CuCe-SAPO-34选择性催化丙烯还原柴油车尾气氮氧化物

doi:10.16085/j.issn.1000-6613.2023-0746

摘要/Abstract

摘要：

采用等体积浸渍法制备CuCe-SAPO-44分子筛催化剂，用于选择性催化丙烯还原柴油车尾气氮氧化物（C₃H₆-SCR）。采用X射线衍射（XRD）、N₂吸附-脱附、紫外可见光谱（UV-Vis）、H₂程序升温还原（H₂-TPR）和NH₃程序升温脱附（NH₃-TPD）等方法对催化剂的物理化学性质进行表征。研究表明，引入的铈与铜物种之间存在相互作用，有利于生成更多的孤立Cu²⁺物种，提高了分子筛催化剂的低温氧化还原性能，从而提高了CuCe-SAPO-34的低温脱硝活性。同时，双金属分子筛骨架上具有丰富的Lewis酸性位，有助于C₃H₆和NO _x 的吸附和活化。当Cu∶Ce=4∶2时，CuCe-SAPO-34催化剂具有最佳的脱硝性能，在含有10%O₂和5%H₂O的柴油车尾气氛围中，在250℃最高能实现90%以上的脱硝效率。

关键词: 分子筛催化剂, 铈, 选择催化还原, 氮氧化物, 丙烯

Abstract:

CuCe-SAPO-44 zeolite catalysts were prepared by incipient wet impregnation method, and their activities of selective catalytic reduction of nitric oxide with propylene (C₃H₆-SCR) were investigated under lean burning condition. These catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption-desorption, UV-vis spectroscopy (UV-Vis), H₂ temperature-programmed reduction (H₂-TPR) and NH₃ temperature-programmed desorption (NH₃-TPD). The results had shown that the interaction between the introduced cerium and copper species was beneficial for generating more isolated Cu²⁺ species which improved the low-temperature redox performance of the CuCe-SAPO-34 zeolite catalysts, and thus enhanced the low-temperature SCR activity. There were abundant Lewis acid sites on the skeleton of the bimetallic zeolite catalysts, which were favorable for the adsorption and activation of NO _x and C₃H₆. When Cu∶Ce=4∶2, CuCe-SAPO-34 exhibited the best de-NO _x activity with a conversion of NO _x more than at 90% when the diesel engine exhaust contained 10% O₂ and 5% H₂O at 250℃.

Key words: zeolite catalysts, cerium, selective catalytic reduction, nitrogen oxide, propylene

中图分类号:

X511

周皞, 王旭瑞, 赵辉爽, 温妮妮, 苏亚欣. CuCe-SAPO-34选择性催化丙烯还原柴油车尾气氮氧化物[J]. 化工进展, 2024, 43(6): 3093-3099.

ZHOU Hao, WANG Xurui, ZHAO Huishuang, WEN Nini, SU Yaxin. Selective catalytic reduction of nitric oxide with propylene over CuCe-SAPO-34 catalysts under diesel engine exhaust[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3093-3099.

图/表 9

表1 CuCe-SAPO-34分子筛催化剂的元素分析

样品	元素质量分数/%
样品	Al	Cu	P	Si	Ce
4Cu4Ce-SAPO-34	16.72	4.19	16.72	3.98	4.17
4Cu2Ce-SAPO-34	17.76	4.28	17.95	4.13	2.04
4Cu1Ce-SAPO-34	18.26	4.39	18.47	4.28	1.14
4Ce-SAPO-34	17.53	—	17.63	4.05	3.98
4Cu-SAPO-34	15.75	4.01	16.35	3.46	—

图1 CuCe-SAPO-34分子筛催化剂的XRD图谱

图2 CuCe-SAPO-34分子筛催化剂的N2吸附-脱附等温线

表2 CuCe-SAPO-34分子筛催化剂的织构特性

样品	比表面积 /m²·g^-1	微孔面积 /m²·g^-1	孔隙体积 /cm³·g^-1
4Cu4Ce-SAPO-34	421.2	395.6	0.148
4Cu2Ce-SAPO-34	555.7	535.0	0.198
4Cu1Ce-SAPO-34	557.7	544.2	0.201
4Cu-SAPO-34	592.5	575.9	0.225
4Ce-SAPO-34	613.5	581.7	0.214

图3 CuCe-SAPO-34分子筛催化剂的紫外可见光谱

图4 CuCe-SAPO-34分子筛催化剂的H2-TPR谱图

图5 CuCe-SAPO-34分子筛催化剂的NH3-TPD谱图

图6 CuCe-SAPO-34分子筛催化剂的NO x 转化率、C3H6转化率和N2选择性

图7 SO2对4Cu2Ce-SAPO-34分子筛催化剂C3H6-SCR活性和稳定性的影响

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