低温脱硝催化剂研究进展

doi:10.19964/j.issn.1006-4990.2021-0602

摘要/Abstract

摘要：

在传统选择性催化还原技术（SCR）催化剂的基础上,分别以钒-钛系催化剂、固溶体催化剂和新型MnO _x 催化剂为重点介绍了近些年低温SCR催化剂的研究进展,综述了不同活性组分的复合型催化剂的制备方法、元素掺杂、反应机理和抗性等,并通过分析不同复合型催化剂的表征总结了催化剂的性能状况以及低温脱硝效率,着重阐述了新型MnO _x 催化剂所具有的优异脱硝特性,认为通过改性提高新型MnO _x 的抗水抗硫性将会成为该领域未来的发展方向和研究热点,最后介绍了不同负载体对新型MnO _x 催化剂的催化效率的影响规律,发现二氧化钛负载体具有良好的抗水性,三氧化二铝负载体能显著增强催化活性,二氧化铈负载体的热稳定性较好。

关键词: SCR催化剂, 钒-钛系催化剂, 固溶体催化剂, 新型MnO _x 催化剂, 抗水抗硫性

Abstract:

On the basis of conventional selective catalytic reduction（SCR） catalysts,the research progress on low-temperature SCR catalysts was introduced by taking V-Ti catalysts,solid solution catalysts and new MnO _x catalysts as key points.The preparation methods,element doping,reaction mechanism and resistance of composite catalysts with different active components were reviewed.By analyzing the characterization of different composite catalysts,the performance and low-temperature denitration efficiency of the catalyst were summarized.The excellent denitration characteristics of the new MnO _x catalyst was emphatically expounded.It was considered that improving the water and sulfur resistance of new MnO _x by modification would become the development direction and research hotspot in this field in the future.Finally,the influence of different carriers on the catalytic efficiency of the new MnO _x catalyst was introduced.It was found that TiO₂ carrier had good H₂O resistance,Al₂O₃ carrier could significantly enhance the catalytic activity,and CeO₂ carrier had good thermal stability.

Key words: SCR catalyst, V-Ti catalyst, solid solution catalyst, new MnO _x catalyst, water and sulfur resistance

中图分类号:

O643.36

余沃晖,张盼,赵一明,查中发,吴瑞龙,齐立强. 低温脱硝催化剂研究进展[J]. 无机盐工业, 2022, 54(10): 57-68.

YU Wohui,ZHANG Pan,ZHAO Yiming,ZHA Zhongfa,WU Ruilong,QI Liqiang. Research progress on low-temperature denitration catalysts[J]. Inorganic Chemicals Industry, 2022, 54(10): 57-68.

图/表 15

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表5

不同负载体的SCR催化剂的性质及特点

负载体	晶型	负载体特性	常见活性组分		催化剂的特性
TiO₂	八面体	弱酸性或无酸性负载,具有路易斯酸性中心,适合负载非惰性金属氧化物	MnO _x /TiO₂		在高Mn负载量下,以微晶和聚合物的形式存在,促进脱硝反应
			MnO _x -CeO₂/TiO₂		在高Mn负载量下,复合催化剂抗水性良好
			Fe-Mn-Ce/TiO₂		TiO₂使活性组分均匀分布在负载体上
γ- Al₂O₃	八面体	支撑和均匀分散活性成分,具有良好分散性、适度氧化还原性、较多酸性位	MnO _x /γ-Al₂O₃		具有良好分散性、适度氧化还原性、较多酸性位、优良NO_x吸附性能以及含有丰富的Mn⁴⁺
γ- Al₂O₃	八面体	支撑和均匀分散活性成分,具有良好分散性、适度氧化还原性、较多酸性位	MnO _x -CeO₂/Al₂O₃		Al³⁺的引入可以减小CeO₂-MnO _x 催化剂的晶粒尺寸,且Al³⁺显著增加了其比表面积和孔容,这是由于微晶尺寸的减小
CeO₂	三角双锥	CeO₂与其他金属氧化物之间的协同作用能提高催化剂活性、选择性及稳定性	LaMnO₃/CeO₂		LaMnO₃和CeO₂之间的相互作用在低温段有利于晶格氧的移动,促进部分NO氧化成NO₂,具有较好的催化性能
CeO₂	三角双锥	CeO₂与其他金属氧化物之间的协同作用能提高催化剂活性、选择性及稳定性	CuO/CeO₂		在高温下不会形成复合物,热稳定性良好
SiO₂	表面不存在空位	酸性氧化物,化学性质比较稳定,具有较好催化效率、催化活性、催化剂负载的牢固性	V-Mo-Ce/TiO₂-SiO₂		SiO₂可以显著增加比表面积,并影响表面原子间的相互作用；SiO₂对于催化剂的脱硝性能影响较小,但在SO₂存在下表现出较好的催化活性
分子筛	四面体	具有规则、稳定的骨架结构和较高的比表面积,及其较高的热和水热稳定性,确保了活性金属的高度分散,以及反应物和产物的高效扩散,促进反应的迅速进行	Fe基 Cu基	ZSM、SSZ、SAPO等系列	①在通电的条件下,Mn的引入提高了Mn-Cu/ZSM-5催化剂的催化性能；②Cu/ZSM-5在NH₃存在时的产物是NH₄HSO₄,且NH₄HSO₄会与Cu（HSO₄）₂相互转化,控制NH₃的量能提高对Cu/SSZ-13回收效果；③Cu-SSZ-13催化剂显示出优异的NH₃-SCR反应性和较强的SO₂耐受性

