Hydrophobic pure-silica *BEA-type zeolite membranes with large pores were prepared on tubular silica supports by hydrothermal synthesis using a secondary growth method and were applied to the separation of alcohol/water mixtures by pervaporation (PV), an alternative energy-efficient process for production of biofuels. Amorphous pure-silica tubular silica supports, free of Al atoms, were used for preparing the membranes. In this study, the effects of the synthesis conditions, such as the H2O/SiO2 and NH4F/SiO2 ratios in the synthetic gel, on the membrane formation process and separation performance were systematically investigated. The successfully prepared dense and continuous membranes exhibited alcohol selectivity and high flux for the separation of ethanol/water and butanol/water mixtures. The pure-silica *BEA membranes obtained under optimal conditions (0.08SiO2:0.5TEAOH:0.7NH4F:8H2O) showed high PV performance with a separation factor of 229 and a flux of 0.62 kg·m−2·h−1 for a 1 wt % n-butanol/water mixture at 318 K. This result was attributed to the hydrophobicity and large pore size of the pure-silica *BEA membrane. This was the first successful synthesis of hydrophobic large-pore zeolite membranes on tubular supports with alcohol selectivity, and the obtained results could provide new insights into the research on hydrophobic membranes with high permeability.
A simple, convenient, reusable, and inexpensive air- and water-purification unit including a one-end sealed porous amorphous-silica (a-silica) tube coated with TiO2 photocatalyst layers has been developed. The porous a-silica layers were formed through outside vapor deposition (OVD). TiO2 photocatalyst layers were formed through impregnation and calcination onto a-silica layers. The resulting porous TiO2-impregnated a-silica tubes were evaluated for air-purification capacity using an acetaldehyde gas decomposition test. The tube (8.5 mm e.d. × 150 mm) demonstrated a 93% removal rate for high concentrations (ca. 300 ppm) of acetaldehyde gas at a single-pass condition with a 250 mL/min flow rate under UV irradiation. The tube also demonstrated a water purification capacity at a rate 2.0 times higher than a-silica tube without TiO2 impregnation. Therefore, the tubes have a great potential for developing compact and in-line VOC removal and water-purification units.
Silicalite-1 membranes with high pervaporation performance were prepared successfully on a silica-particle-coated tubular silica support using a gel-free steam-assisted conversion (SAC) method. The effects of the silica-particle layer formed on the top surface of the silica support and the physical properties of the silica particles themselves on the membrane-formation process were investigated. The silica particles coated served as the additional silica source for growing the silicalite-1 seed crystal layer into the silicalite-1 membrane. As a result, it was possible to form a dense and continuous membrane even under gel-free conditions. Furthermore, it was found that the properties of the silica particles, such as their primary particle diameter, had a determining effect on their solubility during the steam treatment, that is, on the supply rate of the silica source. The silicalite-1 membrane obtained using the spherical-silica-particle-coated support had an approximately 9-μm-thick separation layer and showed very high pervaporation performance, exhibiting a separation factor of 105 and a flux of 3.72 kg m−2 h−1 for a 10 wt % ethanol/water mixture at 323 K. Thus, the gel-free SAC method can be used with a silica support coated with silica particles to readily prepare high-performance membranes without producing any chemical waste.
TiO2-coated porous silica glass tubes containing macropores were fabricated and evaluated for their water-purification capacity using aqueous solutions of methylene blue. From the results of photocatalytic degradation tests at different initial methylene blue concentrations, the equilibrium adsorption constant (K) was determined to be 4.6 × 10−2 L µmol−1, and the Langmuir-Hinshelwood rate constant (kLH) was calculated as 2.6 µM min−1. To determine the influence of ions on the efficiency of methylene blue degradation, we examined both Milli-Q water (soft water) and Contrex water (hard water) as solvents, and confirmed the reduced purification for the Contrex solution. It was, therefore, considered that the presence of inorganic salts decreased the photocatalytic efficiency. Furthermore, variations in the methylene blue decomposition ability were observed between anion-free and cation-free Contrex. Finally, we concluded that the efficiency of photocatalytic decomposition of TiO2 was influenced by multiple parameters, including the presence of anions and cations, as well as the solution pH.