Research progress on the design of zeolite-based core-shell structure catalysts and their reaction mechanism for diesel vehicle exhaust deNOx
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摘要: 柴油机尾气排放的氮氧化物（NOx）是造成环境污染的主要污染源之一。氨选择性催化还原（NH3-SCR）技术是目前最有效的NOx控制技术，而NH3-SCR催化剂的催化活性是该技术的核心。如今，分子筛基NH3-SCR催化剂已在该领域工业化并被广泛应用。但是，随着环保法规日益严苛及柴油机尾气“零排放”要求实施，开发具有更加优异催化活性以及抗中毒性能的分子筛基催化剂，特别是核壳结构催化剂显得尤为重要。本综述着重介绍了三种常用的Beta、ZSM-5、SSZ-13分子筛为内核的核壳结构分子筛基催化剂在NH3-SCR反应中最新的研究进展。还总结了抗高温水热老化，抗硫中毒，抗碳氢中毒以及抗碱金属中毒的反应机理，并解释了核与壳之间的界面效应在该反应中所起的重要作用。最后，对核壳结构分子筛基催化剂未来的发展和应用前景进行了展望。Abstract: Nitrogen oxides (NOx) from diesel engine exhaust is one of the main sources of environmental pollution. Zeolite-based NH3-SCR catalysts have extensively investigated and have shown great promise for the efficient reduction of NOx because of their excellent NH3-SCR performance, robust hydrothermal stability and outstanding N2 selectivity. However, with the increasingly stringent environmental regulations and the implementation of the requirement of “zero emission” of diesel engine exhaust, it is particularly important to develop zeolite-based catalysts with more excellent catalytic activity and anti-poisoning performance, especially core-shell structure catalyst. In this review, we mainly focus on the recent research progress of the core-shell structure zeolite-based catalysts for NH3-SCR reactions with three commonly used Beta, ZSM-5, and SSZ-13 zeolite as the cores, the reaction mechanism of resistance to hydrothermal aging, sulfur poisoning, hydrocarbon poisoning, and alkali metal poisoning, as well as the future development and application prospects of zeolite-based core-shell structure catalysts.
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Key words:
- NH3-SCR /
- zeolite /
- core-shell structure /
- resistance /
- interfacial effects
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图 5 (a) Cu-SSZ-13和 (b-c) Cu-SSZ-13@CZO的TEM照片，(d) CZO外壳的SAED照片，(e) Cu-SSZ-13@CZO的线扫图以及 (f-l) Cu-SSZ-13@CZO的EDS图[25]
Figure 5 Representative TEM results of (a) Cu-SSZ-13, (b-c) Cu-SSZ-13@CZO, (d) SAED patterns for the CZO shell, (e) line scanning of Cu-SSZ-13@CZO and (f-l) EDS mapping of Cu-SSZ-13@CZO[25]
(with permission from ACS Pubilcations)
图 6 Fe/Beta@SBA-15-1催化剂的TEM（a）和HR-TEM图像（b）和（c）；Fe/Beta@SBA-15-2催化剂的TEM图像（d）、（e）和SAED图（f）；Fe/Beta@SBA-15-2的（g）STEM图像、（h）EDS图和（i）线扫图[18]
Figure 6 TEM (a) and HR-TEM images (b) and (c) of Fe/Beta@SBA-15-1 catalyst; TEM image (d), (e) and the SAED pattern (f) of Fe/Beta@SBA-15-2 catalyst; (g) the STEM image, (h) the mapping elemental analyses and (i) the line scanning of a single Fe/Beta@SBA-15-2 microsphere[18]
(with permission from Wiley)
表 1 文献中报道的典型分子筛基核壳结构催化剂在NH3-SCR中的活性
Table 1 Activity of typical zeolite-based core-shell catalysts in NH3-SCR reaction as reported in the literatures
Zeolite based core-shell
catalystsLow-temperature activity
(t50 /℃)Temperature range
(t90 /℃)Test condition Ref. Fe-Beta@CeO2 183 225−565 [NO] = [NH3] = 5.0×10−4, [H2O] = 5%, [O2] = 3%, N2 balance, and GHSV = 50000 h−1 [14] Fe/Beta@Meso-CeO2 190 225−525 [NO] = [NH3] = 5.0×10−4, [O2] = 3%, N2 balance, and GHSV = 125000 h−1 [15] MoFe/Beta@CeO2 200 225−600 [NO] = [NH3] = 5.0×10−4, [H2O] = 10%, [O2] = 3%,
N2 balance, and GHSV = 50000 h−1[16] Fe/Beta@TiO2 275 450 [NO] = [NH3] = [C3H6] = 5.0×10−4, [O2] = 3%, [H2O] = 5%, N2 balance, and GHSV = 50000 h−1 [17] Fe/Beta@SBA-15 270 325−600 [NO] = [NH3] = 5.0×10−4, [O2] = 3%, N2 balance, and GHSV = 125000 h−1 [18] Fe-ZSM-5@CeO2 175 250−400 [NO] = [NH3] = 5.0×10−4, [O2] = 5%, N2 balance, and GHSV = 177000 h−1 [19] Fe-ZSM-5@Ce/mesoporous-silica 200 280−480 [NO] = [NH3] = 1.0×10−3, [O2] = 5%, N2 balance, and GHSV = 20000 h−1 [20] Fe-ZSM-5@silicalite-1 225 275−450 [NO] = [NH3] = 1.0×10−3, [O2] = 5%, N2 balance, and GHSV = 5510 h−1 [21] Cu/ZSM-5@CeO2 180 225−550 [NO] = [NH3] = 1.0×10−3, [O2] = 8%, He balance, and GHSV = 50000 h−1 [22] meso-Cu-SSZ-13@MAS 175 225−550 [NO] = [NH3] = 5.0×10−4, [H2O] = 5%, [O2] = 5%, N2 balance, and GHSV = 400000 h−1 [23] Cu-Ce-La/SSZ- 13@ZSM-5 165 225−450 [NO] = [NH3] = 5.0×10−4, [O2] = 5%, N2 balance, and GHSV = 600000 h−1 [24] Cu-SSZ-13@CZO 210 235−525 [NO] = [NH3] = 5.0×10−4, [O2] = 5%, N2 balance, and GHSV = 60000 h−1 [25] 
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