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EMM-17,一种具有独特11元环孔道和卓越催化异构化性能的新型三维沸石。

EMM-17, a New Three-Dimensional Zeolite with Unique 11-Ring Channels and Superior Catalytic Isomerization Performance.

作者信息

Weston Simon C, Peterson Brian K, Gatt Joseph E, Lonergan William W, Vroman Hilda B, Afeworki Mobae, Kennedy Gordon J, Dorset Douglas L, Shannon Mervyn D, Strohmaier Karl G

机构信息

ExxonMobil Research and Engineering Company , Annandale , New Jersey 08801 , United States.

University of Liverpool , Liverpool L69 3BX , United Kingdom.

出版信息

J Am Chem Soc. 2019 Oct 9;141(40):15910-15920. doi: 10.1021/jacs.9b07102. Epub 2019 Sep 25.

Abstract

A new catalytically active zeolite, designated EMM-17 (ExxonMobil Material-17), with a three-dimensional (3D) 11 × 10 × 10-ring topology has been discovered from high throughput experiments while evaluating a family of new organic structure directing agents (OSDAs), 1-alkyl-4-(pyrrolidin-1-yl)pyridin-1-ium hydroxide. The framework structure was determined by model building techniques and confirmed by diffraction calculations. The EMM-17 structure is a random intergrowth of two polymorphs which have a 3D arrangement of intersecting 11 × 10 × 10-ring pores. EMM-17 is stable to calcination to remove the OSDA and can be reproducibly synthesized in the presence of fluoride using common, inexpensive reagents over a wide Si/Al range from 15 to infinity, enabling the catalyst acidity to be tailored to almost any petrochemical application. Unlike OSDAs for many new zeolite structures, the OSDAs for EMM-17 are prepared in one simple alkylation step, making EMM-17 an easy to prepare, highly accessible, catalytically active zeolite. Zeolites containing odd numbered channel sizes are rare, and this is the first confirmed example of a 3D 11-ring aluminosilicate zeolite with a pore size in between those of the commercially important 10- and 12-ring zeolites such as ZSM-5 and Zeolite-Y, respectively. Catalysts prepared from EMM-17 exhibit significantly higher activity for catalytic isomerization with no loss in selectivity than current state of the art catalysts. Catalytic isomerization of linear to branched alkanes is a critical component of commercial dewaxing, allowing for the improvement of cold flow properties of hydrocarbon fuels and lubricants through selective hydroisomerization of normal paraffins.

摘要

一种新型催化活性沸石,命名为EMM - 17(埃克森美孚材料 - 17),具有三维(3D)11×10×10环拓扑结构,是在评估一系列新型有机结构导向剂(OSDAs)——1 - 烷基 - 4 -(吡咯烷 - 1 - 基)吡啶 - 1 - 氢氧化铵时,通过高通量实验发现的。其骨架结构通过模型构建技术确定,并经衍射计算证实。EMM - 17结构是两种多晶型的随机共生体,具有相交的11×10×10环孔的三维排列。EMM - 17对煅烧稳定,可去除OSDA,并且能够在氟化物存在下,使用常见的廉价试剂在15至无穷大的宽Si/Al范围内可重复合成,从而使催化剂酸度能够针对几乎任何石化应用进行调整。与许多新型沸石结构的OSDAs不同,EMM - 17的OSDAs通过一个简单的烷基化步骤制备,这使得EMM - 17成为一种易于制备、极易获得的催化活性沸石。含有奇数通道尺寸的沸石很少见,这是第一个经证实的三维11环铝硅酸盐沸石的例子,其孔径介于商业上重要的10环和12环沸石(如ZSM - 5和Y型沸石)之间。由EMM - 17制备的催化剂在催化异构化方面表现出明显更高的活性,且选择性不低于当前的先进催化剂。直链烷烃到支链烷烃的催化异构化是商业脱蜡的关键组成部分,通过正构石蜡的选择性加氢异构化可改善烃类燃料和润滑剂的低温流动性能。

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