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DOI: https://doi.org/10.6023/A26050179

研究论文

有机模板剂对ZSM-11分子筛甲醇制丙烯催化性能的影响

  • 原凯 ,
  • 李雨薇 ,
  • 宋鑫鹏 ,
  • 薛羽翔 ,
  • 耿琰娜 ,
  • 句宇廷 ,
  • 樊升 ,
  • 贾翔宇
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  • a长治医学院药学院 药物分子设计与新制剂长治市重点实验室 山西 长治 046000;
    b中国科学院山西煤炭化学研究所 煤炭高效低碳利用全国重点实验室 山西 太原 030001

收稿日期: 2026-06-03

  网络出版日期: 2026-07-02

基金资助

国家自然科学基金(Nos.22402012,22502224)、山西省基础研究计划青年基金(Nos.202403021222314,202503021212409)、山西省高等学校科技创新基金(No.2024L272)和长治医学院博士启动基金(Nos.BS202302,2025BS29)资助项目.

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Effect of Organic Template Agents on the Catalytic Performance of ZSM-11 Zeolite for Conversion of Methanol to Propene

  • Yuan Kai ,
  • Li Yuwei ,
  • Song Xinpeng ,
  • Xue Yuxiang ,
  • Geng Yanna ,
  • Ju Yuting ,
  • Fan Sheng ,
  • Jia Xiangyu
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  • aChangzhi Key Laboratory of Drug Molecular Design and Innovative Pharmaceutics, School of Pharmacy, Changzhi Medical College, Changzhi, Shanxi 046000, PR China;
    bState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, PR China

Received date: 2026-06-03

  Online published: 2026-07-02

Supported by

National Natural Science Foundation of China (Nos. 22402012, 22502224), the Fundamental Research Program of Shanxi province (Nos. 202403021222314, 202503021212409), the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (No. 2024L272), and the Doctoral Scientific Research Foundation of Changzhi Medical College (Nos. BS202302, 2025BS29).

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摘要

分别以1,8-辛二胺（DAO）、四丁基氢氧化铵（TBAOH）和四丁基溴化铵（TBABr）为有机模板剂,采用水热合成法制备了ZSM-11-DAO、ZSM-11-TBAOH和ZSM-11-TBABr三种ZSM-11分子筛。通过多种表征手段,系统研究了有机模板剂对ZSM-11分子筛粒径、酸性质及其甲醇制丙烯（MTP）催化性能的影响。结果表明,ZSM-11-DAO虽含有更高比例的骨架铝原子落位于直孔道,但其粒径较大;ZSM-11-TBAOH和ZSM-11-TBABr均具有较小的粒径,且后者骨架铝原子富集于直孔道内的比例更高。较小的粒径以及更多骨架铝原子在直孔道内的落位分布特征,可有效抑制MTP反应中活性芳烃物种的生成及其向积碳前驱体的演变,从而提高烯烃循环机理的相对贡献。因此,与ZSM-11-DAO和ZSM-11-TBAOH相比,ZSM-11-TBABr在MTP反应中表现出更高的丙烯选择性和更长的催化寿命。

关键词： ZSM-11分子筛; 有机模板剂; 粒径; 酸位分布; 甲醇制丙烯

本文引用格式

原凯 , 李雨薇 , 宋鑫鹏 , 薛羽翔 , 耿琰娜 , 句宇廷 , 樊升 , 贾翔宇 . 有机模板剂对ZSM-11分子筛甲醇制丙烯催化性能的影响[J]. 化学学报, 0 : 26050179 -26050179 . DOI: 10.6023/A26050179

Abstract

Although ZSM-11 zeolite is an encouraging catalyst for converting methanol to propene (MTP), its inadequate catalytic durability hinders realistic application. Herein, three high-silica ZSM-11 zeolites, designated ZSM-11-DAO, ZSM-11-TBAOH and ZSM-11-TBABr, were synthesized hydrothermally using 1,8-octanediamine (DAO), tetrabutylammonium hydroxide (TBAOH) and tetrabutylammonium bromide (TBABr) as the organic template agents, respectively. The effect of organic template agents on the crystal size and acidic properties of ZSM-11 zeolite as well as its catalytic performance and reaction mechanism in MTP was systematically studied through comprehensive characterization techniques such as X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), scanning electron microscopy (SEM), isothermal adsorption of methanol vapor, inductively coupled plasma optical emission spectrometry (ICP-OES), temperature-programmed desorption of ammonia (NH3-TPD), FT-IR spectra of pyridine adsorption (Py-IR), FT-IR spectra of 2,6-ditert-butylpyridine adsorption (dTBPy-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), ultraviolet-visible diffuse reflectance spectroscopy (DR UV-vis), gas chromatography-mass spectrometry (GC-MS) and 13C/27Al/29Si MAS NMR. The results indicate that although ZSM-11-DAO zeolite possesses a higher concentration of framework aluminum atoms (AlF) situated within the straight channels, it features substantially larger crystal size. In contrast, both ZSM-11-TBAOH and ZSM-11-TBABr exhibit comparably smaller crystal size, but the latter contains a greater proportion of AlF preferentially enriched in the straight channels relative to the former. The synergistic effect of reduced crystal size and preferential enrichment of AlF within the straight channels effectively suppresses the formation of reactive aromatic intermediates and impedes their further condensation into coke precursors during MTP reaction; consequently, the propagation of the aromatic-based mechanism is significantly inhibited, and the relative contribution of alkene-based mechanism is improved. Compared to both ZSM-11-DAO and ZSM-11-TBAOH, ZSM-11-TBABr zeolite demonstrates higher selectivity to propene and better catalytic stability in MTP. This study not only presents an effective strategy for improving the catalytic performance of high-silica ZSM-11 zeolite in MTP but also unravels the effect of the crystal size and distribution of acid sites on the formation and evolution of active aromatic intermediates.

Key words： ZSM-11 zeolite; organic template agent; crystal size; distribution of acid sites; methanol to propene

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