表5

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脱硝工艺		脱硝率/%		还原/氧化剂	反应温度/℃	催化剂	工艺缺点
干法脱硝	氧化法	光催化氧化	70~75	TiO₂、硫化镉	无	使用	光子产率低、光源单一
		氧化物氧化	70~80	金属氧化物	无	不使用	需处理废弃金属氧化物
		等离子体氧化	60~90	氨水	无	不使用	能耗大,伴随氨逃逸
	分解法	光催化分解	一般	无	无	使用	反应活化能高,所需温度高
	分解法	热催化分解	一般	无	＞500	使用	反应活化能高,所需温度高
	还原法	光催化还原	一般	NH₃或醇类	无	使用	催化还原效果不理想、反应不完全
		SCR	75~90	NH₃或尿素	100~400	使用	无明显缺点
		SNCR	40~70	NH₃或尿素	800~1 300	不使用	氨逃逸
	吸附法（活性炭和活性焦）	50~80		NH₃或尿素	150~200	使用	抗硫性差、脱硝效率低
湿法脱硝	吸收法	溶液吸收	较高	无	＜150	不使用	产生废液、能耗高、酸循环需求量大
		气相氧化吸收		O₂、O₃、ClO₂等			O₃成本高、ClO₂易造成二次污染
		液相氧化吸收		Fenton试剂、含氯氧化剂等			成本高,易造成二次污染
	生物法	70~80		无	无	不使用	脱硝效率低

催化剂类型	制备方法	n（Fe）/n（Ce）	优点	缺点
Fe_0.5Ce_0.5O₂^[12]	共沉淀法	1∶1	工艺简单、固溶体颗粒均匀	催化剂颗粒易聚合、比表面积低
Fe₁Ce_0.35固溶体^[13]	水热合成法	1∶0.35	纯度高、分散性好、污染小、能耗低	设备昂贵、投资高
Fe_0.2Ce_0.8O_2-_δ^[14]	固相法	1∶4	反应温度低、产物颗粒小、粒度分布窄、比表面积大	污染较大、反应时间长
Fe_0.5Ce_0.5O₂^[15]	溶胶-凝胶法	1∶1	工艺简单	容易导致反应不彻底

催化剂	类型	制备方法	最佳活性（NO _x 转化率）	物质的量比	催化剂特点（活性机理）	文献来源
无负载体	Mn-Ce	表面活性剂模板法	100~200 ℃,＞95%	n（Mn）/n（Ce）=1	较高的比表面积,活性中心均匀,易于吸附NH₃和NO _x,抗硫性突出	[27]
	Mn-Ce	共沉淀法	150 ℃,约为95%	n（Mn）/n（Ce）=1	较高的比表面积,活性中心均匀,易于吸附NH₃和NO _x,抗硫性突出	[27]
	La_1-_x Ce _x MnO₃	溶胶-凝胶法	135 ℃,＞90%	n（Mn）/n（La）/n（Ce）= 1∶0.8∶0.2	Ce掺杂增加了La-Mn氧化物的表面Mn⁴⁺含量、化学吸附氧	[28]
有TiO₂负载体	Mn-Ce-Ho/TiO₂	浸渍法	140~220 ℃,＞90% 180 ℃,约为96%	n（Mn）/n（Ce）/n（Ti）/ n（Ho）=0.4∶0.07∶1∶0.1	提高了Mn⁴⁺含量,使化学吸附氧增加	[30]
	Ru-Mn-Ce/TiO₂	浸渍法	120~250 ℃,几乎100%	无	CMRT-X催化剂脱硝活性降低是由于过量的NH₃氧化以及N₂O副产物生成	[31]
	W-Mn-Ce/TiO₂	浸渍法	160 ℃,几乎100%	无	热稳定性增加,增加了NH₃吸附量和反应活性,但抑制NO吸附	[32]
	Mn-Sb/TiO₂	溶胶-凝胶法	100℃,约为95%	n（Mn）/n（Ti）=0.2 n（Sb）/n（Ti）=0.2	生成更多的还原物质、Mn⁴⁺和表面吸附氧	[33]
	Tm-MnO _x /TiO₂	浸渍法	150~270 ℃,几乎100%	n（Mn）/n（Ti）=1∶3 n（Tm）/n（Ti）=0.1∶1	提高了催化剂的表面酸性、还原性、Mn⁴⁺和表面化学吸附氧浓度	[34]
	Sm-Mn/TiO₂	超声波浸渍法	110~250 ℃,大于80%	n（Mn）/n（Sm）=2∶1	改善了MnO _x 在催化剂表面的分散性,增加了比表面积、路易斯酸位点和O _α 的相对浓度	[35]

催化剂种类	制备方法	烟气工况	脱硝效率	参考文献
Ce_0.4Mn/TiO₂	反向共沉淀法	GSHV=44 000 h^-1, 5%H₂O+220 mg/m³ SO₂	200 ℃-99%下降到73%-4 h	[37]
Fe_0.2Co_0.4Mn-Ce/TiO₂	湿式浸渍法	GSHV=12 000 h^-1, 10%H₂O+440 mg/m³ SO₂	200 ℃-98%下降到90%-4 h	[38]
Co₁Mn₄Ce₅O _x	共沉淀法	GSHV=48 000 h^-1, 10%H₂O+330 mg/m³ SO₂	175 ℃-91%下降到73%-6 h	[39]
Ni₁Mn₄Ce₅O _x	共沉淀法	GSHV=48 000 h^-1, 10%H₂O+330 mg/m³ SO₂	175 ℃-91%下降到76%-6 h	[39]
Mn-Eu/TiO₂	溶胶-凝胶法	GSHV=108 000 h^-1,10%H₂O+220 mg/m³ SO₂	150 ℃-85%下降到70%-25 h	[40]
Nb₂O₅-Mn-Ce/AC	湿式浸渍法	GSHV=14 500 h^-1, 350 mg/m³ SO₂	225 ℃-85%下降到70%-3.5 h	[41]

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