Few-Unit-Cell MFI Zeolite Synthesized using a Simple Di-quaternary Ammonium Structure-Directing Agent.

Synthesis of a pentasil-type zeolite with ultra-small few-unit-cell crystalline domains, which we call FDP (few-unit-cell crystalline domain pentasil), is reported. FDP is made using bis-1,5(tributyl ammonium) pentamethylene cations as structure directing agent (SDA). This di-quaternary ammonium SDA combines butyl ammonium, in place of the one commonly used for MFI synthesis, propyl ammonium, and a five-carbon nitrogen-connecting chain, in place of the six-carbon connecting chain SDAs that are known to fit well within the MFI pores. X-ray diffraction analysis and electron microscopy imaging of FDP indicate ca. 10 nm crystalline domains organized in hierarchical micro-/meso-porous aggregates exhibiting mesoscopic order with an aggregate particle size up to ca. 5 µm. Al and Sn can be incorporated into the FDP zeolite framework to produce active and selective methanol-to-hydrocarbon and glucose isomerization catalysts, respectively.

Twin-free, directly synthesized MFI nanosheets with improved thickness uniformity and their use in membrane fabrication.

Zeolite nanosheets can be used for the fabrication of low-defect-density, thin, and oriented zeolite separation membranes. However, methods for manipulating their morphology are limited, hindering progress toward improved performance. We report the direct synthesis (i.e., without using exfoliation, etching, or other top-down processing) of thin, flat MFI nanosheets and demonstrate their use as high-performance membranes for xylene isomer separations. Our MFI nanosheets were synthesized using nanosheet fragments as seeds instead of the previously used MFI nanoparticles. The obtained MFI nanosheets exhibit improved thickness uniformity and are free of rotational and MEL intergrowths as shown by transmission electron microscopy (TEM) imaging. The nanosheets can form well-packed nanosheet coatings. Upon gel-free secondary growth, the obtained zeolite MFI membranes show high separation performance for xylene isomers at elevated temperature (e.g., p-xylene flux up to 1.5 × 10-3 mol m-2 s-1 and p-/o-xylene separation factor of ~600 at 250°C).

High-performance ammonia-selective MFI nanosheet membranes.

Nanosheet-based MFI membranes, known to be highly selective for hydrocarbon isomer separations, exhibit an NH3/N2 mixture separation factor of 2236 with NH3 permeance of 1.1 × 10-6 mol m-2 s-1 Pa-1, and NH3/H2 separation factor of 307 with NH3 permeance of 2.3 × 10-6 mol m-2 s-1 Pa-1 at room temperature. Consistent with a competitive sorption-based separation, lower operating temperatures and higher pressures result in increased separation factor. At 323 K, with an equimolar mixed feed of NH3/N2, the fluxes and separation factors at 3 and 7 bar are 0.13 mol m-2 s-1 and 191, and 0.26 mol m-2 s-1 and 220, respectively. This performance compares favorably with that of other membranes and suggests that MFI membranes can be used in separation and purification processes involving mixtures of NH3/N2/H2 encountered in ammonia synthesis and utilization. The membranes also exhibit high performance for the separation of ethane, n-propane and n-butane from H2.