不同分子筛负载锰铈催化剂的低温NH<sub>3</sub>-SCR脱硝性能

黄增斌; 李翠清; 王振; 徐胜美; 冯凌波; 王虹; 宋永吉; 张伟

不同分子筛负载锰铈催化剂的低温NH₃-SCR脱硝性能

北京石油化工学院绿色化学与催化材料研究所, 北京 102617

基金项目:

国家自然科学基金 21343009

详细信息

通讯作者:
李翠清, Tel:010-81292124, E-mail:licuiqing@bipt.edu.cn

中图分类号: O643
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- 文章访问数: 380
- HTML全文浏览量: 248
- PDF下载量: 28
- 被引次数: 0
出版历程
- 收稿日期: 2016-04-15
- 修回日期: 2016-07-19
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-11-10

Performance of Mn-Ce catalysts supported on different zeolites in the NH₃-SCR of NO_x

Beijing Institute of Petrochemical Technology, Research Institute of Green Chemistry and Catalytic Material, Beijing 102617, China

Funds:

the National Natural Science Foundation of China 21343009

摘要

摘要: 分别以β、ZSM-5和USY分子筛为载体，采用浸渍法制备了锰铈催化剂，对其低温NH₃-SCR反应性能进行了评价，并采用XRD、BET、NH₃-TPD、H₂-TPR以及XPS对催化剂进行了表征。结果表明，三种分子筛负载的锰铈催化剂均具有较好的低温NH₃-SCR反应活性，其中，Mn-Ce/USY的催化性能最好，在107℃时NO_x转化率可达到90%。负载锰铈后催化剂的比表面积和孔体积均有所下降；活性组分MnO_x主要以无定型态分布于催化剂表面，且在ZSM-5上检测到聚集的CeO₂。催化剂表面弱酸对低温NH₃-SCR反应起主要作用，催化剂表面上活性组分的表面浓度和氧化态明显不同，较高的Mn⁴⁺/Mn³⁺原子比和吸附氧表面浓度对提高催化剂的低温NH₃-SCR反应活性有利。
- NH₃-SCR /
- 锰 /
- 铈 /
- 分子筛 /
- NO_x
Abstract: With various zeolites such as β, ZSM-5 and USY as the support, a series of Mn-Ce catalysts were prepared by impregnation method and characterized by XRD, BET, NH₃-TPD, H₂-TPR and XPS; their catalytic performance in the NH₃-SCR of NO_x at low temperature was investigated. The results show that all these catalysts are highly active in the NH₃-SCR reaction at low temperature; especially, over the Mn-Ce/USY catalyst, the conversion of NO_x reaches 90% at 107℃. After loaded of manganese and cerium, the specific surface area and pore volume of supported catalysts are decreased. Amorphous MnO_x as the active component and crystalline CeO₂ are detected on the surface of ZSM-5 zeolite. The weak acid sites on the catalyst surface probably play an important role in the NH₃-SCR at low temperature. Meanwhile, a high atomic ratio of Mn⁴⁺/Mn³⁺ and concentration of adsorbed oxygen may also promote the NH₃-SCR reaction at low temperature.
- NH₃-SCR /
- manganese /
- cerium /
- zeolite /
- NO_x

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图 1 不同载体负载的Mn-Ce催化剂的XRD谱图

Figure 1 XRD patterns of the Mn-Ce catalysts supported on different zeolites

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图 2 不同载体负载的Mn-Ce催化剂的H₂-TPR谱图

Figure 2 H₂-TPR profiles of Mn-Ce catalysts supported on different zeolites

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图 3 不同载体负载的Mn-Ce催化剂的NH₃-TPD谱图

Figure 3 NH₃-TPD profiles of the Mn-Ce catalysts supported on different zeolites

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图 4 不同载体负载的Mn-Ce催化剂的XPS谱图

Figure 4 XPS spectra of the Mn-Ce catalysts supported on different zeolites

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图 5 不同载体负载的Mn-Ce催化剂的NO_x转化率

Figure 5 NO_x conversion for NH₃-SCR over the Mn-Ce catalysts supported on different zeolites

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表 1 不同载体负载的Mn-Ce催化剂的BET及孔径

Table 1 BET surface area and pore size distribution of the Mn-Ce catalysts supported on different zeolites

Catalyst	Pore size d/nm	Pore volume v/(cm³·g^-1)	A_BET/(m²·g^-1)
β	45.51	0.95	492.08
Mn-Ce/β	45.76	0.87	306.74
USY	43.22	0.86	520.35
Mn-Ce/USY	44.06	0.79	362.27
ZSM-5	41.44	0.73	302.25
Mn-Ce/ZSM-5	42.99	0.69	199.38

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表 2 不同载体负载的Mn-Ce催化剂的H₂-TPR表征

Table 2 H₂-TPR results of the Mn-Ce catalysts supported on different zeolites

Catalyst	Temperature for the low temperature reduction peak t/℃	Area for the low temperature reduction peak
Mn-Ce/ZSM-5	345	24.6
Mn-Ce/USY	350	29.7
Mn-Ce/β	340	22.9

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表 3 不同载体负载的Mn-Ce催化剂的NH₃-TPD表征

Table 3 NH₃-TPD results of the Mn-Ce catalysts supported on different zeolites

Catalyst	Low temperature of desorption peaks t/℃	Peak area of low temperature desorption peak
Mn-Ce/ZSM-5	160	30.3
Mn-Ce/USY	155	31.1
Mn-Ce/β	157	30.6

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表 4 催化剂Mn 2p_3/2 XPS表征

Table 4 Results of curve-fittings on the Mn 2p_3/2 peak in XPS patterns of the Mn-Ce catalysts

Catalyst	Mn⁴⁺w_atom/%	Mn⁴⁺E_B/eV	Mn³⁺w_atom/%	Mn³⁺E_B/eV	Mn⁴⁺/Mn³⁺(atomic ratio)
Mn-Ce/ZSM-5	59.6	642.7	40.4	641.2	1.48
Mn-Ce/USY	92.7	642.7	7.3	641.2	12.70
Mn-Ce/β	62.1	642.7	37.9	641.2	1.64

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表 5 催化剂O 1s XPS表征

Table 5 Results of curve-fittings on the O 1s speak in XPS patterns of the Mn-Ce catalysts

Catalyst	Chemisorbed oxygen w_atom/%	Chemisorbed oxygen E_B/eV	Lattice oxygen w_atom/%	Lattice oxygen E_B/eV
Mn-Ce/ZSM-5	73.9	532.2	26.1	529.5
Mn-Ce/USY	95.5	532.2	4.5	529.5
Mn-Ce/β	91.7	532.2	8.3	529.5

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