Research progress of microwave-induced catalytic denitrification

doi:10.16085/j.issn.1000-6613.2020-1073

Abstract

Abstract:

The development of economical and efficient flue gas denitrification technology is an important research direction of air pollution control, in which microwave-induced catalytic denitrification has become a hotspot. This paper summarizes the research results of domestic and foreign researchers on microwave-induced catalytic treatment of NO_x in recent years, and introduces the related researches of microwave reduction denitrification and microwave oxidative denitrification, with the focuses on the usage of ammonium bicarbonate and activate carbon as reducing agent, and ZSM-5, metal oxide and perovskite-type mixed oxide as catalysts. Finally, it is proposed that the development of microwave catalytic oxidative denitrification and the exploration of its reaction mechanism are the important directions for the development of new flue gas denitrification technology.

Key words: catalyst, reduction, oxidation, microwave denitrification

摘要：

发展经济高效的烟气脱硝技术是大气污染控制领域的重要研究方向，利用微波诱导催化技术开展烟气脱硝已成为当前热点方向。本文对近年国内外研究人员关于微波诱导催化治理烟气NO_x的研究成果进行了综述，详细介绍了微波还原脱硝和微波氧化脱硝相关成果，重点讨论了以碳酸氢铵和活性炭为还原剂的微波诱导还原催化脱硝技术以及ZSM-5、金属氧化物和钙钛矿型混合氧化物微波催化还原脱硝技术。最后通过对比微波还原脱硝和微波氧化脱硝两种方法，提出研发微波催化氧化脱硝技术、探究其反应机理是开发新型烟气脱硝技术的重要方向。

关键词: 催化剂, 还原, 氧化, 微波脱硝

CLC Number:

HAO Runlong, QIAN Zhen, FU Le, YUAN Bo. Research progress of microwave-induced catalytic denitrification[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2747-2752.

郝润龙, 钱真, 符乐, 袁博. 微波诱导催化脱硝研究进展[J]. 化工进展, 2021, 40(5): 2747-2752.

Figures/Tables 6

References 32

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催化剂	还原剂	最佳反应条件			NO_x转化率 /%	SO₂转化率 /%	优缺点	参考文献
催化剂	还原剂	反应温度/℃	微波功率/W	O₂体积分数/%	NO_x转化率 /%	SO₂转化率 /%	优缺点	参考文献
Ni/HZSM-5	CH₄	225	200	2	96.0	—	Ni/HZSM-5脱硝效率高；但稳定性差，反应过程中易失活	[12]
Co/HZSM-5	CH₄	200	200	2	80.0	—	Ni/HZSM-5脱硝效率高；但稳定性差，反应过程中易失活	[12]
Ga-A型分子筛	尿素	104~113	259~280	—	92.0	—	在Ga-A型分子筛和尿素共同使用时微波脱硝效果好，但尿素作为还原剂会被消耗	[13]
Ga-A沸石	NH₄HCO₃	80~120	259~280	14~19	95.45	—	沸石和NH₄HCO₃在微波辐射下脱硝效率高；但NH₄HCO₃受热易分解，产生CO₂	[14]
沸石	NH₄HCO₃	200~250	211~280	—	86.5	99.1	沸石和NH₄HCO₃在微波辐射下脱硝效率高；但NH₄HCO₃受热易分解，产生CO₂	[15]
CuO	AC	350	420	—	92.5	<90.0	脱硝效率高，但脱硫效率不理想	[16]
Mn₂O₃		—			87.5	—
ZnO		—			87.5	—
CuO	AC	350	350	7.9	94.1	99.8	脱除效率高，但AC作为吸收剂会被消耗	[17]
Mn₂O₃	AC	300	400	5.8	98.7	—	AC在微波作用下选择性反应，减少其消耗量	[18]
CeO₂	AC	350	250	5	100.0	—	基本实现100%脱硝，但AC作为还原剂会被消耗	[19]
NiO_x-CeO₂		300	150		100.0	—
MnO_x-CeO₂		350	200		100.0	—
FeO_x-CeO₂		350	200		100.0	—

催化剂	还原剂	最佳反应条件			NO_x转化率 /%	SO₂转化率 /%	优缺点	参考文献
催化剂	还原剂	反应温度/℃	微波功率/W	O₂体积分数/%	NO_x转化率 /%	SO₂转化率 /%	优缺点	参考文献
Ni/HZSM-5	CH₄	225	200	2	96.0	—	Ni/HZSM-5脱硝效率高；但稳定性差，反应过程中易失活	[12]
Co/HZSM-5	CH₄	200	200	2	80.0	—	Ni/HZSM-5脱硝效率高；但稳定性差，反应过程中易失活	[12]
Ga-A型分子筛	尿素	104~113	259~280	—	92.0	—	在Ga-A型分子筛和尿素共同使用时微波脱硝效果好，但尿素作为还原剂会被消耗	[13]
Ga-A沸石	NH₄HCO₃	80~120	259~280	14~19	95.45	—	沸石和NH₄HCO₃在微波辐射下脱硝效率高；但NH₄HCO₃受热易分解，产生CO₂	[14]
沸石	NH₄HCO₃	200~250	211~280	—	86.5	99.1	沸石和NH₄HCO₃在微波辐射下脱硝效率高；但NH₄HCO₃受热易分解，产生CO₂	[15]
CuO	AC	350	420	—	92.5	<90.0	脱硝效率高，但脱硫效率不理想	[16]
Mn₂O₃		—			87.5	—
ZnO		—			87.5	—
CuO	AC	350	350	7.9	94.1	99.8	脱除效率高，但AC作为吸收剂会被消耗	[17]
Mn₂O₃	AC	300	400	5.8	98.7	—	AC在微波作用下选择性反应，减少其消耗量	[18]
CeO₂	AC	350	250	5	100.0	—	基本实现100%脱硝，但AC作为还原剂会被消耗	[19]
NiO_x-CeO₂		300	150		100.0	—
MnO_x-CeO₂		350	200		100.0	—
FeO_x-CeO₂		350	200		100.0	—

