机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展

doi:10.16085/j.issn.1000-6613.2022-1932

摘要/Abstract

摘要：

Cu-SSZ-13催化剂具有优异的CHA骨架结构，在机动车尾气脱硝领域具有很好的应用前景，目前在欧洲已经实现商业应用。为解决尾气中硫氧化物和水热冲击对Cu-SSZ-13骨架和活性位点产生的损害问题，对其进行改性是目前的研究重点。本文归纳了近年来针对Cu-SSZ-13催化活性位点的研究进展以及水热老化、硫中毒导致其失活的机理研究成果；重点论述了针对Cu-SSZ-13催化活性和耐受性能提升的最新改性方法（包括创建新型纳米结构、构建中毒牺牲位点、金属掺杂改性等），以期为提升Cu-SSZ-13催化性能和抗中毒性能研究提供新思路；对Cu-SSZ-13改性技术的未来发展进行展望，提出通过特定金属掺杂和新颖制备方法来控制沸石内的离子种类可实现调控活性位点的创新思路。最后针对性讨论了催化剂改性过程中需要解决的关键问题。

关键词: Cu-SSZ-13, NH₃-选择性催化还原, 水热失活, 硫中毒, 改性

Abstract:

Cu-SSZ-13 is an excellent deNO _x catalyst with CHA skeleton structure, and thus it possesses good application prospect in the field of vehicle exhaust deNO _x and has been applied commercially in Europe. However, the hydrothermal deactivation and sulfur poisoning of Cu-SSZ-13 will cause serious damage to the CHA skeleton structure and active sites of Cu-SSZ-13 and has limited its development. In order to solve these problems, the modification of Cu-SSZ-13 catalyst has become the focus of current research. The recent research progress on the active sites of Cu-SSZ-13 catalyst and the mechanism of its deactivation caused by hydrothermal aging and sulfur poisoning were summarized. Also, the latest modification methods aimed at improving the catalytic activity and tolerance of Cu-SSZ-13, such as creating new nanostructures, constructing poisoning sacrifice sites, metal doping modification, were discussed, which provides a new thought for enhancing the catalytic performance and anti-poisoning performance of Cu-SSZ-13. Furthermore, the future development of Cu-SSZ-13 modification technology was prospected with the innovative idea of regulation of the active site by specific metal doping and novel preparation methods to control the type of ions in the zeolite. Finally, the essential problems to be solved in catalyst modification were discussed.

Key words: Cu-SSZ-13, NH₃-SCR, hydrothermal deactivation, sulfur poisoning, modification

中图分类号:

X511

王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.

WANG Jingang, ZHANG Jianbo, TANG Xuejiao, LIU Jinpeng, JU Meiting. Research progress on modification of Cu-SSZ-13 catalyst for denitration of automobile exhaust gas[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4636-4648.

图/表 8

图1 分子筛结构

图2 Cu-SSZ-13中Cu2+、[Cu(OH)]+和Brønsted酸的位点结构[15]

图3 NH3-SCR反应的E-R和L-H机制示意图

图4 柴油车尾气后处理系统

图5 分子筛的原子沉积原理示意图

图6 金属掺杂改性机理示意图

图7 不同Nb负载的情况下活性测试变化[89]

图8 不同厚度的核壳催化剂活性测试变化[92]

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