作中,通过离子交换法制备了一系列 Fe-沸石催化剂(Fe-MOR、Fe-ZSM-5 和 Fe-BEA),并研究了它们在有或没有丙烯存在时用于氨选择性催化还原(NH3-SCR)的催化活性。结果表明,在测试温度范围内(150-550°C),这些 Fe-沸石在没有丙烯的情况下具有相对较高的活性;然而,在丙烯存在下,所有的催化活性都受到抑制。在 350°C 下丙烯结焦后,Fe-MOR 仍保持相对较高的活性,NOx 转化率接近 80%,而 Fe-BEA 为 38%,Fe-ZSM-5 为 24%。研究发现,Fe-沸石催化剂的孔结构是形成积碳的主要因素之一。与 ZSM-5 和 HBEA 相比,MOR 沸石具有丙烯扩散的一维结构,相对较低的酸度,不易失活。在 Fe-沸石催化剂表面观察到含氮有机化合物(如异氰酸酯)。位阻主要发生在 Fe(3+)位上,NO 在这些位上被活化和氧化。此外,设计并测试了一种新型的全配方 Fe-BEA 整体式催化剂涂层,对其进行了 MOR 改性,明显减少了丙烯中毒失活的现象,在 500°C 下暴露于 700ppm C(3)H(6)时,NO(x)转化率达到 90%。

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