催化剂	最佳反应条件			NO_x 转化率/%	优缺点	参考文献
催化剂	反应温度/℃	微波功率/W	O₂体积分数/%	NO_x 转化率/%	优缺点	参考文献
Fe/NaZSM-5	300	16~18	2	70.0	20%Fe负载量的脱硝效果最佳，但总体脱硝效率偏低	[20]
Cu-ZSM-5	500~550	100	5	—	微波提高Cu-ZSM-5、Fe-ZSM-5稳定性和耐氧性，但其脱硝效率低	[21]
Fe-ZSM-5	400~600	100	5	—	微波提高Cu-ZSM-5、Fe-ZSM-5稳定性和耐氧性，但其脱硝效率低	[21]
MeO_x/Al₂O₃(Me=Cu,Mn,Fe)	250	100	10	94.8	CeCuMnO_x/Al₂O₃脱硝效率高，但其稳定性差且所含金属元素偏多	[23]
BaMn_xMg_1-_xO₃	250	<150	10	99.8	微波显著提高BaMn_xMg_1-_xO₃脱硝率，但Mn和Mg之间比例难控制	[25]
BaMnO₃	300	<150	10	93.7	脱硝效率好，但Ba和A位之间比例难控制，催化剂制备难度大	[26]
Ba_0.8Ca_0.2MnO₃	250			92.3
Ba_0.8K_0.2MnO₃	250			99.9
Ba_0.8La_0.2MnO₃	250			95.5
BaMoO₃	300	<150	10	93.7	Fe取代Me位的催化剂方便回收利用，但其脱硝效率低	[27]
BaCoO₃	250	<150		99.8
BaFeO₃	250	1000		64.1
MgCo₂O₄	300	<100	10	69.7	脱除效率高，但复合催化剂制备成本高	[28]
MgCo₂O₄-BaCO₃	250	<100	10	99.6	脱除效率高，但复合催化剂制备成本高	[28]

催化剂	最佳反应条件			NO_x 转化率/%	优缺点	参考文献
催化剂	反应温度/℃	微波功率/W	O₂体积分数/%	NO_x 转化率/%	优缺点	参考文献
Fe/NaZSM-5	300	16~18	2	70.0	20%Fe负载量的脱硝效果最佳，但总体脱硝效率偏低	[20]
Cu-ZSM-5	500~550	100	5	—	微波提高Cu-ZSM-5、Fe-ZSM-5稳定性和耐氧性，但其脱硝效率低	[21]
Fe-ZSM-5	400~600	100	5	—	微波提高Cu-ZSM-5、Fe-ZSM-5稳定性和耐氧性，但其脱硝效率低	[21]
MeO_x/Al₂O₃(Me=Cu,Mn,Fe)	250	100	10	94.8	CeCuMnO_x/Al₂O₃脱硝效率高，但其稳定性差且所含金属元素偏多	[23]
BaMn_xMg_1-_xO₃	250	<150	10	99.8	微波显著提高BaMn_xMg_1-_xO₃脱硝率，但Mn和Mg之间比例难控制	[25]
BaMnO₃	300	<150	10	93.7	脱硝效率好，但Ba和A位之间比例难控制，催化剂制备难度大	[26]
Ba_0.8Ca_0.2MnO₃	250			92.3
Ba_0.8K_0.2MnO₃	250			99.9
Ba_0.8La_0.2MnO₃	250			95.5
BaMoO₃	300	<150	10	93.7	Fe取代Me位的催化剂方便回收利用，但其脱硝效率低	[27]
BaCoO₃	250	<150		99.8
BaFeO₃	250	1000		64.1
MgCo₂O₄	300	<100	10	69.7	脱除效率高，但复合催化剂制备成本高	[28]
MgCo₂O₄-BaCO₃	250	<100	10	99.6	脱除效率高，但复合催化剂制备成本高	[28]

催化剂	氧化剂	最佳反应条件			NO_x转化率 /%	SO₂转化率 /%	优缺点	参考文献
催化剂	氧化剂	反应温度/℃	微波功率/W	O₂质量分数/%	NO_x转化率 /%	SO₂转化率 /%	优缺点	参考文献
FeCu/沸石	—	—	280	—	91.7	79.6	脱硝效率好，但脱硫效率低	[29]
沸石	KMnO₄	—	259	—	98.4	96.8	脱除效率高，但KMnO₄具有强腐蚀性和毒性	[30]
—	O₂/H₂O/SO₂	80	260	2~8	89.3	97.0	微波和光催化技术结合为烟气脱硝控制领域提供了新思路，但其反应成本和能耗偏高	[31]