烃类催化裂解高选择性制低碳烯烃的分子筛催化剂

doi:10.11949/0438-1157.20230845

摘要/Abstract

摘要：

乙烯、丙烯等低碳烯烃是化学工业重要的基础原料。近年来，全球低碳烯烃的需求量持续增加，发展不同原料催化裂解增产低碳烯烃的技术仍将是主流方向。围绕催化裂解高效制备低碳烯烃工艺，阐述了分子筛催化剂制备及其催化裂解性能的研究进展，尤其是基于ZSM-5分子筛综述了催化裂解催化剂的研制及性能调控的研究进展，包括用于增产低碳烯烃的ZSM-5分子筛的高效合成及结构形貌控制，探讨了通过元素改性、多级孔结构制备对ZSM-5分子筛的织构性质、酸性质的调变，分析总结了其对原料转化率、低碳烯烃选择性和催化剂稳定性的影响，阐明了不同微观结构性质的ZSM-5分子筛催化剂上催化裂解增产低碳烯烃的构效关系，为精准调控ZSM-5分子筛的结构性质研究提供新思路，为设计烃类催化裂解制低碳烯烃工艺关键催化剂奠定基础。

关键词: 分子筛, ZSM-5, 催化, 性能调控, 选择性, 低碳烯烃

Abstract:

Light olefins such as ethylene and propylene are the most important basic raw materials in the chemical industry. In recent years, the global demand for light olefins has continued to increase, and the development of technology to increase the production of light olefins through catalytic cracking of different raw materials will remain the main direction. In this work, we focus on the efficient production of light olefins by catalytic cracking process and the research progress in the preparation and catalytic cracking performance of zeolite catalysts, especially in the synthesis and performance modulation mainly based on ZSM-5 zeolites is reviewed. For the increase of production of light olefins, ZSM-5 zeolites by using diversified synthesis method are provided, its modulation of texture and acid properties of ZSM-5 zeolites by modification with different elements, preparation of hierarchical porous structures are introduced, and the effects on feedstock conversion, light olefins selectivity and catalyst stability are emphatically discussed. The structure-activity relationship of catalytic cracking over the ZSM-5 catalysts to increase the production of light olefins is summarized and elucidated. Finally, the new ways for improving the regulation of light olefin distribution by precisely regulating ZSM-5 zeolites is further prospected, which lays the foundation for designing key catalysts for catalytic cracking hydrocarbons to produce light olefins.

Key words: molecular sieves, ZSM-5, catalysis, performance regulation, selectivity, light olefin

中图分类号:

O 643.3

刘琦, 陈子康, 朴宇, 肖鹏, 葛亚粉, 巩雁军. 烃类催化裂解高选择性制低碳烯烃的分子筛催化剂[J]. 化工学报, 2024, 75(1): 120-137.

Qi LIU, Zikang CHEN, Yu PIAO, Peng XIAO, Yafen GE, Yanjun GONG. Zeolite catalysts for catalytic cracking of hydrocarbon to increase light olefins selectivity[J]. CIESC Journal, 2024, 75(1): 120-137.

图/表 10

图1 ZSM-5分子筛的拓扑结构 [32]

Fig.1 Framework structure of ZSM-5 zeolite[32]

表1 不同分子筛催化剂的催化裂解性能

Table 1 The catalytic cracking performance of different zeolite catalysts

分子筛	硅铝比	实验条件	转化率/%	产物收率/%				文献
分子筛	硅铝比	实验条件	转化率/%	低碳烯烃	乙烯	丙烯	丁烯	文献
MCM-68	51	己烷, 550℃	45.0	—	12.0	50.0	—	[16]
丝光沸石	45	己烷, 550℃	45.3	—	14.0	41.0	—	[16]
ZSM-5	45	己烷, 550℃	59.0	—	20.0	37.0	—	[16]
Beta	41	己烷, 550℃	64.0	—	20.0	37.0	—	[16]
ZSM-5纳米片	54	正庚烷, 550℃	85.8	—	—	31.0	—	[33]
Y	10.7	正辛烷, 460℃, 空速3.88 h^-1	93.0	—	—	—	—	[35]
Beta	40	十二烷, 550℃	98.0	49.7	7.8	25.5	16.4	[38]
ZSM-5(块状,500 nm)	50	十二烷, 550℃	98.0	40.4	12.9	17.9	9.6	[38]
MCM-22	52	1-丁烯, 550℃, 空速5 h^-1	83.0	—	12.0	29.5	—	[41]

图2 (a)单MFI纳米片的结构模型；(b)MFI纳米片沿b轴形成多层堆叠；(c)单层结构的随机组合[57]；(d), (e)本课题组合成的片状结构ZSM-5分子筛SEM图和HRTEM图[59]；(f), (g)模板剂和F体系合成ZSM-5纳米片示意图及催化裂解性能[63]；(h), (i)柱支撑HZSM-5纳米片的SEM图和HRTEM图[65]

Fig.2 (a) Structure model for the single MFI nanosheet; (b) Many MFI nanosheets form either multilamellar stacking along the b-axis; (c) A random assembly of unilamellar structure[57]; (d), (e) The SEM and HRTEM images of ZSM-5 zeolite with a sheet-like structure combined in our group[59]; (f), (g) Schematic diagram of the synthesis of ZSM-5 nanosheets using template and fluoride and their catalytic cracking performance[63]; (h), (i) SEM and HRTEM images of the pillared HZSM-5 nanosheet zeolite[65]

