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镍掺杂对用于CO-SCR反应的Fe/CeO催化剂抗氧性能的促进作用:活性测试与机理研究

Promotion effect of Ni doping on the oxygen resistance property of Fe/CeO catalyst for CO-SCR reaction: Activity test and mechanism investigation.

作者信息

Li Shuhao, Chen Xiaogen, Wang Feng, Xie Zongli, Hao Zerong, Liu Lijun, Shen Boxiong

机构信息

School of Energy and Environmental Engineering, Tianjin Key Laboratory of Energy Utilization and Pollutant Control, Hebei University of Technology, Tianjin 300401, China; Faculty of Science, Engineering and Technology, Swinburne University of Technology, Melbourne, VIC 3122, Australia.

School of Energy and Environmental Engineering, Tianjin Key Laboratory of Energy Utilization and Pollutant Control, Hebei University of Technology, Tianjin 300401, China.

出版信息

J Hazard Mater. 2022 Jun 5;431:128622. doi: 10.1016/j.jhazmat.2022.128622. Epub 2022 Mar 4.

Abstract

Catalytic reduction of NO using CO, which is usually present in the flue gas of the iron and steel industry, is considered as an economical and eco-friendly de-NO method (CO-SCR). However, the oxygen present in the flue gas will significantly inhibit the CO-SCR activity of the catalyst, thereby limiting its industrial application. Herein, catalysts based on iron and cerium oxides were prepared and modified with different metals to investigate their performance for the CO-SCR reaction in the presence of oxygen. The results show that the Fe/CeO catalyst can reach 99% NO conversion at 200 °C, but its activity decreased dramatically to 42.7% when the oxygen is present (0.5 vol%). By contrast, the NO conversion of Ni-doped Fe/CeO catalyst demonstrated significant enhanced oxygen resistance and could achieve 92% even at 150 °C in the presence of 0.5 vol% oxygen. Characterization techniques such as N adsorption, XRD, SEM/TEM, XPS, H-TPR, and in situ DRIFT were employed to investigate the mechanism of the improved oxygen resistance property of Ni-doped catalyst. The results show that the doped Ni can interact with Fe species, increases the BET surface area of the catalyst and generates more surface oxygen vacancies (SOV) and surface synergetic oxygen vacancy (SSOV) in CO-SCR reaction, thereby improving the redox performance of the catalyst. In situ DRIFT results show that the better redox performance of NiFe/CeO catalyst is conducive to the conversion of adsorbed NO species to the reactive intermediate NO species during the reaction. Meanwhile, the enhanced SOV/SSOV in the NiFe/CeO catalyst can remain active in the presence of oxygen. Therefore, the NiFe/CeO catalyst exhibits a promising catalytic activity in CO-SCR reaction when oxygen is present.

摘要

利用钢铁工业烟气中通常存在的一氧化碳对一氧化氮进行催化还原,被认为是一种经济且环保的脱硝方法(一氧化碳选择性催化还原法,即CO-SCR)。然而,烟气中存在的氧气会显著抑制催化剂的CO-SCR活性,从而限制其工业应用。在此,制备了基于铁和铈氧化物的催化剂,并用不同金属对其进行改性,以研究它们在氧气存在下的CO-SCR反应性能。结果表明,Fe/CeO催化剂在200℃时可实现99%的一氧化氮转化率,但当存在氧气(0.5体积%)时,其活性急剧下降至42.7%。相比之下,镍掺杂的Fe/CeO催化剂的一氧化氮转化率表现出显著增强的抗氧性,即使在存在0.5体积%氧气的情况下,在150℃时也能达到92%。采用诸如氮吸附、X射线衍射、扫描电子显微镜/透射电子显微镜、X射线光电子能谱、氢气程序升温还原以及原位漫反射红外傅里叶变换光谱等表征技术,来研究镍掺杂催化剂抗氧性改善的机理。结果表明,掺杂的镍可与铁物种相互作用,增加催化剂的比表面积,并在CO-SCR反应中产生更多的表面氧空位(SOV)和表面协同氧空位(SSOV),从而提高催化剂的氧化还原性能。原位漫反射红外傅里叶变换光谱结果表明,NiFe/CeO催化剂较好的氧化还原性能有利于反应过程中吸附态的一氧化氮物种转化为活性中间体一氧化氮物种。同时,NiFe/CeO催化剂中增强的SOV/SSOV在氧气存在下仍能保持活性。因此,NiFe/CeO催化剂在有氧气存在的CO-SCR反应中表现出有前景的催化活性。

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