Fine-tuned,molecular-composite,organosilica membranes for highly efficient propylene/propane separation via suitable pore size

Fine-tuned, molecular-composite, organosilica membranes were fabricated via the co-condensation of organosilica precursors bis(triethoxysilyl)acetylene (BTESA) and bis(triethoxysilyl)benzene (BTESB). Fourier transform infrared and UV–vis spectra confirmed the co-condensation behaviors of BTESA and BTESB. The evolution of the network structure indicated that the incorporated BTESB decreased the membrane pore size, which was determined by a modified gas translation model according to the steric effect of the phenyl groups. The incorporation of BTESB to BTESA finely tuned the membrane structure and endowed the resultant composite membrane with improved separation properties. The BTESAB 9:1 membrane (molar ratio of BTESA/BTESB was 9:1) exhibited high C₃H₆ permeance at 4.5 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹ and a C₃H₆/C₃H₈ permeance ratio of 33 at 50°C. One of the most important developments of this study involved clearly defining the relationship between membrane pore size and C₃H₆/C₃H₈ separation performance for organosilica membranes in single and binary separation systems.     

High-performance molecular-separation ceramic membranes derived from oxidative cross-linked polytitanocarbosilane

Polytitanocarbosilane (TiPCS)-derived ceramic membranes were fabricated using a pre-ceramic polymer. Special attention was focused on a process of thermal-oxidative curing that was used to induce cross-linking and the effect of this process on the ceramic yield, thermal stability, oxidation resistance, and microstructure of TiPCS. The cross-linked TiPCS powders showed a ceramic yield and thermal stability that were higher than that from the non-cross-linked version. In addition, the cross-linked TiPCS with uniform micropores showed higher levels of N₂ and CO₂ adsorption capacity, BET surface area, and micropore volume than the non-cross-linked versions, and the cross-linking process enhanced the stability of the pore structure at high temperature. The cross-linked TiPCS membranes showed high H₂ permeance (1.49 × 10⁻⁶ mol/(m² s Pa)) with sub-nanopores (H₂/SF₆ selectivity: 12 000, H₂/N₂: 10), and in addition higher oxidation resistance than their non-cross-linked counterparts. Furthermore, the influence of the concentration of the TiPCS precursor coating solution was optimized and the hydrothermal stability of the membranes at high temperatures was also evaluated. The optimized membrane demonstrated great performance for the pervaporation removal of methanol in binary azeotropic systems of either MeOH/butyl acetate or MeOH/toluene, and it also showed high hydrothermal stability with excellent dehumidification performance under high temperatures.     

Reverse osmosis performance of organosilica membranes and comparison with the pervaporation and gas permeation properties

Hybrid organosilica membranes were successfully prepared using bis(triethoxysilyl)ethane (BTESE) and applied to reverse osmosis (RO) desalination. The organosilica membrane calcined at 300^°C almost completely rejected salts and neutral solutes with low‐molecular‐weight. Increasing the operating pressure led to an increase in water flux and salt rejection, while the flux and rejection decreased as salt concentration increased. The water permeation mechanism differed from the viscous flow mechanism. Observed activation energies for permeation were larger for membranes with a smaller pore size, and were considerably larger than the activation energy for water viscosity. The organosilica membranes exhibited exceptional hydrothermal stability in temperature cycles up to 90^°C. The applicability of the generalized solution‐diffusion (SD) model to RO and pervaporation (PV) desalination processes were examined, and the quantitative differences in water permeance were accurately predicted by the application of generalized transport equations. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1298–1307, 2013     

A photocatalytic membrane reactor for gas-phase reactions using porous titanium oxide membranes

