Evaluation of fine structure of tubular zeolite NaA membrane by FTIR-ATR and FIB-TEM.

A zeolite NaA (LTA) membrane supported by an alumina porous support tube for pervaporation (PV) dehydration of ethanol was characterized by transmission electron microscopy (TEM) using a focused ion beam (FIB) thin-layer specimen preparation technique and by Fourier transform infrared attenuated total reflectance method (FTIR-ATR) using a diamond prism as the waveguide. FIB-TEM clearly presented cross-section images up to about 15 microm depth from the membrane surface. FTIR-ATR monitored the Si-O asymmetric stretching vibration spectrum. The Si-O spectrum was compared with the TEM image and their relationships were discussed. By combining the two methods, we could study the thickness of surface LTA crystals, the grain boundary, the LTA/alumina interface structure and the crystallinity and density of materials inside of the alumina porous support. Consequently, fine structure changes of the LTA membrane corresponding to the hydrothermal synthesis condition could be sensitively detected.

Evaluation of the dehydration performance of zeolite NaA membrane on porous alumina tube by the alumina X-ray diffraction intensity.

A zeolite NaA (A-type zeolite of ca. 0.4 nm pore size; Linde Type A, LTA) membrane for the dehydration of alcohol was characterized by X-ray diffraction analysis (XRD). Also, the relationship between the X-ray absorption and the EtOH/H2O pervaporation (PV) dehydration performance (water selectivity and permeation flux) of the LTA membrane was first investigated. The LTA membranes used here were gel-synthesized hydrothermally on an alumina porous support tube. Since diffraction lines from the alumina generate from a deeper layer than those of the LTA crystal, and are absorbed by both the surface LTA crystal and materials embedded in the alumina porous support, the alumina (113) diffraction line was intensively monitored to estimate the overall X-ray absorption by the LTA membrane. The intensity of the alumina (113) diffraction line showed a good correlation with the PV dehydration performance of the LTA membrane, that is, lower values with the water selectivity and higher values with the permeation flux. The lower diffraction intensity means stronger X-ray absorption by the LTA membrane. The major factor causing the difference in the X-ray absorption is the thickness or quantity of materials embedded in an alumina porous support, rather than those of the surface LTA crystal. These phenomena can be used conveniently (without real PV experiments) to determine the EtOH/H2O PV dehydration performance of the LTA membrane.

FTIR-ATR study of the surface of a tubular zeolite NaA membrane ultrasonically reacted with water and acetic acid.

For the dehydration process of biomass alcohol using a zeolite NaA (LTA) membrane supported by an alumina porous support tube, it is very important to understand damage of the surface crystal, which may be caused by acetic acid. Therefore, the surface structure and the chemical composition of the LTA membrane that reacted with water or acetic acid (pH 3-4) were investigated by the Fourier Transform Infrared Attenuated Total Reflectance method (FTIR-ATR), with a diamond prism as the waveguide, scanning electron microscope and an energy-dispersive X-ray analysis. For leaching experiments using water and acetic acid, ultrasonication was applied to promote the leaching rate and to surely prepare damaged membranes as a model experiment. The Si-O asymmetric stretching vibration spectra of the original LTA membranes showed a bimodal peak. LTA membranes after water leaching also showed the same peak. However, for the LTA membrane reacted with acetic acid of pH 3, damage of the surface LTA crystal and the loss of sodium by dissolution were clearly observed. Also, its Si-O spectral shape was broad, which suggests amorphous-like substances secondarily formed on the membrane surface. Sodium acetate was not detected for all LTA membranes reacted with acetic acid. To evaluate surface-damaged and sodium-loss membranes, FTIR-ATR can sensitively detect a Si-O spectral change corresponding to the surface structure and the chemical composition of the LTA membrane.

Characterization of zeolite NaA membrane by FTIR-ATR and its application to the rapid evaluation of dehydration performance.

A zeolite NaA (LTA) membrane supported by an alumina porous support tube was characterized by Fourier Transform Infrared Attenuated Total Reflectance method (FTIR-ATR) with a diamond prism as the waveguide. A method using the FTIR-ATR was developed to estimate rapidly the EtOH/H2O pervaporation (PV) performance of the membrane. The Si-O asymmetric stretching vibration region of LTA membrane spectra synthesized hydrothermally on seeded alumina substrates showed a bimodal peak (830 - 1200 cm(-1)). The two peaks were assigned to a surface LTA directly derived from the seed crystal (1012 cm(-1)), and to LTA and/or amorphous substances embedded in the alumina porous support (930 cm(-1)). The spectrum from LTA membrane synthesized on nonseeded alumina substrate, however, showed a single broad peak similar to the powder-formed one. These results indicate that the Si-O spectral shape of the LTA membrane is influenced strongly by the synthesis method. Also, the FTIR-ATR of the LTA membrane can detect the Si-O peaks as part of the depth information. It was first shown that the relative ratio (930 cm(-1)/1012 cm(-1)) of the two Si-O peaks from the LTA membranes on seeded alumina substrates closely relates to the water selectivity (alpha) in the PV of EtOH/H2O mixture; the alpha increases exponentially with the peak ratio. This result suggests that the differences in the vertical distribution of LTA crystal and amorphous material strongly affect the dehydration performance in the EtOH/H2O PV, that is, the amorphous-like material embedded in the alumina porous support plays an important role. The relative peak ratio measurement can be used for the rapid evaluation of the dehydration performance of the membrane.