Textural evolution and phase transformation in titania membranes: Part 1. -unsupported membranes

Textural evolution in sol–gel derived nanostructured unsupported titania membranes has been studied using differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermal gravimetry (TG), X-ray diffraction (XRD) and N2 adsorption. The anatase-to-rutile phase transformation kinetics were studied using the Avrami model. The precursor gel had a surface area of ca. 165 m2 g–1, which after heat treatment at 600 °C for 8 h reduced to zero. Undoped titania-gel layers transformed to more than 95% rutile after calcination at 600 °C for 8 h. The causes of surface-area reduction and pore growth were anatase crystallite growth and the enhanced sintering of rutile during transformation. Lanthanum oxide was identified as a suitable dopant for shifting the transformation temperature to ca. 850 °C. Lanthanum oxide doped titania showed an improved stability of porous texture compared to that of the undoped titania membranes

Analysis and theory of gas transport in microporous sol-gel derived ceramic membranes

Sol-gel modification of mesoporous alumina membranes is a very successful technique to improve gas separation performance. Due to the formed microporous top layer, the membranes show activated transport and molecular sieve-like separation factors. This paper concentrates on the mechanism of activated transport (also often referred to as micropore diffusion or molecular sieving). Based on a theoretical analysis, results from permeation and separation experiments with H2, CO2, O2, N2, CH4 and iso-C4H10 on microporous sol-gel modified supported ceramic membranes are integrated with sorption data.\ud \ud Gas permeation through these membranes is activated, and for defect-free membranes the activation energies are in the order of 13¿15 kJ.mol¿1 and 5¿6 kJ.mol¿1 for H2 and CO2 respectively. Representative permeation values are in the order of 6×10¿7 mol.m¿2.s¿1.Pa¿1 and 20×10¿7 mol.m¿2.s¿1.Pa¿1 for H2 at 25°C and 200°C, respectively. Separation factors for H2/CH4 and H2/iso-butane are in the order of 30 and 200 at 200°C, respectively, for high quality membranes.\ud \ud Processes which strongly determine gas transport through microporous materials are sorption and micropore diffusion. Consequently, the activation energy for permeation is an apparent one, consisting of a contribution from the isosteric heat of adsorption and the activation energy for micropore diffusion. An extensive model is given to analyse these contributions.\ud \ud For the experimental conditions studied, the analysis of the gas transport mechanism shows that interface processes are not rate determining. The calculated activation energies for micropore diffusion are 21 kJ.mol¿1 and 32 kJ.mol¿1 for H2 and CO2, respectively. Comparison with zeolite diffusion data shows that these activation energies are higher than for zeolite 4A (dpore=4Å), indicating that the average pore size of the sol-gel derived membranes is probably smaller

Synthesis and textural properties of unsupported and supported rutile (TiO2) membranes

Two approaches were postulated for improving the stability of porous texture of titania membranes: (1) retarding the phase transformation and grain growth; (2) avoiding the phase transformation. Based on the second approach, rutile membranes were made directly from a rutile sol, prepared by the precipitation of titania on SnO2 nuclei. The rutile membranes were stable up to 800 °C, with a porosity of ca. 40%, whereas normal titania membranes (starting with anatase) show very little porosity above 600 °C. Alumina substitution retards grain growth and pore growth at 850 °C for unsupported as well as supported membranes. \u

High-temperature catalyst supports and ceramic membranes: Metastability and particle packing

Parameters and/or processes responsible for the stability of catalyst supports and ceramic membranes are discussed. Two major parameters/processes were identified which are responsible for the stability of sol-gel derived nanostructured oxides at elevated temperatures. They are metastable-to-stable phase transformation and structure and packing of primary particles within the aggregate. Based on these observations, strategies to develop thermostable nanostructured oxides for high-temperature membrane and catalyst applications are discussed by taking titania and titania-alumina nanocomposites as examples

Textural evolution and phase transformation in titania membranes: Part 2. - Supported membranes

Nanostructural evolution and phase transformation in supported and unsupported titania membranes have been studied using Raman spectroscopy, X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM). Densification of unsupported membranes started at ca. 450 °C and reached more than 97% density at 600 °C, whereas the supported membranes had a density of only ca. 70–75% even at 700 °C when calcined for 8 h. At 700 °C the average crystallite size of supported and unsupported membranes was ca. 20 and 70 nm, respectively. This behaviour is primarily attributed to the decrease in the driving force for sintering due to the stress developed during the constrained sintering of a film attached to a rigid support and to the inhibition of the reorganization process within the film, resulting in lower coordination numbers in supported membranes. Supported membranes showed a higher transformation temperature (slower rate of transformation) than did the unsupported. Supported and unsupported membranes, calcined for 8 h, transformed to ca. 90% rutile (calculated from Raman spectrum) after calcination at 850 and 650 °C, respectively. This difference in phase transformation behaviour is attributed primarily to the large stress which is developed in a constrained environment owing to the negative volume change during the anatase–rutile transformation

Synthesis, characterisation and gas permeation studies on microporous silica and alumina-silica membranes for separation of propane and propylene

Microporous silica membranes are known to exhibit molecular sieving effects. However, separation of nearly equal sized molecules is difficult to carry out by size exclusion. Introducing sorption selectivity and keeping the kinetics favourable to facilitate a good contribution of permeation from sorption is a possible solution to enhance selectivity of adsorbing molecules. Results are presented in this paper on the synthesis of a microporous silica membrane with commendable permselectivity between helium and propylene. Modifications are performed on the membrane to improve its almost non-selective nature to propylene/propane mixtures to give practical separation values. Gas separation results on the modified membranes are presented. Surface selectivity on the newly added alumina surface layer is identified as the helping mechanism in realising this separation

Tailor-Made Nanostructured Ion Selective MCM-48 Membranes

Mesoporous templated MCM-48 silica was prepared using a C16 surfactant as template. The MCM-48 powders and thin films were characterized by different techniques. Two types of porous supports were used, namely macroporous ¿-alumina and silicon microsieves. The supported MCM-48 layers were applied as liquid permeable membranes in pressure-driven nanofiltration and electric field-mediated ion transport experiments