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在 SO2 和 H2O 存在的情况下,Mn/CeO2、Mn/ZrO2 和 Mn/Ce-ZrO2 用于低温选择性催化还原 NO 与 NH3 的对比研究。

A comparative study of Mn/CeO2, Mn/ZrO2 and Mn/Ce-ZrO2 for low temperature selective catalytic reduction of NO with NH3 in the presence of SO2 and H2O.

机构信息

College of Environmental Science and Engineering, Nankai University, Tianjin 300071, China.

出版信息

J Environ Sci (China). 2013 Apr 1;25(4):791-800. doi: 10.1016/s1001-0742(12)60109-0.

Abstract

Ce-ZrO2 is a widely used three-way catalyst support. Because of the large surface area and excellent redox quality, Ce-ZrO2 may have potential application in selective catalytic reduction (SCR) systems. In the present work, Ce-ZrO2 was introduced into a low-temperature SCR system and CeO2 and ZrO2 supports were also introduced to make a contrastive study. Mn/CeO2, Mn/ZrO2 and Mn/Ce-ZrO2 were prepared by impregnating these supports with Mn(NO3)2 solution, and have been characterized by N2-BET, XRD, TPR, TPD, XPS, FT-IR and TG. The activity and resistance to SO2 and H2O of the catalysts were investigated. Mn/Ce-ZrO2 and Mn/CeO2 were proved to have better low-temperature activities than Mn/ZrO2, and yielded 98.6% and 96.8% NO conversion at 180 degrees C, respectively. This is mainly because Mn/Ce-ZrO2 and Mn/CeO2 had higher dispersion of manganese oxides, better redox properties and more weakly adsorbed oxygen species than Mn/ZrO2. In addition, Mn/Ce-ZrO2 showed a good resistance to SO2 and H2O and presented 87.1% NO conversion, even under SO2 and H2O treatment for 6 hours, and the activity of Mn/Ce-ZrO2 was almost restored to its original level after cutting off the injection of SO2 and H2O. This was due to the weak water absorption and weak sulfation process on the surface of the catalyst.

摘要

Ce-ZrO2 是一种广泛应用的三效催化剂载体。由于其具有较大的比表面积和良好的氧化还原性能,Ce-ZrO2 在选择性催化还原(SCR)系统中可能具有潜在的应用前景。本工作将 Ce-ZrO2 引入低温 SCR 系统,并引入 CeO2 和 ZrO2 载体进行对比研究。采用浸渍法制备了 Mn/CeO2、Mn/ZrO2 和 Mn/Ce-ZrO2 催化剂,通过 N2-BET、XRD、TPR、TPD、XPS、FT-IR 和 TG 对催化剂进行了表征。考察了催化剂的活性、抗 SO2 和 H2O 性能。结果表明,Mn/Ce-ZrO2 和 Mn/CeO2 具有较好的低温活性,在 180°C 时分别达到 98.6%和 96.8%的 NO 转化率。这主要是因为 Mn/Ce-ZrO2 和 Mn/CeO2 中 MnOx 的分散度较高,氧化还原性能较好,弱吸附氧物种较多,而 Mn/ZrO2 则相反。此外,Mn/Ce-ZrO2 具有较好的抗 SO2 和 H2O 性能,在 SO2 和 H2O 处理 6 小时后仍能保持 87.1%的 NO 转化率,且在停止注入 SO2 和 H2O 后,其活性几乎恢复到原始水平。这是由于催化剂表面的水吸收较弱和硫酸盐化过程较弱。

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