图3 在不同体系下合成分子筛示意图及分子筛形貌图：(a)~(c)无有机模板剂合成体系[68,71,74]；(d)无溶剂合成体系[75,77]

Fig.3 Schematic for synthesizing zeolites in different systems and theirs morphology images: (a)—(c) organic-free synthesis system[68,71,74]; (d) solvent-free synthesis system[75,77]

图4 (a)传统金属改性ZSM-5分子筛的机理图[83]；(b)~(e)Fe、Mn改性ZSM-5分子筛的催化性能及裂解正辛烷反应网络[90]

Fig.4 (a) Schematic of possible mechanism for ZSM-5 modified by metal cations[83]; (b)—(e) Catalytic performance of Fe and Mn modified ZSM-5 and reaction network for cracking n-octane[90]

图5 (a)~(d)原位合成引入金属对分子筛Al分布的影响示意图及其催化性能[95-96]；(e)EFAL和BAS密度与己烷裂解反应速率的关系[97]；(f)~(i)ZSM-5分子筛Al物种的变化对催化裂解反应的影响[98]

Fig.5 (a)—(d) Schematic of the effect of introducing metals on the Al distribution of zeolites by in-situ synthesis and their catalytic performance[95-96]; (e) EFAL and BAS densities as a function of rate per site of the hexane cracking reaction[97]; (f)—(i) The effect of changes in Al species of ZSM-5 zeolites for catalytic cracking reaction[98]

表2 不同金属改性ZSM-5分子筛的孔性质

Table 2 The pore properties of different metal modified ZSM-5 zeolites

催化剂	改性金属及含量（质量分数）	ΔS_比表面积/ （m²/g）	ΔS_{微孔表面积}/ （m²/g）	ΔS_外表面积/ （m²/g）	ΔV_孔体积/ （cm³/g）	ΔV_微孔体积/ （cm³/g）	ΔV_介孔体积/ （cm³/g）	文献
1K/HZ-280	K, 1%	-97.0	—	—	-0.03	—	—	[81]
Ca-ZSM-5	Ca, —	-78.0	—	—	—	—	—	[82]
ZSM-5-Cs	Cs, —	-50.0	—	—	0.00	-0.02	—	[83]
0.5Fe/H-ZSM-5	Fe, 0.5%	-32.5	-13.5	-19.0	-0.02	-0.02	0.00	[87]
0.5Cu/H-ZSM-5	Cu, 0.5%	-13.3	-7.7	-5.6	-0.01	-0.01	+0.01	[87]
0.5Ni/H-ZSM-5	Ni, 0.5%	-34.9	-24.7	-10.2	-0.01	-0.02	0.00	[87]
Au/ZSM-5-8.5	Au, 0.5%	-47.0	+10.0	—	-0.03	+0.01	—	[93]
0.5%Au/ZSM-5	Au, 0.5%	-14.8	+6.1	—	-0.01	0.00	—	[94]
0.5%Au/2.0%La-ZSM-5	Au, 0.5%; La, 2.0%	-32.9	-4.6	—	-0.02	0.00	—	[94]

表3 不同金属改性ZSM-5分子筛的酸性质

Table 3 The acid properties of different metal modified ZSM-5 zeolites

催化剂	改性金属及含量（质量分数）	Δ总酸量/（mmol/g）	Δ弱酸量/（mmol/g）	Δ中强酸量/（mmol/g）	Δ强酸量/（mmol/g）	ΔB酸量/（mmol/g）	ΔL酸量/（mmol/g）	文献
1K/HZ-280	K, 1%	—	-0.02	—	—	—	—	[81]
ZSM-5-Cs	Cs, —	-0.86	—	—	—	—	—	[83]
Gd/HZSM-5	Gd, 7.54%	0.00	-0.01	—	+0.01	-0.17	-0.01	[84]
0.5Fe/H-ZSM-5	Fe, 0.5%	-0.22	-0.07	-0.03	-0.11	—	—	[87]
0.5Cu/H-ZSM-5	Cu, 0.5%	-0.16	-0.04	-0.04	-0.07	—	—	[87]
0.5Ni/H-ZSM-5	Ni, 0.5%	-0.17	-0.06	+0.04	-0.14	—	—	[87]
Zr-Z5	Zr, —	-0.12	-0.06	—	-0.06	-0.19	+0.07	[89]
Ag-Z5	Ag, —	-0.30	-0.38	—	+0.08	-1.56	+1.26	[89]
Au/ZSM-5-8.5	Au, 0.5%	-0.02	+0.01	-0.02	-0.01	—	—	[93]
0.5%Au/ZSM-5	Au, 0.5%	-0.02	-0.01	0.00	-0.01	—	—	[94]
0.5%Au/2.0%La-ZSM-5	Au, 0.5%; La, 2.0%	-0.05	-0.01	-0.02	-0.02	—	—	[94]

图6 “金属氧簇/分子筛”复合体（OX/ZEO）活性相材料微结构示意图

Fig.6 Schematic of the microstructure of “metal-oxygen cluster/zeolite” single-phase composite (OX/ZEO)

图7 (a)CuO x /ZSM-5复合催化剂的制备；(b)不同样品的微结构及失活行为；(c)不同样品的NH3-TPD曲线；(d)~(f)不同样品的催化裂解反应性能[108]

Fig.7 (a) Schematic of the preparation process of the CuO x /ZSM-5 catalyst; (b) The microstructure and deactivation behavior of different samples; (c) The NH3-TPD profiles of different samples; (d)—(f) The catalytic performance of different samples[108]

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