分子筛吸附脱除有机硫的研究进展

doi:10.16085/j.issn.1000-6613.2023-2260

摘要/Abstract

摘要：

由于工业原料中硫化物的毒性与腐蚀性会对工业生产和生态健康带来不利影响，采用最优的脱硫技术实现硫化物的深度脱除意义重大。本文以吸附脱除复杂有机硫为调研范围，首先概述了吸附脱硫的优势与涉及的物理、化学吸附过程；随后以具有丰富孔结构和大比表面积的分子筛为调研对象，按照其孔道尺寸的不同，综述了微孔（FAU、MFI、β）、介孔（MCM-41、SBA-15、KIT-6、MCM-48）和多级孔分子筛在吸附脱除有机硫中的应用现状；进一步分析了分子筛脱硫性能的影响因素，包括活性组分种类、含量与分散度的影响，分子筛微观形貌与孔结构的影响，分子筛酸性位的影响等。分析可知，最后指出了分子筛脱硫剂的脱硫性能与分子筛载体自身的微观结构和表面性质密切相关，通过精确设计与可控制备脱硫剂使其具备硫容大、脱硫精度高、选择性高、孔结构稳定、寿命长、可再生利用等优良特质将是今后研究的重要方向。

关键词: 分子筛, 有机硫化物, 脱硫剂, 吸附脱硫

Abstract:

Due to the toxicity and corrosiveness of sulfides in industrial raw materials, which can adversely affect industrial production and ecological health, it is of great significance to use optimal desulfurization technology to achieve deep removal of sulfides. This paper took the adsorptive removal of complex organic sulfides as the research scope. Firstly, it described the advantages of adsorption desulfurization and the physical and chemical adsorption processes involved. Subsequently, it took zeolites with abundant pore structure and large specific surface area as the research object, and reviewed the application status of the microporous (FAU, MFI, Beta), mesoporous (MCM-41, SBA-15, KIT-6, MCM-48) and hierarchical zeolites in the adsorptive removal of organic sulfides in accordance with their different pore sizes. The factors affecting the desulfurization performance of zeolites, including the type, content and dispersion of active components, the micromorphology, pore structure and acid sites of zeolites were further analyzed. The analysis indicated that the desulfurization performance of zeolite desulfurizers was closely related to the microstructure of zeolite supports and the surface property. Through precise design and controlled synthesis to obtain the desulfurizers with large sulfur capacity, high desulfurization accuracy, high selectivity, stable pore structure, long service life, renewable use and other excellent qualities would be the important direction of future research.

Key words: zeolites, organic sulfides, desulfurizers, adsorptive desulfurization

中图分类号:

TE644

杨润农, 白帆飞, 林梓荣, 孙永明, 尹祥. 分子筛吸附脱除有机硫的研究进展[J]. 化工进展, 2025, 44(1): 329-340.

YANG Runnong, BAI Fanfei, LIN Zirong, SUN Yongming, YIN Xiang. Research progress on adsorptive removal of organic sulfides by zeolite[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 329-340.

图/表 7

参考文献 53

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样品名称	吸附硫化物	穿透硫容/mmol S·g^-1	平衡吸附硫容/mmol S·g^-1	参考文献
Y	TH	0.20（<1×10^-6）	—	[20]
ZSM-5	DMS	0.132（<2×10^-5）	—	[24]
ZSM-5	TH	—	0.04	[44]
β	TH+BT	0.156（<1×10^-6）	—	[29]
MCM-41	BT	0.02（<1×10^-6）	—	[42]
MCM-41	TH	—	0.16	[33]
SBA-15	BT	0.03（<1×10^-6）	—	[42]
KIT-6	BT	0.04（<1×10^-6）	—	[42]
KIT-6	TH	0.0336	—	[39]
Cu/Y	TH	0.95（<1×10^-6）	—	[20]
酸修饰的Y	TH	0.85（<1×10^-7）	—	[45]
Ce-ZSM-5	TH	—	0.16	[44]
Cu-ZSM-5	TH	—	0.08	[44]
Fe-ZSM-5	TH	—	0.06	[44]
Ni-ZSM-5	TH	—	0.15	[44]
Cu/β	TH+BT	0.239（<1×10^-6）	—	[29]
Ag/β	TH+BT	0.237（<1×10^-6）	—	[29]
Al-MCM-41	未知	0.25（<1×10^-4）	—	[46]
Fe-MCM-41	TH	—	0.165	[33]
Co-MCM-41	TH	—	0.162	[33]
Zn-MCM-41	TH	—	0.165	[33]
Cu/SBA-15	TH	—	0.155	[47]
La₂O₃/SBA-15	TH+BT+DBT	0.11	—	[35]
Cu-KIT-6	TH	—	0.398	[48]
CeO₂/KIT-6	TH	0.14	—	[37]
La₂O₃/KIT-6	TH	0.2	—	[38]
Ni/KIT-6	TH	0.195	—	[39]
Cu-MCM-48	TH	—	0.87	[40]
微-介孔氧化硅	BT	0.122（<1×10^-6）	—	[42]
微-介孔ZSM-5	TH	—	0.13	[44]
微-介孔ZSM-5	TH	—	0.057	[43]
Ni/微-介孔ZSM-5	TH	—	0.168	[43]
Cu/微-介孔ZSM-5	TH	—	0.44	[49]

样品名称	吸附硫化物	穿透硫容/mmol S·g^-1	平衡吸附硫容/mmol S·g^-1	参考文献
Y	TH	0.20（<1×10^-6）	—	[20]
ZSM-5	DMS	0.132（<2×10^-5）	—	[24]
ZSM-5	TH	—	0.04	[44]
β	TH+BT	0.156（<1×10^-6）	—	[29]
MCM-41	BT	0.02（<1×10^-6）	—	[42]
MCM-41	TH	—	0.16	[33]
SBA-15	BT	0.03（<1×10^-6）	—	[42]
KIT-6	BT	0.04（<1×10^-6）	—	[42]
KIT-6	TH	0.0336	—	[39]
Cu/Y	TH	0.95（<1×10^-6）	—	[20]
酸修饰的Y	TH	0.85（<1×10^-7）	—	[45]
Ce-ZSM-5	TH	—	0.16	[44]
Cu-ZSM-5	TH	—	0.08	[44]
Fe-ZSM-5	TH	—	0.06	[44]
Ni-ZSM-5	TH	—	0.15	[44]
Cu/β	TH+BT	0.239（<1×10^-6）	—	[29]
Ag/β	TH+BT	0.237（<1×10^-6）	—	[29]
Al-MCM-41	未知	0.25（<1×10^-4）	—	[46]
Fe-MCM-41	TH	—	0.165	[33]
Co-MCM-41	TH	—	0.162	[33]
Zn-MCM-41	TH	—	0.165	[33]
Cu/SBA-15	TH	—	0.155	[47]
La₂O₃/SBA-15	TH+BT+DBT	0.11	—	[35]
Cu-KIT-6	TH	—	0.398	[48]
CeO₂/KIT-6	TH	0.14	—	[37]
La₂O₃/KIT-6	TH	0.2	—	[38]
Ni/KIT-6	TH	0.195	—	[39]
Cu-MCM-48	TH	—	0.87	[40]
微-介孔氧化硅	BT	0.122（<1×10^-6）	—	[42]
微-介孔ZSM-5	TH	—	0.13	[44]
微-介孔ZSM-5	TH	—	0.057	[43]
Ni/微-介孔ZSM-5	TH	—	0.168	[43]
Cu/微-介孔ZSM-5	TH	—	0.44	[49]

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