沸石孔道结构及酸位可及性对苯与丁烯烷基化性能的影响

张凯瑞; 刘建超; 汤琼; 刘雷; 董晋湘

doi:10.11949/0438-1157.20260312

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沸石孔道结构及酸位可及性对苯与丁烯烷基化性能的影响

催化、动力学与反应器 | 更新时间：2026-07-09

- 沸石孔道结构及酸位可及性对苯与丁烯烷基化性能的影响
- Effect of Zeolite Pore Structure and Acid Site Accessibility on the Alkylation Performance of Benzene with Butene
- 化工学报 2026年
- 作者机构：
  
  太原理工大学化学与化工学院，山西太原 030024
- 作者简介：
  
  张凯瑞（1994—），女，博士研究生，careyrui@163.com
  汤琼（1991—），女，博士，讲师，monanfan@163.com
  刘雷（1978—），男，博士，教授，liulei@tyut.edu.cn
- 基金信息：
  
  国家自然科学基金项目(22478276;22508281)
- DOI：10.11949/0438-1157.20260312
  中图分类号： TQ 426;TQ241.1
- 收稿：2026-03-12，
  
  修回：2026-07-08，
  
  录用：2026-07-09，
- 稿件说明：
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张凯瑞, 刘建超, 汤琼, 等. 沸石孔道结构及酸位可及性对苯与丁烯烷基化性能的影响[J/OL]. 化工学报, 2026.

ZHANG Kairui, LIU Jianchao, TANG Qiong, et al. Effect of Zeolite Pore Structure and Acid Site Accessibility on the Alkylation Performance of Benzene with Butene[J/OL]. CIESC Journal, 2026.
张凯瑞, 刘建超, 汤琼, 等. 沸石孔道结构及酸位可及性对苯与丁烯烷基化性能的影响[J/OL]. 化工学报, 2026. DOI： 10.11949/0438-1157.20260312.

ZHANG Kairui, LIU Jianchao, TANG Qiong, et al. Effect of Zeolite Pore Structure and Acid Site Accessibility on the Alkylation Performance of Benzene with Butene[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260312.

摘要

仲丁基苯是生产苯酚和甲乙酮的重要中间体，其高效合成对酚酮联产具有重要意义。针对传统工业催化剂（固体磷酸、离子液体）存在的设备腐蚀、分离困难及环境污染等问题，本工作基于苯与丁烯烷基化反应，以沸石分子筛为绿色固体酸催化剂，系统比较了三种不同孔道结构的沸石——十元环MFI（HZSM-5）、十二元环BEA（Hβ）及带有十二元环超笼MWW（HMCM-22）——的催化性能，重点揭示了孔道拓扑结构与酸位可及性对烷基化行为的调控规律。结果表明，HZSM-5受限于十元环孔道及有限外表面酸位，扩散受阻，几乎没有催化活性；Hβ具有十二元环三维孔道，转化率提升至59.7%，但扩散路径长导致副反应增多，仲丁基苯选择性降至79.5%，且积碳严重；HMCM-22凭借其独特的十二元环超笼体系及外表面Brønsted酸位占比约45%的结构优势，在优化反应条件下，实现了80%以上的丁烯转化率和近100%的仲丁基苯选择性。提出了基于孔道结构与酸位分布差异化设计的催化剂设计策略，为烷基化催化剂的设计提供了理论参考。

Abstract

Sec-butylbenzene is an important intermediate for the production of phenol and methyl ethyl ketone

and its efficient synthesis is essential for the phenol–ketone co-production process. To overcome the inherent drawbacks of conventional industrial catalysts (solid phosphoric acid and ionic liquids)

such as equipment corrosion

difficult separation

and environmental pollution

this work employed zeolites as environmentally benign solid acid catalysts for the benzene/butene alkylation reaction. Three zeolites with distinct pore architectures—10 MR MFI (HZSM-5)

12 MR BEA (Hβ)

and 12 MR supercages MWW (HMCM-22)—were systematically compared. The study aims to elucidate the regulatory roles of pore topology and acid site accessibility on the alkylation performance. The results demonstrate that HZSM-5 exhibits negligible catalytic activity

attributable to the synergistic constraints of its 10 MR channels and the scarcity of accessible external surface acid sites

leading to diffusion limitations. Hβ

possessing a three‑dimensional 12 MR channel system

achieves a butene conversion of 59.7%; however

the extended diffusion pathways facilitate undesirable side reactions

resulting in a decreased sec‑butylbenzene selectivity of 79.5% and pronounced coke deposition. In contrast

HMCM-22 takes advantage of its unique 12 MR supercage architecture together with a substantial proportion of external surface Brønsted acid sites (approximately 45% of the total)

attaining over 80% butene conversion and nearly 100% sec‑butylbenzene selectivity under optimized reaction conditions. Based on these findings

a catalyst design strategy rooted in the differentiated engineering of pore architecture and acid site distribution is proposed

offering a theoretical framework for the rational design of alkylation catalysts.

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references

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