酸性金属氧化物对锰铈氧化物催化剂脱硝温度窗口的调控作用

doi:10.1016/S1872-2067(14)60106-6

催化学报 ›› 2014, Vol. 35 ›› Issue (8): 1281-1288.DOI: 10.1016/S1872-2067(14)60106-6

酸性金属氧化物对锰铈氧化物催化剂脱硝温度窗口的调控作用

聂久远^a, 吴晓东^b,c, 马子然^b, 许腾飞^a, 司知蠢^c, 陈磊^c, 翁端^b,c

a. 清华大学材料学院新型陶瓷与精细工艺国家重点实验室, 北京 100084;
b. 清华大学材料学院先进材料教育部重点实验室, 北京 100084;
c. 清华大学深圳研究生院, 广东深圳 518055

收稿日期:2014-03-30 修回日期:2014-04-11 出版日期:2014-08-01 发布日期:2014-08-05
通讯作者: 吴晓东
基金资助:
国家重点基础研究发展计划（973计划，2010CB732304）；国家高技术研究发展计划（863计划，2013AA065302）；国家自然科学基金（51202126）.

Tailored temperature window of MnO_x-CeO₂ SCR catalyst by addition of acidic metal oxides

Jiuyuan Nie^a, Xiaodong Wu^b,c, Ziran Ma^b, Tengfei Xu^a, Zhichun Si^c, Lei Chen^c, Duan Weng^b,c

a. State Key Laboratory of New Ceramics & Fine Process, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China;
b. The Key Laboratory of Advanced Materials of Ministry of Education, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China;
c. Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, Guangdong, China

Received:2014-03-30 Revised:2014-04-11 Online:2014-08-01 Published:2014-08-05
Supported by:
This work was supported by the National Basic Research Program of China (973 Program, 2010CB732304), the National High Technology Research and Development Program of China (863 Program, 2013AA065302), and the National Natural Science Foundation of China (51202126).

摘要/Abstract

摘要：

利用溶胶-凝胶法，采用三种酸性金属氧化物（氧化铌、氧化钨和氧化钼）对锰铈复合氧化物催化剂进行了改性. 测试了催化剂的氮氧化物选择性催化还原（SCR）活性，以筛选对应不同温度窗口的合适酸性氧化物改性剂. 同时评价了催化剂的NO氧化和NH₃氧化活性. 利用X射线衍射、BET比表面积测试、H₂程序升温还原、NH₃/NO_x程序升温脱附和NH₃/NO_x吸附红外光谱等手段对催化剂进行了表征. MnO_x-CeO₂催化剂表现出良好的低温（100-150 ℃）活性. 酸性金属氧化物的添加削弱了催化剂的氧化还原特性，从而抑制了NH₃的活化和NO₂辅助的快速SCR反应. 与此同时，相对高温（250-350 ℃）区NH₃的氧化也受到了抑制，B酸和L酸上的NH₃吸附得以增强. 因此，催化剂的SCR脱硝温度窗口向高温移动，改性效果Nb₂O₅ < WO₃ < MoO₃.

关键词: 选择性催化还原, 锰铈复合氧化物, 酸性金属氧化物, 温度窗口, 氧化还原位, 酸性位

Abstract:

A MnO_x-CeO₂ catalyst was modified with various acidic metal oxides (Nb₂O₅, WO₃, and MoO₃) using a sol-gel method. The activities of the obtained catalysts were measured for the selective catalytic reduction (SCR) of NO_x with NH₃ to screen suitable acidic metal oxides for different temperature windows. The catalytic activities for NO and NH₃ oxidation were also evaluated. The catalysts were characterized by X-ray diffraction, N₂ adsorption, H₂ temperature-programmed reduction, NH₃/NO_x temperature-programmed desorption analyses, and infrared spectroscopic measurements of NH₃/NO_x adsorption. The MnO_x-CeO₂ catalyst exhibited the greatest low-temperature (100-150 ℃) activity. The addition of acidic metal oxides weakened the redox properties of the catalyst, resulting in inhibition of the partial oxidation of the adsorbed NH₃ and NO₂-assisted fast SCR reactions. Meanwhile, the oxidation of NH₃ at relatively high temperatures (250-350 ℃) was suppressed, and the adsorption of NH₃ on Brönsted and Lewis acid sites was strengthened. Consequently, the temperature window of SCR reaction shifted to higher temperatures in the order Nb₂O₅< WO₃< MoO₃.

Key words: Selective catalytic reduction, MnO_x-CeO₂ mixed oxide, Acidic metal oxide, Temperature window, Redox site, Acid site

聂久远, 吴晓东, 马子然, 许腾飞, 司知蠢, 陈磊, 翁端. 酸性金属氧化物对锰铈氧化物催化剂脱硝温度窗口的调控作用[J]. 催化学报, 2014, 35(8): 1281-1288.

Jiuyuan Nie, Xiaodong Wu, Ziran Ma, Tengfei Xu, Zhichun Si, Lei Chen, Duan Weng. Tailored temperature window of MnO_x-CeO₂ SCR catalyst by addition of acidic metal oxides[J]. Chinese Journal of Catalysis, 2014, 35(8): 1281-1288.

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酸性金属氧化物对锰铈氧化物催化剂脱硝温度窗口的调控作用

Tailored temperature window of MnO_x-CeO₂ SCR catalyst by addition of acidic metal oxides

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酸性金属氧化物对锰铈氧化物催化剂脱硝温度窗口的调控作用

Tailored temperature window of MnOx-CeO2 SCR catalyst by addition of acidic metal oxides

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Tailored temperature window of MnO_x-CeO₂ SCR catalyst by addition of acidic metal oxides