分子筛限域丙烷脱氢催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2024-0476

摘要/Abstract

摘要：

在“双碳”目标的背景下，丙烷直接脱氢制丙烯技术在近年得到迅速推广应用。替代催化剂的开发是丙烷脱氢新型工艺开发的核心问题。分子筛因能将金属团簇封装在孔道内或锚定于骨架上，而成为制备高效、稳定脱氢催化剂的理想载体。本文从不同活性中心的角度出发，系统阐述了铂基、铑基、锌基、钴基等分子筛限域催化剂的合成方法，金属纳米团簇与分子筛骨架间相互作用以及催化作用机制的研究进展，分析了分子筛限域催化剂在高温下关键组分流失、活性中心团聚的不足，提出了强化金属与分子筛相互作用的调控思路。最后指出为早日实现工业替代，分子筛限域催化剂还应从基础科学问题和适应于工业条件的催化剂放大两方面进行深入研究。

关键词: 丙烷脱氢, 催化剂, 分子筛, 限域效应

Abstract:

In response to the Dual Carbon Targets, propane direct dehydrogenation technology has been rapidly applied in recent years. The development of alternative catalysts is a core issue in the development of novel processes. Zeolites, capable of encapsulating metal clusters within the pores or anchoring them on the framework, have become an ideal support for preparing highly-efficient and stable dehydrogenation catalysts. The synthesis methodologies for zeolite-confined catalysts, including those based on platinum, rhodium, zinc, cobalt, have been systematically described according to their different active centers. Research progress on the interactions between metal nanoclusters and zeolite frameworks, as well as their catalytic mechanisms, has been reviewed. The limitations of zeolite-confined catalysts, such as key component loss at high temperature and active center aggregation, have been identified. Strategies to strengthen the interaction between metals and zeolite frameworks have been proposed. It is prospected that, in order to accelerate industrial application of zeolite-confined catalysts, further research is necessary to be conducted on both fundamental scientific issues and scaling up of the catalysts suitable for industrial conditions.

Key words: propane dehydrogenation, catalysts, zeolite, confinement effects

中图分类号:

O643.3

洪学思, 吴省, 宋磊, 缪长喜, 杨为民. 分子筛限域丙烷脱氢催化剂的研究进展[J]. 化工进展, 2024, 43(10): 5517-5526.

HONG Xuesi, WU Xing, SONG Lei, MIAO Changxi, YANG Weimin. Review on zeolite confined catalysts for propane dehydrogenation[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5517-5526.

图/表 7

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催化剂	反应温度/℃	原料组成	质量空速/h^-1	转化率/%	选择性/%	反应时间/h	参考文献
CrO _x /Al₂O₃	575~590	工业级丙烷	—	45	91.9	生产周期	[7]
Pt-Sn/Al₂O₃	580~640	工业级丙烷	—	35	90.7	生产周期	[7]
0.72%Pt1.0%Zn@S-1-H	550	C₃H₈/N₂=1/3	3.6	47.4~40.4	93.2~99.2	216.7	[12]
0.45%Pt/1.10%Zn@S-1-Fin	600	C₃H₈	12	48.3~44.9	97.1~96.9	80	[14]
0.19%Pt/2.56%Zn-SPP	550	C₃H₈/He=1:3	1350	42.5	>99	288	[16]
0.2%Pt/1.4%Sn@S-1	550	C₃H₈/N₂=1/3	3.6	35~45	97~99	300	[19]
0.26%Pt/0.47%Sn-Si-Beta	550	C₃H₈/N₂=1/19	1	25.2~27.5	99.1~99.9	24	[22]
0.092%Pt/0.82%Ga@S-1	600	C₃H₈/N₂=1/19	0.65	41.5~45.9	92~95	24	[28]
0.35%Rh/1.93%In@S-1	550	C₃H₈	8	23~25	99	5500	[35]
3.28%Zn@MFI-P	580	C₃H₈	7.85	25~34	95	4	[38]
0.98%Co@S-1	590	C₃H₈/H₂/N₂=5/4/5	3.7	30~35	93	12	[46]
1.728%Fe/H-ZKD-1	600	C₃H₈/N₂=1/24	19.8	22.63	96	12	[49]

催化剂	反应温度/℃	原料组成	质量空速/h^-1	转化率/%	选择性/%	反应时间/h	参考文献
CrO _x /Al₂O₃	575~590	工业级丙烷	—	45	91.9	生产周期	[7]
Pt-Sn/Al₂O₃	580~640	工业级丙烷	—	35	90.7	生产周期	[7]
0.72%Pt1.0%Zn@S-1-H	550	C₃H₈/N₂=1/3	3.6	47.4~40.4	93.2~99.2	216.7	[12]
0.45%Pt/1.10%Zn@S-1-Fin	600	C₃H₈	12	48.3~44.9	97.1~96.9	80	[14]
0.19%Pt/2.56%Zn-SPP	550	C₃H₈/He=1:3	1350	42.5	>99	288	[16]
0.2%Pt/1.4%Sn@S-1	550	C₃H₈/N₂=1/3	3.6	35~45	97~99	300	[19]
0.26%Pt/0.47%Sn-Si-Beta	550	C₃H₈/N₂=1/19	1	25.2~27.5	99.1~99.9	24	[22]
0.092%Pt/0.82%Ga@S-1	600	C₃H₈/N₂=1/19	0.65	41.5~45.9	92~95	24	[28]
0.35%Rh/1.93%In@S-1	550	C₃H₈	8	23~25	99	5500	[35]
3.28%Zn@MFI-P	580	C₃H₈	7.85	25~34	95	4	[38]
0.98%Co@S-1	590	C₃H₈/H₂/N₂=5/4/5	3.7	30~35	93	12	[46]
1.728%Fe/H-ZKD-1	600	C₃H₈/N₂=1/24	19.8	22.63	96	12	[49]

分类	技术方案	参考文献
前处理	配体保护法	[12]，[13]，[19]
前处理	多模板剂法	[14]
后处理	浸渍法	[16]，[17]
	脱铝处理法	[18]
	固相研磨法	[23]
	重结晶法	[25]

分类	技术方案	参考文献
前处理	配体保护法	[12]，[13]，[19]
前处理	多模板剂法	[14]
后处理	浸渍法	[16]，[17]
	脱铝处理法	[18]
	固相研磨法	[23]
	重结晶法	[25]

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