School of Mechanical Engineering, Shanghai Jiao Tong University
Shanghai Marine Diesel Engine Research Institute

甲烷(CH4)是一种重要的温室气体,其引发温室效应的能力是等量 CO2的 25 倍。 船用天然气发动机排气中存在低浓度(0.05%~0.5%)CH4泄露。 CH4化学结构稳定,起燃温度高,低浓度 CH4难以被捕集利用,催化氧化是去除尾气中低浓度 CH4的主要方式。 贵金属钯(Pd)是完全氧化低浓度CH4性能良好的催化材料。 针对 Pd 基催化剂低温活性、可靠性以及研发成本等问题,本文介绍了目前 Pd 基催化剂主要研究进展。 首先明晰了催化剂的 Pd 粒径和价态分布、Pd 分散状态、载体种类以及强金属-载体间相互作用(SMSI)等对甲烷氧化活性的影响规律;其次,总结了目前公认的 Pd基催化剂表面甲烷氧化机理和反应路径;之后,详细阐述了 Pd 基催化剂运行过程中高温烧结、水中毒及硫中毒等多种失活机制;最后,总结了当前低浓度甲烷完全氧化面临的主要挑战以及未来甲烷氧化催化剂的发展方向,并简要提出了 Pd 基催化剂的性能改善策略。

Methane ( CH4) is an important greenhouse gas that is 25 times that its CO2 equivalent.There is low concentration (0.05% ~0.5%) CH4 leakage in marine natural gas engine exhaust. It is dif⁃ficult to capture and utilize low concentration CH4 because of its stable chemical structure and high ig⁃nition temperature. Catalytic oxidation is the main method to remove low concentration CH4 from tailgas. The noble metal palladium (Pd) is the best catalytic material for the complete oxidation of lowconcentration CH4. In this paper, the main research progress of Pd-based catalysts is reviewed for theirlow-temperature activity, reliability and development cost. Firstly, the effects of Pd particle size andvalence distribution, Pd dispersion state, type of support and strong metal-support interaction (SMSI)on methane oxidation activity are clarified; then, the mechanism of methane oxidation on the surface ofPd-based catalysts is summarized; in addition, the deactivation mechanisms of Pd-based catalysts,such as high temperature sintering, water poisoning and sulfur poisoning, are described in detail; final⁃ly, the main challenges and the future development of Pd-based catalysts for the complete oxidation oflow concentration methane are summarized, and the strategies for improving the performance of Pdbased catalysts are proposed.

国家自然科学基金青年基金(52106173); 国家自然科学基金青年基金(52006142)

0 引 言
1 低浓度甲烷催化氧化技术
2 钯基甲烷氧化催化剂简介
3 钯基催化剂的构效关系研究
3.1 Pd粒径分布对催化活性的影响
3.2 Pd分散态及价态分布对催化活性的影响
3.3 载体对催化活性的影响
3.4 强金属-载体间相互作用对催化活性的影响
4 Pd基催化剂的甲烷氧化机理研究
5 Pd基催化剂的失活机制研究
5.1 高温失活机制
5.2 水中毒机制
5.3 硫中毒机制
6 前景展望

赵旭腾, 侯进, 王一男, 等. 钯基催化剂氧化低浓度甲烷的研究进展[J]. 能源环境保护, 2023, 37(2):106-116.

ZHAO Xuteng, HOU Jin, WANG Yinan, et al. Research progress of palladium-based catalysts for oxidation oflow concentration methane[J]. Energy Environmental Protection, 2023, 37(2): 106-116.