锆修饰载体对锰铈复合催化剂NH3-SCR性能的影响

doi:10.16085/j.issn.1000-6613.2023-1919

摘要/Abstract

摘要：

采用水热法合成不同比例的铈锆载体，通过浸渍法将MnO _x 作为活性组分制备一系列复合催化剂，并考察其在以NH₃为还原剂的选择性催化还原NO _x 反应（NH₃-SCR）中的脱硝活性。通过XRD、Raman、SEM、N₂吸脱附、H₂-TPR、NH₃-TPD、XPS等技术手段对催化剂的结构、形貌、表面酸性、表面氧化价态等进行了表征。结果表明，水热法制备的Ce _n Zr_1-_n 较CeO₂载体具有更好的NH₃-SCR催化活性，8Mn/Ce _n Zr_1-_n 催化剂均有性能提升，其中8Mn/Ce_0.8Zr_0.2催化剂具有最佳的催化活性，其T₅₀和T₉₀分别为100.2℃和130.2℃，工作温度窗口为245.5℃（130.2~377.2℃），并且159.6~349.0℃范围内保持100%的NO转化率，具有更好的低温还原性能和更多的酸性位点，有利于反应物在更低的温度被吸附还原；其表面高价的Mn⁴⁺物种相对含量更高，有利于提升NH₃-SCR催化活性。

关键词: 稀土元素, NH₃选择性催化还原, 氮氧化物, 催化技术

Abstract:

A hydrothermal method was employed to synthesize cerium-zirconium (Ce _n Zr_1-_n ) supports with different ratios, and a series of composite catalysts were then prepared by impregnating MnO _x as the active component. The catalytic performance of these catalysts in the selective catalytic reduction of NO _x with ammonia (NH₃-SCR) was investigated. The catalysts were characterized by various techniques such as XRD, Raman, SEM, N₂ adsorption-desorption, H₂-TPR, NH₃-TPD, and XPS, to examine their structure, morphology, surface acidity, and surface oxidation state. The results indicated that Ce _n Zr_1-_n prepared by the hydrothermal method exhibited better NH₃-SCR catalytic activity than CeO₂ supports. Similarly, 8Mn/Ce _n Zr_1-_n catalysts show improved performance. Among them, the 8Mn/Ce_0.8Zr_0.2 catalyst exhibited the best catalytic activity, with T₅₀ and T₉₀ of 100.2℃ and 130.2℃, respectively. The working temperature window was 245.5℃ (130.2—377.2℃), and 100% NO conversion rate was maintained between 159.6℃ and 349.0℃. The catalyst demonstrated better low-temperature reduction performance and more acidic sites, which facilitated the adsorption and reduction of reactants at low temperatures. Furthermore, it had a relative high content of high-valence Mn⁴⁺ species on the surface, which contributed to enhancing NH₃-SCR catalytic activity.

Key words: rare earth element, ammonia-selective catalytic reduction, nitrogen oxide, catalysis technology

中图分类号:

O643

高梓寒, 杨润农, 王钊颖, 宋燕海, 覃斌, 余林. 锆修饰载体对锰铈复合催化剂NH₃-SCR性能的影响[J]. 化工进展, 2024, 43(11): 6206-6214.

GAO Zihan, YANG Runnong, WANG Zhaoying, SONG Yanhai, QIN Bin, YU Lin. Influence of zirconium modified carriers on the NH₃-SCR performance of manganese-cerium composite catalysts[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6206-6214.

图/表 13

图1 不同铈锆比载体及负载锰催化剂的NO转化率

表1 不同铈锆比载体及负载锰催化剂的起燃温度、完全转化温度、最高NO转化率和温度窗口

催化剂名称	T₅₀/℃	T₉₀/℃	最高NO转化率/%	工作温度窗口/℃
Ce	—	—	35.7	—
Ce_0.9Zr_0.1	—	—	48.3	—
Ce_0.8Zr_0.2	364.3	—	53.4	—
Ce_0.7Zr_0.3	—	—	48.8	—
Mn/Ce	104.0	150.4	98.0	150.4~353.5
Mn/Ce_0.9Zr_0.1	102.7	132.3	99.1	132.3~368.1
Mn/Ce_0.8Zr_0.2	100.2	130.2	100.0	130.2~375.7
Mn/Ce_0.7Zr_0.3	112	141.2	99.8	141.2~377.2

图2 不同铈锆比载体及负载锰催化剂的XRD图谱

图3 不同铈锆比载体及锰催化剂的Raman图谱

图4 不同铈锆比载体及锰催化剂的SEM图

图5 Mn/Ce0.8Zr0.2催化剂低倍数SEM图

图6 Mn/Ce0.8Zr0.2催化剂Mapping图

图7 不同铈锆比载体及负载锰催化剂的N2吸附-脱附曲线（内嵌图为BJH孔径分布图）

表2 不同铈锆比载体及负载锰催化剂的比表面积、孔容和平均孔径

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Ce	117.6	0.196	3.057
Ce_0.8Zr_0.2	125.7	0.183	3.057
Mn/Ce	106.1	0.192	3.063
Mn/Ce_0.8Zr_0.2	104.7	0.147	3.063

图8 不同铈锆比载体及负载锰催化剂的H2-TPR和NH3-TPD曲线

表3 不同铈锆比载体及负载锰催化剂H2消耗量和NH3脱附量

催化剂	H_总/mmol·g^-1	H_低温/mmol·g^-1	相对酸性位点总量
Ce	1.202	0.639	4.48
Ce_0.8Zr_0.2	1.447	0.848	4.97
Mn/Ce	1.564	1.095	4.94
Mn/Ce_0.8Zr_0.2	1.776	1.211	5.12

图9 不同铈锆比载体及负载锰催化剂的XPS图谱

表4 不同铈锆比载体及负载锰催化剂的表面元素组成

催化剂	Ce³⁺/(Ce³⁺+Ce⁴⁺)	Mn⁴⁺/(Mn³⁺+Mn⁴⁺)	O_A/(O_A+O_L)
Ce	0.179	—	0.225
Ce_0.8Zr_0.2	0.204	—	0.264
Mn/Ce	0.224	0.602	0.167
Mn/ Ce_0.8Zr_0.2	0.184	0.658	0.174

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锆修饰载体对锰铈复合催化剂NH₃-SCR性能的影响

Influence of zirconium modified carriers on the NH₃-SCR performance of manganese-cerium composite catalysts

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