RESUMEN
A new aluminosilicate zeolite, denoted EMM-28, has been successfully synthesized on a large scale using 1,1-(3,3-(1,3-phenylene)bis(propane-3,1-diyl))bis(1-methylpyrrolidinium) hydroxide as an organic structure directing agent (OSDA), which was scaled up to an â¼20 g scale with a yield of 77%. It crystallizes as thin plates (40-100 nm in thickness), and the corresponding powder X-ray diffraction (PXRD) pattern shows significant peak broadening which makes it insufficient for structure determination. Continuous rotation electron diffraction (cRED) data collected from 13 crystals were successfully used to solve and refine the structure of EMM-28. This illustrates that cRED data are capable of performing structure determination despite limited PXRD data quality. EMM-28 has a unique framework structure containing supercavities, >21 Å in size, connected by one-dimensional 10-ring channels. High-resolution transmission electron microscopy (HRTEM) confirmed the structure model. The structure of EMM-28 is related to several known zeolite structures with large cavities.
RESUMEN
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.
RESUMEN
The aluminosilicate zeolite ZSM-43 (where ZSM = Zeolite Socony Mobil) was first synthesized more than 3 decades ago, but its chemical structure remained unsolved because of its poor crystallinity and small crystal size. Here we present optimization of the ZSM-43 synthesis using a high-throughput approach and subsequent structure determination by the combination of electron crystallographic methods and powder X-ray diffraction. The synthesis required the use of a combination of both inorganic (Cs+ and K+) and organic (choline) structure-directing agents. High-throughput synthesis enabled a screening of the synthesis conditions, which made it possible to optimize the synthesis, despite its complexity, in order to obtain a material with significantly improved crystallinity. When both rotation electron diffraction and high-resolution transmission electron microscopy imaging techniques are applied, the structure of ZSM-43 could be determined. The structure of ZSM-43 is a new zeolite framework type and possesses a unique two-dimensional channel system limited by 8-ring channels. ZSM-43 is stable upon calcination, and sorption measurements show that the material is suitable for adsorption of carbon dioxide as well as methane.
