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通过起始的FAU沸石和铝源相结合的方法高质量合成纳米尺寸的CHA沸石。

High-quality synthesis of a nanosized CHA zeolite by a combination of a starting FAU zeolite and aluminum sources.

作者信息

Tanigawa Takuya, Tsunoji Nao, Sadakane Masahiro, Sano Tsuneji

机构信息

Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan.

出版信息

Dalton Trans. 2020 Aug 7;49(29):9972-9982. doi: 10.1039/d0dt01013h. Epub 2020 Jun 2.

Abstract

A chabazite (CHA zeolite) was synthesized using high-silica faujasite (FAU) zeolites with a Si/Al ratio of 93, an additional alumina source (aluminum hydroxide) combined with seed crystals, and N,N,N-trimethyl-1-adamantammonium hydroxide. We compared the crystallization behavior of the starting material (HSY + Al) with that of other combinations of silica/alumina sources (high-silica and low-silica FAU, fumed silica, and aluminum hydroxide). HSY + Al rapidly yielded nanosized CHA zeolites with a crystal size of approximately 70 nm, exhibited high product crystallinity and high yield and offered a wide synthesis window. A combination of analytic experiments using electrospray-ionization mass spectrometry and nuclear magnetic resonance (NMR) suggested that in the early stage, the pre-introduced CHA seeds provide a crystal nucleus and the FAU zeolites decompose to form oligomer species in the liquid phase. Meanwhile, aluminum hydroxide retains its solid phase. Subsequent crystallization of the zeolites is accelerated by the liquid silicate oligomer and solid aluminate sources, resulting in a high yield and rapid synthesis of nanosized CHA zeolites. We observed that phosphorus-modified CHA zeolites synthesized using HSY + Al perform well as a catalyst for ethanol conversion reactions. Controlled Si/Al ratios and additional phosphorus modifications improve catalytic durability, thereby exhibiting a higher propylene yield from the reaction within the zeolite pore system.

摘要

使用硅铝比为93的高硅八面沸石(FAU)沸石、额外的氧化铝源(氢氧化铝)与晶种以及N,N,N-三甲基-1-金刚烷基氢氧化铵合成了菱沸石(CHA沸石)。我们将起始原料(HSY + Al)的结晶行为与其他硅/铝源组合(高硅和低硅FAU、气相二氧化硅和氢氧化铝)的结晶行为进行了比较。HSY + Al能快速生成晶体尺寸约为70 nm的纳米级CHA沸石,具有高的产物结晶度和高收率,并且提供了较宽的合成窗口。使用电喷雾电离质谱和核磁共振(NMR)的分析实验组合表明,在早期阶段,预先引入的CHA晶种提供了晶核,FAU沸石在液相中分解形成低聚物物种。同时,氢氧化铝保持其固相。随后,沸石的结晶通过液态硅酸盐低聚物和固态铝酸盐源加速,从而实现了纳米级CHA沸石的高收率和快速合成。我们观察到,使用HSY + Al合成的磷改性CHA沸石作为乙醇转化反应的催化剂表现良好。可控的硅/铝比和额外的磷改性提高了催化耐久性,从而在沸石孔系统内的反应中表现出更高的丙烯收率。

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