单晶多级孔ZSM-5分子筛酸性质对正庚烷催化裂解反应传质性能的影响

doi:10.16085/j.issn.1000-6613.2023-2088

摘要/Abstract

摘要：

采用L-赖氨酸作为介孔模板剂，通过调控铝源（偏铝酸钠）添加量改变分子筛硅铝比，在单晶分子筛内部引入晶内介孔，成功地合成了一系列具有不同硅铝比的单晶多级孔ZSM-5分子筛，研究了其酸性质对正庚烷催化裂解反应传质性能的影响。利用X射线衍射（XRD）、N₂物理吸附、氨气程序升温脱附（NH₃-TPD）、吡啶红外（Py-IR）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）等表征了单晶多级孔ZSM-5分子筛的物理结构、酸性质和微观形貌。同时，利用零长柱（ZLC）装置测试获取了正庚烷在单晶多级孔ZSM-5分子筛中的表观扩散系数，用于反映其传质性能。研究结果表明，随着硅铝比的提高，单晶多级孔ZSM-5分子筛的物理结构基本保持一致；传质性能随酸量的减少而提升，催化裂解性能随酸量的增加而提高。当单晶多级孔ZSM-5分子筛的Si/Al从80提高至140，正庚烷的表观扩散系数提升了87%以上；当单晶多级孔ZSM-5分子筛的Si/Al=80时，正庚烷的转化率最高可达97.5%，乙烯和丙烯的选择性分别为24.3%和35.1%。

关键词: L-赖氨酸, 硅铝比, 单晶多级孔ZSM-5分子筛, 传质, 催化, 反应

Abstract:

Single-crystalline hierarchical ZSM-5 zeolite with intracrystalline mesopore was successfully synthesized by using L-lysine as a mesoporous template, and the Si/Al ratio was changed by adjusting the adding amount of aluminum source (sodium metaaluminate). Then the effect of acidic properties on zeolite’s activity and mass transfer in n-heptane catalytic cracking was investigated in detail. The physical structure, acidic properties and micromorphology of single-crystalline hierarchical ZSM-5 zeolite were characterized by using X-ray diffraction (XRD), nitrogen physical adsorption, ammonia temperature-programmed desorption (NH₃-TPD), pyridine infrared (Py-IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In addition, the zero-length column (ZLC) device was employed to test the apparent diffusivity of n-heptane in single-crystalline hierarchical ZSM-5 zeolite,which was used to characterize its mass transfer performance. The results showed that the physical structure of single-crystalline hierarchical ZSM-5 zeolite kept almost the same with the increase of Si/Al ratio, while the zeolite’s mass transfer performance was improved with the decrease of acid amount, but the catalytic cracking performance was enhanced with the increase of acid amount. When the Si/Al ratio of the single-crystalline hierarchical ZSM-5 zeolite increased from 80 to 140, the apparent diffusivity of n-heptane could be improved by more than 87%. When the Si/Al ratio was 80, the conversion rate of n-heptane could reach up to 97.5%, and the selectivity of ethylene and propylene were 24.3% and 35.1%, respectively.

Key words: L-lysine, Si/Al ratio, single-crystalline hierarchical ZSM-5 zeolite, mass transfer, catalysis, reaction

中图分类号:

TQ032.4

谢小金, 张晓雪, 刘晓玲, 崇明本, 程党国, 陈丰秋. 单晶多级孔ZSM-5分子筛酸性质对正庚烷催化裂解反应传质性能的影响[J]. 化工进展, 2024, 43(5): 2661-2672.

XIE Xiaojin, ZHANG Xiaoxue, LIU Xiaoling, CHONG Mingben, CHENG Dangguo, CHEN Fengqiu. Effect of acidic properties of single-crystalline hierarchical ZSM-5 zeolite on its activity and mass transfer in n-heptane catalytic cracking[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2661-2672.

图/表 13

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样品名称	SiO₂	TPAOH	Al₂O₃	Na₂O	L-赖氨酸	H₂O	温度和时间
Z5-Si/Al-80	1	0.450	0.00625	0.015	0.4	9	90℃ (2天)+170℃ (2天)
Z5-Si/Al-100	1	0.450	0.005	0.015	0.4	9	90℃ (2天)+170℃ (2天)
Z5-Si/Al-140	1	0.450	0.0035	0.015	0.4	9	90℃ (2天)+170℃ (2天)

样品名称	SiO₂	TPAOH	Al₂O₃	Na₂O	L-赖氨酸	H₂O	温度和时间
Z5-Si/Al-80	1	0.450	0.00625	0.015	0.4	9	90℃ (2天)+170℃ (2天)
Z5-Si/Al-100	1	0.450	0.005	0.015	0.4	9	90℃ (2天)+170℃ (2天)
Z5-Si/Al-140	1	0.450	0.0035	0.015	0.4	9	90℃ (2天)+170℃ (2天)

参数	单位	Z5-Si/Al-80	Z5-Si/Al-100	Z5-Si/Al-140
NH₃-W	℃	167	162	159
	mmol/g	0.174	0.136	0.071
NH₃-S	℃	348	343	335
	mmol/g	0.215	0.162	0.114
总酸量	mmol/g	0.389	0.298	0.185
B-200℃	mmol/g	0.085	0.072	0.038
B-350℃	mmol/g	0.060	0.049	0.028
外表面酸量	mmol/g	0.013	0.008	0.007
微孔内部酸量	mmol/g	0.072	0.064	0.031
Si/Al		86.7	98.7	136.6

参数	单位	Z5-Si/Al-80	Z5-Si/Al-100	Z5-Si/Al-140
NH₃-W	℃	167	162	159
	mmol/g	0.174	0.136	0.071
NH₃-S	℃	348	343	335
	mmol/g	0.215	0.162	0.114
总酸量	mmol/g	0.389	0.298	0.185
B-200℃	mmol/g	0.085	0.072	0.038
B-350℃	mmol/g	0.060	0.049	0.028
外表面酸量	mmol/g	0.013	0.008	0.007
微孔内部酸量	mmol/g	0.072	0.064	0.031
Si/Al		86.7	98.7	136.6

温度/℃	表观扩散系数D_eff/10^-18m²·s^-1
温度/℃	Z5-Si/Al-80	Z5-Si/Al-100	Z5-Si/Al-140
100	4.28	5.68	8.01
110	23.13	42.87	44.83
120	36.78	59.26	99.25
130	48.06	76.49	363.47
140	48.84	144.57	2635.33