钾对Cu-SSZ-13催化剂脱硝性能及水热稳定性影响的研究

doi:10.19964/j.issn.1006-4990.2024-0642

Abstract

Abstract:

To explore the mechanism of the synergistic effect of chemical poisoning and high-temperature hydrothermal aging on the NH₃-SCR performance of Cu-SSZ-13 catalysts，various samples were generated by subjecting the catalysts to poisoning and high-temperature treatment on an engine test bench.The physicochemical properties of catalyst coatings at different locations within the monolithic catalyst were investigated by using BET，SEM，NH₃-TPD，and H₂-TPR.The results revealed that K deposition on the fresh catalyst displaced isolated Cu²⁺ and protons on framework Brønsted acid sites，leading to a reduction in the number of active Cu²⁺ ions in the catalyst framework，a decrease in acidity without crystal structure damage，and partial pore blockage.During the high-temperature hydrothermal aging process，the presence of K exacerbated the collapse of the zeolite framework and accelerated the transformation of Cu²⁺into Cu _x O _y species，which in turn inhibited the recombination of Al（OH）₃，leading to a significant decrease in specific surface area and redox properties.The deNO _x activity of the catalyst was examined by means of a fixed-bed reactor，and it was found that K weakened the activity and undermined the hydrothermal stability of the catalyst.After poisoning，the deNO _x efficiency of CZ at 200 ℃ and 500 ℃ was decreased from 92.84% and 89.38% to 85.64% and 83.22%（KCZ-1），respectively.After aging，the deNO _x efficiency of KCZ-HT1 at 200 ℃ and 500 ℃ was further deteriorated to 74.24% and 76.02%，a decrease of 15.7% and 10.8% compared to the unpolluted aged sample（CZ-HT）.In addition，the deposition of K in the catalyst was decreased along the gas flow direction，and the higher deposition at the front end resulted in poorer stability of the catalyst than at the back end.These findings provided an important basis for optimizing the design of anti-poisoning catalysts.This study clarified the mechanism by which K synergistically deteriorated catalyst activity and high-temperature hydrothermal stability through proton displacement and active site competition，etc，highlighting the sensitivity of D6R site Cu²⁺ to K poisoning and the significant impact on the stability of 8MRs site Cu²⁺ during aging，providing a theoretical basis for the targeted design of anti-poisoning catalysts.

Key words: Cu-SSZ-13, K poisoning, high-temperature hydrothermal stability, NH₃-SCR, deNO _x performance

CLC Number:

TQ127.2

FENG Xi, LÜ Liang, SUN Rui, LAI Yineng, YANG Lan, WANG Ruifang. Study on effect of potassium on deNO _x performance and hydrothermal stability of Cu-SSZ-13 catalysts[J]. Inorganic Chemicals Industry, 2025, 57(12): 123-130.

Figures/Tables 6

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References 26

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样品	WHTC-冷		WHTC-热		WHTC 加权排放量/（g·kW^-1·h^-1）	法规限值/ （g·kW^-1·h^-1）
样品	NO _x 排放量/（g·kW^-1·h^-1）	平均温度/ ℃	NO _x 排放量/（g·kW^-1·h^-1）	平均温度/ ℃	WHTC 加权排放量/（g·kW^-1·h^-1）	法规限值/ （g·kW^-1·h^-1）
DCZ	0.62	225.7	0.11	253.0	0.18	0.46
DCZ-HT	0.68	230.7	0.27	258.2	0.33
KCZ	0.72	227.9	0.12	257.4	0.20
KCZ-HT	1.00	224.2	0.40	256.3	0.48

催化剂	比表面积^a/ （m²·g^-1）	孔容^a/ （cm³·g^-1）	w（Cu）^b/ %	w（K）^b/ %
堇青石载体	13.67	0.02
H-SSZ-13	528.16	0.27
CZ	520.61	0.26
CZ-HT	489.31	0.24	2.76
KCZ-1	497.19	0.25
KCZ-HT1	405.98	0.20	2.63	1.21
KCZ-2	504.57	0.26
KCZ-HT2	453.81	0.23	2.79	0.37

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on effect of potassium on deNO _x performance and hydrothermal stability of Cu-SSZ-13 catalysts

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[1]	TAN Renjun, LUO Shizhong, WANG Tao, DU Peining, JING Fangli. Study on NH₃-SCR performance of manganese based catalysts doped with different elements [J]. Inorganic Chemicals Industry, 2023, 55(7): 115-121.
[2]	ZHOU Wei,ZHANG Gengrui,YU Haibin,MA Xinbin,LIU Fei,LIU Jiaxu. Study on solvent effect on preparation of MnO _x -ZSM-5 deNO _x catalysts [J]. Inorganic Chemicals Industry, 2022, 54(8): 138-144.