催化学报 ›› 2011, Vol. 32 ›› Issue (7): 1227-1233.DOI: 10.3724/SP.J.1088.2011.10245

• 研究论文 • 上一篇    下一篇

改性 ZrO2-MnO2 基整体式催化剂上 NH3 选择性催化还原 NO

邱春天, 林涛*, 张秋林, 徐海迪, 陈耀强, 龚茂初*   

  1. 四川大学绿色化学与技术教育部重点实验室, 四川成都 610064
  • 收稿日期:2011-03-01 修回日期:2011-04-07 出版日期:2011-07-18 发布日期:2014-11-28

Selective Catalytic Reduction of NO with NH3 on Modified ZrO2-MnO2 Monolithic Catalysts

QIU Chuntian, LIN Tao*, ZHANG Qiulin, XU Haidi, CHEN Yaoqiang, GONG Maochu*   

  1. Key Laboratory of Green Chemistry & Technology of the Ministry of Education, Sichuan University, Chengdu, 610064, Sichuan, China
  • Received:2011-03-01 Revised:2011-04-07 Online:2011-07-18 Published:2014-11-28

摘要: 采用共沉淀法制备了 ZrO2-MnO2 催化剂, 考察了 CeO2, MoO3 和 WO3 的添加对 ZrO2-MnO2 整体式催化剂上 NH3 选择性催化还原 (NH3-SCR)NOx 的影响, 并利用低温 N2 吸附-脱附、X 射线衍射、X 射线光电子能谱、NH3 和 NO 程序升温脱附等方法对催化剂进行了表征. 结果表明催化剂物相为 Mn0.2Zr0.8O1.8 固溶体, CeO2 和 WO3 分散在其中; 添加 MoO3 或 WO3 后, 样品中出现了新的中强酸位, 强吸附的 NO 物种增加, 从而有利于催化剂中高温活性的提高. 另外, Mn 和 Ce 物种主要分别以 Mn4+ 和 Ce4+ 形式存在. 在 NH3-SCR 反应中, CeO2 的添加提高了 ZrO2-MnO2 催化剂的低温活性, 但反应温度窗口较窄; 继续添加 MoO3 或 WO3 后, 催化剂表现出良好的低温活性和宽的反应温度窗口, 其中 WO3/CeO2/ZrO2-MnO2 催化剂上 NO 的起燃温度为 176 oC, 且反应温度在 240~424 oC 范围内, NOx 转化率大于 90%, 具有良好的低温活性和宽的温度窗口.

关键词: 氮氧化物, 选择性催化还原, 整体式催化剂, 二氧化锆, 二氧化锰, 氧化铈, 三氧化钨

Abstract: A ZrO2-MnO2 catalyst was prepared by the co-precipitation method, and modified with CeO2, MoO3, and WO3 by impregnation. The catalytic activity of the monolithic catalysts for selective catalytic reduction of NOx with NH3 (NH3-SCR) was studied. All the catalysts were characterized by low temperature nitrogen adsorption-desorption, X-ray diffraction, X-ray photoelectron spectroscopy, and NH3/NO-temperature-programmed desorption. The results show that the phase of the catalysts is Mn0.2Zr0.8O1.8 solid solution, and CeO2 and WO3 are well dispersed in catalysts. When adding MoO3 or WO3 into the catalyst, some medium-strength acid sites and the strongly adsorbed NO species that are beneficial to the elevated temperature catalytic activity increase. Mn and Ce exist as Mn4+ and Ce4+. The low temperature SCR activity is improved by the modification with CeO2, but the temperature window of the reaction is relatively narrow. When MoO3 or WO3 is introduced into CeO2/ZrO2-MnO2, the catalyst exhibits better catalytic performance and wider temperature window. The light-off temperature of WO3/CeO2/ZrO2-MnO2 is 176 oC, and the NOx conversion is over 90% in the temperature range of 240–424 oC, and it has good low-temperature activity and wide temperature window.

Key words: nitrogen oxides, selective catalytic reduction, monolithic catalyst, zirconium dioxide, manganese dioxide, cerium oxide, tungsten trioxide