Photocatalytic membrane reactors using porous titanium oxide membranes having pore sizes of several nanometers were utilized for a gas-phase reaction of methanol. Air mixed with methanol (MeOH) vapor, the concentration of which was controlled in the range of 500–6000 ppm, was fed to the photocatalytic membrane reactor in the range of 50–500 cm³/min using several types of flow patterns. Photocatalysis with membrane permeation resulted in a large decomposition rate, compared to photocatalysis without membrane permeation. The characteristics of the reaction such as decomposition ratio of MeOH, the conversion of the decomposed MeOH to CO₂ and H₂O were found to be a function of the residence time in the reactor. The photocatalytic reaction was analyzed based on pseudo-first-order kinetics to ascertain its simplicity, and the fitted curves were found to be in a relatively good agreement with the experimental data. Apparent rate constants with and without membrane permeation were 2.5 and 1.5×10⁻⁶ m s⁻¹, respectively, indicating that the performance of the photocatalytic reaction system with membrane permeation was enhanced.     

Correlation between the Izumiyama porcelain ceramics and the red-overglaze enamels of the Kakiemon-style porcelains

The Kakiemon-style porcelains made from 17th century at Arita are famous Japanese porcelains, characterized mainly by their colored underglaze and overglaze and by their original design of coloring spatial patterns in the porcelain surface. Raw materials of the red-overglaze enamels have been investigated by means of X-ray diffraction and X-ray absorption spectra using synchrotron radiations. It is found that Izumiyama porcelain ceramics of yellow color can produce the Kakiemon red-overglaze enamels by thermal treatment and water-washing, where Izumiyama is a collecting place of the raw porcelain ceramic at Arita. The brightness of the red-overglaze enamels is related on the local structure around Fe ions and the electronic band states of Fe ions near a Fermi level in α-Fe₂O₃, in addition to the spatial density of the α-Fe₂O₃ fine particles. The structural and electronic properties are slightly affected by an electron-hybridization between Fe ions of α-Fe₂O₃ and oxygen ions of the (SiO₂–Al₂O₃) complexes in the red overglaze.     

An innovative modularity of heat circulation for fractional distillation

A novel modularity of heat circulation for distillation process, which reduces the energy consumption, is proposed. By incorporating compressors and heat exchangers, the heat of the distillate is recuperated and exchanged with the heat of the feed streams. The proposed technology achieves the reduction in the required energy more than 75% as compared with a benchmark process which uses external heat source for heating. This shows the proposed modularity of heat circulation for distillation process is very promising technology to drastically reduce energy demand for distillation.     

Anticorrosive behavior of hydroxyapatite as an environmentally friendly pigment

From the point of view of waste recycling, hydroxyapatite (HAp) can be synthesized using the waste sludge from semiconductor process. The possibility of using HAp as an anticorrosive pigment was investigated. The water absorption of coating pigmented with anticorrosive pigment, HAp, red lead (RL) and zinc potassium chromate (ZPC), and the corrosion at interface between coating and substrate were monitored using AC impedance technique. The amount of absorbed water decreased in the order of ZPC- > HAp- > RL-pigmented > unpigmented film. However, the water absorbed into HAp- or ZPC-pigmented film seems to be beneficial to anticorrosive function. The anticorrosive performance of HAp is superior or at least comparable to those of ZPC and RL, which have been known as representative anticorrosive pigments. It seems that the anticorrosive properties of HAp is mainly achieved by passivating the substrate, namely the soluble component of HAp reacts with Fe to form iron phosphate in the presence of water.     

Development of spectroscopic transmission-type four detector polarimeter

We have developed a spectroscopic transmission-type four detector polarimeter (T-FDP). It consists of a detector head and a multichannel spectrometer equipped with a two-dimensional CCD detector. Inside the T-FDP, three cubic beam splitters are aligned in a straight line and they are rotated relative to each other. From the responses of the spectroscopic T-FDP to five inputs with known polarization states it is possible to determine the characteristic matrices of the T-FDP at various wavelengths. The trajectories of the experimentally measured polarization states on the Poincaré sphere agree well with theoretical predictions. These results demonstrate the feasibility of using the T-FDP for spectroscopic ellipsometry.