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高硅 EU-1 晶种合成 EU-1/ZSM-48 共结晶沸石:调控相比例和提高长晶相稳定性。

Synthesis of EU-1/ZSM-48 Co-Crystalline Zeolites from High-Silica EU-1 Seeds: Tailoring Phase Proportions and Promoting Long Crystalline-Phase Stability.

机构信息

State Key Laboratory of Heavy Oil Processing and the Key Laboratory of Catalysis of CNPC, China University of Petroleum-Beijing, 102249, Beijing, P. R. China.

State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, 430071, Wuhan, P. R. China.

出版信息

Chemistry. 2018 May 2;24(25):6595-6605. doi: 10.1002/chem.201705805. Epub 2018 Apr 17.

DOI:10.1002/chem.201705805
PMID:29417639
Abstract

A facile, specific, seed-assisted strategy for the synthesis of EU-1/ZSM-48 co-crystalline zeolites in the presence of hexamethonium ions (HM ) has been developed. EU-1/ZSM-48 co-crystalline zeolites with various phase proportions, with EU-1 in the range of 25 wt %-86 wt %, were obtained by adding high-silica EU-1 seeds (SiO /Al O ratio of 300) and adjusting the synthesis parameters. Not only can the phase proportions of EU-1/ZSM-48 co-crystalline zeolites be controlled, but also the stability period for co-crystallization of the two phases can be extended through varying the amount of EU-1 seeds and the HM template. Moreover, with the increase of the EU-1 proportion in the EU-1/ZSM-48 co-crystalline, the framework SiO /Al O ratios of EU-1 phase promotes steadily. Major differences in acidity and textural properties of the EU-1/ZSM-48 co-crystalline zeolites (Coz) were found with varying phase proportions, due to their distinct topological structures, crystal morphology and asymmetry between the EU-1 and ZSM-48 phases. For instance, the EU-1/ZSM-48 zeolite containing 75 wt % of EU-1 (Coz-75) possesses specific acidity and mesoporous characteristics, showing an excellent catalytic activity and stability in n-hexane cracking reaction. Compared to EU-1, ZSM-48, and a mechanical mix of the two zeolites (Mix-75), Coz-75 resulted in the highest hexane conversion and yields of light olefins, with a propylene yield, in particular, up to 38.3 wt %, which is 6.3 % more than that of the Mix-75 sample.

摘要

在六甲基铵离子(HM)存在下,开发了一种简便、特异、种子辅助的合成 EU-1/ZSM-48 共结晶沸石的方法。通过添加高硅 EU-1 种子(SiO2/Al2O3 比为 300)和调整合成参数,可以获得 EU-1/ZSM-48 共结晶沸石,其 EU-1 相的比例在 25wt%-86wt%范围内变化。不仅可以控制 EU-1/ZSM-48 共结晶沸石的相比例,还可以通过改变 EU-1 种子的用量和 HM 模板来延长两相共结晶的稳定期。此外,随着 EU-1/ZSM-48 共结晶中 EU-1 比例的增加,EU-1 相的骨架 SiO2/Al2O3 比稳步提高。由于 EU-1/ZSM-48 共结晶沸石(Coz)具有不同的拓扑结构、晶体形态和 EU-1 相与 ZSM-48 相之间的不对称性,因此不同相比例的 Coz 在酸量和织构性质上存在明显差异。例如,含有 75wt%EU-1 的 EU-1/ZSM-48 沸石(Coz-75)具有特定的酸度和中孔特性,在正己烷裂化反应中表现出优异的催化活性和稳定性。与 EU-1、ZSM-48 和两种沸石的机械混合物(Mix-75)相比,Coz-75 导致正己烷转化率和轻烯烃收率最高,特别是丙烯收率高达 38.3wt%,比 Mix-75 样品高 6.3%。

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