Synthesis of C-Plane Oriented Hexagonal Tungsten Oxide Membranes on Tubular Substrates and Their Acetic Acid/Water Separation Performances.

Hexagonal tungsten oxide (h-WO3) membrane is a novel candidate for dehydration of acetic acid (CH3COOH)/water mixtures owing to its molecular sieving property and acidic resistance. Meanwhile, c-plane orientation is an important factor for h-WO3 membranes because the pores of h-WO3 run along its c-axis. However, so far, high c-plane orientation has not been successful on tubular substrates. Here, the effect of synthesis conditions of h-WO3 membranes on tubular substrates against c-plane orientation and CH3COOH/water separation performance are investigated. The h-WO3 membranes were prepared by hydrothermal synthesis from a precursor sol containing various amounts of sodium tungstate (Na2WO4) in the presence of tubular substrates with seeds embedded on their outside surface. The seeding method and the amount of Na2WO4 in the precursor sol significantly affected both crystal orientation and densification of the membrane. A precursor sol with appropriate amounts of Na2WO4 was essential to simultaneously satisfy high c-plane orientation and densification of the membrane while excess Na2WO4 drastically decreased the degree of c-plane orientation. A highly c-plane oriented h-WO3 membrane was successfully obtained under the optimized condition, which exhibited a maximum separation factor of 40.0 and a water permeance of 1.53 × 10-7 mol·m-2·s-1·Pa-1 in a 90:10 wt % CH3COOH/water mixture. The water permeance approximately doubled compared to the previous report, possibly owing to the significantly higher degree of c-plane orientation. Furthermore, it was found that its separation ability can be maintained while stored in 90:10 wt % CH3COOH/water mixture with pH < 0 for more than 500 h.

Synthesis of MOR Zeolite/Magnetite Composite via Seed Assisted Method.

MOR zeolite is an effective adsorbent for separating organic molecules from various solutions owing to its large windows of 0)65 × 0)70 nm and its relatively high silica-alumina ratio which provides higher hydrophobicity. Fine powdery MOR zeolite is desirable for adsorption of organic molecules considering its larger surface area; however, fine particles are difficult to remove from solutions after treatment. Intensification of magnetic susceptibility through combination with magnetic particles ensure quick and easy removal of fine adsorbents by magnetic force. Meanwhile, seed assisted method is a powerful technique to direct and accelerate zeolite synthesis by adding seed crystals into the precursor sol prior to hydrothermal synthesis. In this work, we selected magnetite as the magnetic particle and propose the hydrothermal synthesis of MOR zeolite/magnetite composite via seed assisted method for the first time. MOR zeolite/magnetite composite with high MOR zeolite crystallinity was obtained by synthesizing for only 6 hours at 463 K when adding seed crystals, while no sign of crystallization was observed even after 24 hours in their absence. In addition, pre-milling of seed crystals together with magnetite was found to be effective to incorporate magnetite into MOR zeolite during crystallization and to decrease the primary crystal size of the crystallized MOR zeolite.