Construction of hierarchical micro-mesoporous Silicalite-1 zeolite and its catalytic performance in vapor-phase Beckmann rearrangement

HUANG Wenbin; ZHANG Yunmei; BAI Tianyu; XU Zhen; ZHOU Yasong; WEI Qiang

doi:10.11949/0438-1157.20260861

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Construction of hierarchical micro-mesoporous Silicalite-1 zeolite and its catalytic performance in vapor-phase Beckmann rearrangement

更新时间：2026-08-03

- Construction of hierarchical micro-mesoporous Silicalite-1 zeolite and its catalytic performance in vapor-phase Beckmann rearrangement
- CIESC Journal (2026)
- 作者机构：
  
  中国石油大学（北京）重质油全国重点实验室，北京 102249
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20260861
  CLC： TQ426.94
- Received：21 June 2026，
  
  Revised：2026-08-02，
  
  Accepted：03 August 2026，
- 稿件说明：
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HUANG Wenbin, ZHANG Yunmei, BAI Tianyu, et al. Construction of hierarchical micro-mesoporous Silicalite-1 zeolite and its catalytic performance in vapor-phase Beckmann rearrangement[J/OL]. CIESC Journal, 2026.
DOI：

HUANG Wenbin, ZHANG Yunmei, BAI Tianyu, et al. Construction of hierarchical micro-mesoporous Silicalite-1 zeolite and its catalytic performance in vapor-phase Beckmann rearrangement[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260861.

摘要

气相贝克曼重排是生产己内酰胺（CPL）的绿色工艺。MFI型Silicalite-1分子筛是该反应中应用最广泛的催化剂，但其单一的微孔结构严重限制了反应物环己酮肟（CHO）和产物CPL的扩散，导致副反应增多。本文以正丁胺体系合成的Silicalite-1（NE-S-1）为对象，系统对比了原位引入十六烷基三甲基溴化铵（CTAB）、三乙醇胺（TEA）以及氢氧化钠（NaOH）碱处理三种介-微孔构筑策略。结果表明，CTAB虽能大幅增加介孔体积，但会严重破坏微孔结构，导致催化活性下降；TEA主要起形貌调节作用，无法有效构筑介孔；相比之下，焙烧后碱处理（S-1-NaOH-2）可在保留微孔骨架的同时引入平均孔径3.8 nm的丰富介孔，并将末端硅羟基重构为富含氢键的硅羟基窝，生成高效活性中心。该样品在保持高转化率（>95%）的同时，将CPL选择性提升至95%以上，实现了高活性与高选择性的协同优化。

Abstract

Vapor-phase Beckmann rearrangement is a green process for the production of ε-caprolactam (CPL). MFI-type Silicalite-1 zeolite is the most widely used catalyst for this reaction; however

its sole microporous structure severely restricts the diffusion of both the reactant cyclohexanone oxime (CHO) and the product CPL

leading to increased side reactions. In this study

using Silicalite-1 synthesized in a n-butylamine system (NE-S-1) as the object

three strategies for constructing hierarchical micro-mesoporous structures were systematically compared: in-situ incorporation of cetyltrimethylammonium bromide (CTAB)

addition of triethanolamine (TEA)

and post-synthesis alkali treatment with sodium hydroxide (NaOH). The results show that although CTAB significantly increases the mesopore volume

it severely damages the microporous structure

resulting in decreased catalytic activity. TEA mainly acts as a morphology regulator and fails to effectively generate mesopores. In contrast

post-synthesis alkali treatment (S-1-NaOH-2) introduces abundant mesopores with an average pore size of 3.8 nm while preserving the microporous framework

and simultaneously reconstructs the terminal silanols into hydrogen-bond-rich silanol nests

generating highly efficient active centers. This sample achieves a synergy of high activity and high selectivity

maintaining a high conversion (>95%) while increasing the CPL selectivity to over 95%.

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references

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