MnOx/MWCNTs低温氨选择性催化还原NOx硫中毒机理

doi:10.3866/PKU.WHXB201207062

物理化学学报 >> 2012, Vol. 28 >> Issue (09): 2175-2182.doi: 10.3866/PKU.WHXB201207062

MnO_x/MWCNTs低温氨选择性催化还原NO_x硫中毒机理

罗红成¹, 黄碧纯^1,2, 付名利^1,2, 吴军良^1,2, 叶代启^1,2

1. 华南理工大学环境科学与工程学院, 广州 510006;
2. 华南理工大学工业聚集区污染控制与生态修复教育部重点实验室, 广州 510006

收稿日期:2012-06-18 修回日期:2012-07-06 发布日期:2012-08-02
通讯作者: 黄碧纯 E-mail:cebhuang@scut.edu.cn
基金资助:
国家自然科学基金(209077034)资助项目

SO₂ Deactivation Mechanism of MnO_x/MWCNTs Catalyst for Low-Temperature Selective Catalytic Reduction of NOx by Ammonia

LUO Hong-Cheng¹, HUANG Bi-Chun^1,2, FU Ming-Li^1,2, WU Jun-Liang^1,2, YE Dai-Qi^1,2

1. College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006, P. R. China;
2. Key Laboratory of the Ministry of Education for Pollution Control and Ecosystem Restoration in Industry Clusters, South China University of Technology, Guangzhou 510006, P. R. China

Received:2012-06-18 Revised:2012-07-06 Published:2012-08-02
Supported by:
The project was supported by the National Natural Science Foundation of China (209077034).

摘要/Abstract

摘要：

以经过浓硝酸和等离子体放电预处理后的多壁碳纳米管(MWCNTs)为载体, 锰氧化物(MnO_x)为活性组分, 采用等体积浸渍法制备MnO_x/MWCNTs 催化剂. 利用热重分析(TGA)、扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、程序升温还原/脱附(TPR/TPD)以及傅里叶变换红外(FTIR)光谱对催化剂进行表征, 探讨SO₂对催化剂低温氨选择性催化还原(SCR)NO_x活性的影响及SO₂中毒机理. 结果表明, 低温下SO₂对MnO_x/MWCNTs 催化剂活性有明显毒化作用. 反应温度越高, SO₂浓度越大, 催化剂SCR活性下降越快. 活性中心Mn原子硫酸化是催化剂失活的主要原因. 另外, 催化剂表面生成硫酸铵盐以及SO₂对NO吸附的抑制作用也一定程度上造成了催化剂的失活.

关键词: 多壁碳纳米管, 选择性催化还原, 二氧化硫, 中毒机理

Abstract:

Manganese oxides supported on multi-walled carbon nanotubes (MnO_x/MWCNTs) catalysts were prepared by pore volume impregnation using MWCNTs as the catalyst support which was pretreated by concentrated nitric acid and oxygen dielectric barrier discharge plasma. The catalysts were characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction/desorption (TPR/ TPD), and Fourier transform infrared (FTIR) spectroscopy. The effect of SO₂ on the activity of the catalysts for low-temperature selective catalytic reduction (SCR) of NOx by ammonia and the SO₂ poisoning mechanism were investigated. The results showed that SO₂ had an obvious poisoning effect on the SCR activity of MnO_x/MWCNTs at low temperature. The activity decreased more rapidly as reaction temperature and SO₂ concentration increased. The observed deactivation was attributed to the sulfation of the active center atoms. Formation of ammonium sulfate on the catalyst surface and the inhibiting effect of SO₂ on NO adsorption also resulted in the deactivation of the catalysts to some extent.

Key words: Multi-walled carbon nanotubes, Selective catalytic reduction, Sulfur dioxide, Poisoning mechanism

罗红成, 黄碧纯, 付名利, 吴军良, 叶代启. MnO_x/MWCNTs低温氨选择性催化还原NO_x硫中毒机理[J]. 物理化学学报, 2012, 28(09), 2175-2182. doi: 10.3866/PKU.WHXB201207062

LUO Hong-Cheng, HUANG Bi-Chun, FU Ming-Li, WU Jun-Liang, YE Dai-Qi. SO₂ Deactivation Mechanism of MnO_x/MWCNTs Catalyst for Low-Temperature Selective Catalytic Reduction of NOx by Ammonia[J]. Acta Phys. -Chim. Sin. 2012, 28(09), 2175-2182. doi: 10.3866/PKU.WHXB201207062

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201207062

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I09/2175

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MnO_x/MWCNTs低温氨选择性催化还原NO_x硫中毒机理

SO₂ Deactivation Mechanism of MnO_x/MWCNTs Catalyst for Low-Temperature Selective Catalytic Reduction of NOx by Ammonia

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MnO_x/MWCNTs低温氨选择性催化还原NO_x硫中毒机理

SO₂ Deactivation Mechanism of MnO_x/MWCNTs Catalyst for Low-Temperature Selective Catalytic Reduction of NOx by Ammonia