Cu-SAPO-44分子筛的制备及其C3H6-SCR脱硝性能

doi:10.16085/j.issn.1000-6613.2022-0815

摘要/Abstract

摘要：

分别采用以硫酸铜为铜源、环己胺为单模板剂，以硫酸铜为铜源、环己胺为模板剂、聚乙二醇（PEG2000）为协同模版剂，以Cu-TEPA（四乙烯五胺）和环己胺共模板剂3种制备方法，一步水热合成Cu-SAPO-44分子筛催化剂，用于选择性催化丙烯还原柴油机车尾气氮氧化物（C₃H₆-SCR）。采用X射线衍射、N₂吸附-脱附、扫描电镜、紫外可见光谱、H₂程序升温还原和NH₃程序升温脱附等方法对催化剂进行表征，考察不同模板剂对Cu-SAPO-44物理化学特性和C₃H₆-SCR性能的影响。结果表明，以Cu-TEPA为模板剂制备Cu-SAPO-44时，Cu-TEPA既作为结构导向剂又提供活性铜物种，合成的分子筛结晶度高，铜负载量大，具有更多的活性Cu²⁺和丰富的表面酸性，为C₃H₆-SCR反应提供了大量的活性位点，因此具有最佳的脱硝性能。在含有10% O₂和5% H₂O的稀薄燃烧烟气条件下，在300~350℃可实现90%以上的NO _x 转化率和N₂选择性。而引入PEG2000对提高Cu-SAPO-44分子筛的脱硝效果不明显。经过50h的持续脱硝反应测试，Cu-SAPO-44(T)催化剂表现出良好的反应稳定性。

关键词: 模板剂, Cu-SAPO-44, 选择性催化还原, 一氧化氮, 丙烯

Abstract:

Cu-SAPO-44 catalysts were synthesized by three preparation methods: copper sulfate as copper source and cyclohexylamine as single template; copper sulfate as copper source, cyclohexylamine as template and polyethylene glycol (PEG2000) as synergistic template; and Cu-TEPA (tetraethylenepentamine) and cyclohexylamine as co-templates. These catalysts were used for selective catalytic reduction of nitric oxide with propylene (C₃H₆-SCR) under diesel engine exhaust. These zeolites were characterized by X-ray diffraction (XRD), N₂ adsorption-desorption, scanning electron microscopy (SEM), UV-vis spectroscopy (UV-vis), H₂ temperature-programmed reduction (H₂-TPR) and NH₃ temperature-programmed desorption (NH₃-TPD). The results showed that Cu-TEPA template not only acted as structure directing agent, but also provided active copper species. Then, Cu-SAPO-44 catalyst prepared with Cu-TEPA template had high crystallinity, large copper loading, more active Cu²⁺ ions and rich surface acidity, which provided a large number of active sites for C₃H₆-SCR reaction. Therefore, it had the best de-NO _x performance, which could obtain more than 90% NO _x conversion and about 90% N₂ yield at 300—350℃ under lean burning condition containing 10% O₂ and 5% H₂O. However, the introduction of surfactant PEG2000 had little effect on improving the activity of Cu-SAPO-44 catalyst. The Cu-SAPO-44(T) catalyst indicated appropriate reaction stability in long term test of 50hours.

Key words: template, Cu-SAPO-44, selective catalytic reduction, nitric oxide, propylene

中图分类号:

X511

周皞, 张恒, 温妮妮, 王旭瑞, 徐璐, 李玮, 苏亚欣. Cu-SAPO-44分子筛的制备及其C₃H₆-SCR脱硝性能[J]. 化工进展, 2023, 42(3): 1373-1382.

ZHOU Hao, ZHANG Heng, WEN Nini, WANG Xurui, XU Lu, LI Wei, SU Yaxin. Preparation and de-NO _x performance of C₃H₆-SCR over Cu-SAPO-44 catalyst[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1373-1382.

图/表 13

表1 不同模板剂合成的Cu-SAPO-44催化剂的各元素成分

催化剂样品	元素质量分数/%
催化剂样品	Cu	Al	P	Si
Cu-SAPO-44(S)	3.992	14.655	14.692	5.595
Cu-SAPO-44(P)	3.986	14.630	14.720	5.837
Cu-SAPO-44(T)	5.016	15.021	13.463	6.654

图1 Cu-SAPO-44催化剂C3H6-SCR性能测试装置1—减压阀；2—质量流量计；3—电磁阀；4—预热炉；5—注射泵；6—反应器；7—FTIR红外光谱仪

图2 不同模板剂合成的Cu-SAPO-44催化剂和纯SAPO-44分子筛XRD谱图

图3 不同模板剂合成的Cu-SAPO-44催化剂氮气吸附脱附等温曲线和孔径分布图

表2 不同模板剂合成的Cu-SAPO-44催化剂的孔隙结构参数

催化剂样品	比表面积/m²·g^-1	孔容量/cm³·g^-1	孔径/nm
Cu-SAPO-44(S)	602	0.226	1.788
Cu-SAPO-44(T)	488	0.182	1.498
Cu-SAPO-44(P)	577	0.216	1.498

图4 不同模板剂合成的Cu-SAPO-44催化剂和纯SAPO-44分子筛SEM图像

图5 不同模板剂合成的Cu-SAPO-44催化剂的UV-vis吸收谱图

表3 不同模板剂合成的Cu-SAPO-44催化剂中铜物种的峰面积和百分比

催化剂样品	孤立Cu²⁺		CuO
催化剂样品	峰面积	比例/%	峰面积	比例/%
Cu-SAPO-44(S)	94.60	28.8	234.43	71.2
Cu-SAPO-44(T)	59.04	33.3	118.02	66.7
Cu-SAPO-44(P)	77.48	30.7	174.80	69.3

图6 不同模板剂合成的Cu-SAPO-44催化剂H2-TPR谱图

图7 不同模板剂合成的Cu-SAPO-44催化剂NH3-TPD谱图

图8 不同模板剂合成Cu-SAPO-44催化剂的NO x 转化率、C3H6转化率和N2选择性［测试条件：NO 500mL/m3，C3H6 500mL/m3，O2 100L/m3，H2O 50L/m3，空速15L/(g·h)］

图9 250℃时不同模板剂合成Cu-SAPO-44催化剂中孤立Cu2+含量与NO x 转化速率之间的关系

图10 Cu-SAPO-44(T)催化剂的脱硝持久性测试[测试条件：NO 500mL/m3，C3H6 500mL/m3，O2 100L/m3，空速15L/(g·h)]

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Cu-SAPO-44分子筛的制备及其C₃H₆-SCR脱硝性能

Preparation and de-NO _x performance of C₃H₆-SCR over Cu-SAPO-44 catalyst

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