非热等离子体协同锰铁双金属催化剂直接催化还原NO

doi:10.16085/j.issn.1000-6613.2022-0107

摘要/Abstract

摘要：

传统氨选择性催化还原（NH₃-SCR）法在大气污染物NO的脱除中得到广泛应用，但仍存在催化剂有毒、操作温度高及氨逃逸等缺点，不能满足日益增多的低温应用场景和更高的环保要求。本文采用浸渍法制备了SBA-15分子筛负载的锰铁双金属催化剂，研究了非热等离子体协同催化剂低温下直接催化还原NO的性能。活性测试结果表明，室温下等离子体输出电压为12kV时，等离子体协同催化的NO转化率达到97.8%。表征结果显示等离子体协同反应前后催化剂的孔道结构和物理形貌未见明显变化。在线质谱分析结果表明，等离子体协同催化作用下，NO被直接分解为N₂和O₂。由机理分析可知，不同价态Mn物种间的电子传递削弱了催化剂表面吸附态NO分子中N—O键，使得等离子体分解NO的能耗下降。

关键词: 氮氧化物, 非热等离子体, 催化剂, 化学过程, 反应工程

Abstract:

Although the traditional ammonia selective catalytic reduction (NH₃-SCR) has been widely used in the removal of atmospheric pollutant NO, there are still some flaws such as catalyst toxicity, high and narrow operating temperature, and ammonia emission. Herein, the manganese-iron bimetallic catalyst supported on SBA-15 molecular sieve was prepared by the impregnation method, and the performance of the manganese-iron catalyst to directly decompose NO under non-thermal plasma at low temperature was investigated. The activity test results showed that the NO conversion reached 97.8% when the plasma output voltage was 12kV at room temperature. The characterization results showed that the pore structure and physical morphology of the catalyst did not change significantly after the reaction. The online mass spectrometry analysis results showed that under the synergistic catalysis of plasma, NO was directly decomposed into N₂ and O₂. The mechanism analysis showed that the electron transfer between different valence Mn species weakened the N—O bond of the NO adsorbed on catalyst surface, and the energy consumption of the plasma to decompose NO was also reduced.

Key words: nitrogen oxide, non-thermal plasma, catalyst, chemical processes, reaction engineering

中图分类号:

O643

谭潇, 齐随涛, 周一鸣, 石利斌, 程光旭, 伊春海, 杨伯伦. 非热等离子体协同锰铁双金属催化剂直接催化还原NO[J]. 化工进展, 2022, 41(11): 5850-5857.

TAN Xiao, QI Suitao, ZHOU Yiming, SHI Libin, CHENG Guangxu, YI Chunhai, YANG Bolun. Direct catalytic reduction of NO by bimetallic ferromanganese catalyst under non-thermal plasma[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 5850-5857.

图/表 8

图1 等离子体协同催化时能量密度两大因素对NO转化率的影响

图2 不同电压下等离子体单独和协同MnFe/SBA-15催化剂对NO转化率的影响

图3 MnFe/SBA-15催化剂反应前后表征结果对比图

表1 MnFe/SBA-15催化剂的BET比表面积、孔容及孔径

样品	比表面积^①/m²·g^-1	孔容^②/cm³·g^-1	平均孔径^②/nm
反应前	422.29	0.66	6.42
反应后	410.15	0.66	6.40

图4 MnFe/SBA-15催化剂反应前后的Mn 2p和O 1s XPS谱图

表2 MnFe/SBA-15催化剂反应前后表面不同O和Mn元素质量分数

样品	X_O/%		X_Mn/%
样品	表面吸附氧及氧空位（O_α）	晶格氧（O_β）	Mn⁴⁺	Mn³⁺	Mn²⁺
反应前	95.0	5.0	17.8	57.2	27.0
反应后	96.3	3.7	5.1	64.0	30.9

图5 等离子体协同MnFe/SBA-15催化剂分解NO的在线质谱分析结果

图6 非热等离子体协同MnFe/SBA-15催化剂直接催化还原NO机理示意图

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