小晶粒ZSM-11分子筛的合成及其正辛烷催化裂化反应性能

doi:10.16085/j.issn.1000-6613.2023-1503

化工进展 ›› 2024, Vol. 43 ›› Issue (10): 5527-5532.DOI: 10.16085/j.issn.1000-6613.2023-1503

• 工业催化 • 上一篇

小晶粒ZSM-11分子筛的合成及其正辛烷催化裂化反应性能

任申勇(), 武宗会, 付国宁, 申宝剑

中国石油大学(北京)化学工程与环境学院，重质油全国重点实验室，北京 102249

收稿日期:2023-08-29 修回日期:2023-12-22 出版日期:2024-10-15 发布日期:2024-10-29
通讯作者: 任申勇
作者简介:任申勇（1977—），男，副教授，博士生导师，研究方向为工业催化材料。E-mail：shenyong@cup.edu.cn。
基金资助:
国家自然科学基金创新研究群体科学基金(22021004)

Synthesis of small-sized ZSM-11 zeolite and its performance in n-octane catalytic cracking

REN Shenyong(), WU Zonghui, FU Guoning, SHEN Baojian

State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering and Environment, China University of Petroleum, Beijing 102249, China

Received:2023-08-29 Revised:2023-12-22 Online:2024-10-15 Published:2024-10-29
Contact: REN Shenyong

摘要/Abstract

摘要：

采用传统水热合成法，以聚丙烯酰胺（PAM）为介孔模板剂，动态晶化合成小晶粒多级孔ZSM-11分子筛。并采用预晶化液法以减少有机模板剂的用量，降低合成成本。通过X射线衍射仪、低温N₂物理吸附、扫描电子显微镜和化学吸附仪等多种手段对合成样品进行了系统表征。考察了介孔模板剂的用量对合成小晶粒ZSM-11分子筛颗粒尺寸的影响及其催化裂化反应性能的影响。研究发现，在合成凝胶中加入聚丙烯酰胺并不会改变ZSM-11的拓扑结构，但会显著影响分子筛的形貌、孔结构及分子筛的酸性。合成的ZSM-11晶粒尺寸大幅度减小，同时出现介孔结构，样品的酸量和酸强度均增加。在正辛烷催化裂化微反评价中小晶粒ZSM-11分子筛表现出更高的活性稳定性、更少的氢转移反应和更高的丙烯收率。

关键词: ZSM-11分子筛, 小晶粒, 催化裂化, 丙烯

Abstract:

Small grained hierarchical pore ZSM-11 zeolites were synthesized by dynamic crystallization using conventional hydrothermal synthesis with polyacrylamide (PAM) as the mesoporous template agent. In order to reduce the amount of organic template agent and the synthesis cost, ZSM-11 zeolite was synthesized by a pre-crystallization liquid method. A variety of techniques including XRD, cryogenic N₂ physisorption, SEM, and NH₃-TPD were used to characterize the synthesized samples. The relation of PAM with zeolite particle size and catalytic cracking reaction performance was investigated. It was found that the addition of PMA to the synthesis gel did not change the topology of ZSM-11 zeolites but significantly affected the morphology, pore structure, and acidity of the zeolites. The particle size of ZSM-11 zeolites would be greatly reduced, with the formation of mesoporous structure, and the amount of acid and acid strength of the sample were increased. In the evaluation of n-octane catalytic cracking reaction, the small crystal sized ZSM-11 gave higher reactivity, less hydrogen transfer reaction, and higher yield of propene.

Key words: ZSM-11 zeolite, small grains, catalytic cracking, propene

中图分类号:

O643.32

任申勇, 武宗会, 付国宁, 申宝剑. 小晶粒ZSM-11分子筛的合成及其正辛烷催化裂化反应性能[J]. 化工进展, 2024, 43(10): 5527-5532.

REN Shenyong, WU Zonghui, FU Guoning, SHEN Baojian. Synthesis of small-sized ZSM-11 zeolite and its performance in n-octane catalytic cracking[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5527-5532.

图/表 8

图1 固定床连续微型反应器评价装置示意图

图2 小晶粒ZSM-11分子筛的XRD谱图

图3 ZSM-11分子筛的N2吸附脱附等温线及BJH分布曲线

表1 小晶粒ZSM-11分子筛的比表面积及孔体积数据

样品	S_BET/m²·g^-1	S_Micro/m²·g^-1	S_ext/m²·g^-1	V_total/cm³·g^-1	V_Micro/cm³·g^-1	V_Meso/cm³·g^-1
Z11	365	282	83	0.20	0.14	0.06
Z11-0.1	396	283	113	0.41	0.14	0.27
Z11-0.4	476	365	111	0.45	0.18	0.27
Z11-0.6	414	299	115	0.40	0.15	0.25
Z11-0.8	396	297	99	0.35	0.15	0.21

图4 ZSM-11分子筛的SEM图

图5 小晶粒ZSM-11分子筛样品的NH3-TPD谱图

图6 ZSM-11分子筛的正辛烷转化率随时间的变化曲线

图7 ZSM-11分子筛的产物分布图

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小晶粒ZSM-11分子筛的合成及其正辛烷催化裂化反应性能

Synthesis of small-sized ZSM-11 zeolite and its performance in n-octane catalytic cracking

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