High-performance ceramic membranes with a separation layer of metal oxide nanofibers

In conventional fabrication of ceramic separation membranes, the particulate sols are applied onto porous supports. Major structural deficiencies under this approach are pin-holes and cracks, and the dramatic losses of flux when pore sizes are reduced to enhance selectivity. We have overcome these structural deficiencies by constructing hierarchically structured separation layer on a porous substrate using lager titanate nanofibers and smaller boehmite nanofibers. This yields a radical change in membrane texture. The resulting membranes effectively filter out species larger than 60 nm at flow rates orders of magnitude greater than conventional membranes. This reveals a new direction in membrane fabrication.

Ceramic membranes for separation of proteins and DNA by in situ growth of alumina nanofibres with a nanomesh of metal oxide nanofibres

Ceramic membranes were fabricated by in situ synthesis of alumina nanofibres in the pores of an alumina support as a separation layer, and exhibited a high permeation selectivity for bovine serum albumin relative to bovine hemoglobin (over 60 times) and can effectively retain DNA molecules at high fluxes.

High-flux ceramic membranes with a nanomesh of metal oxide nanofibers

Traditional ceramic separation membranes, which are fabricated by applying colloidal suspensions of metal hydroxides to porous supports, tend to suffer from pinholes and cracks that seriously affect their quality. Other intrinsic problems for these membranes include dramatic losses of flux when the pore sizes are reduced to enhance selectivity and dead-end pores that make no contribution to filtration. In this work, we propose a new strategy for addressing these problems by constructing a hierarchically structured separation layer on a porous substrate using large titanate nanofibers and smaller boehmite nanofibers. The nanofibers are able to divide large voids into smaller ones without forming dead-end pores and with the minimum reduction of the total void volume. The separation layer of nanofibers has a porosity of over 70% of its volume, whereas the separation layer in conventional ceramic membranes has a porosity below 36% and inevitably includes dead-end pores that make no contribution to the flux. This radical change in membrane texture greatly enhances membrane performance. The resulting membranes were able to filter out 95.3% of 60-nm particles from a 0.01 wt % latex while maintaining a relatively high flux of between 800 and 1000 L/m2·h, under a low driving pressure (20 kPa). Such flow rates are orders of magnitude greater than those of conventional membranes with equal selectivity. Moreover, the flux was stable at approximately 800 L/m2·h with a selectivity of more than 95%, even after six repeated runs of filtration and calcination. Use of different supports, either porous glass or porous alumina, had no substantial effect on the performance of the membranes; thus, it is possible to construct the membranes from a variety of supports without compromising functionality. The Darcy equation satisfactorily describes the correlation between the filtration flux and the structural parameters of the new membranes. The assembly of nanofiber meshes to combine high flux with excellent selectivity is an exciting new direction in membrane fabrication.

Fouling of tubular ceramic membranes during processing of cane sugar juice

This paper examines the fouling characteristics of four tubular ceramic membranes with pore sizes 300 kDa, 0.1 μm and 0.45 μm installed in a pilot plant at a sugar factory for processing clarified cane sugar juices. All the membranes, except the one with a pore size of 0.45 μm, generally gave reproducible results through the trials, were easy to clean and could handle operation at high volumetric concentration factors. Analysis of fouled and cleaned ceramic membranes revealed that polysaccharides, lipids and to a lesser extent, polyphenols, as well as other colloidal particles cause fouling of the membranes. Electrostatic and hydrophobic forces cause strong aggregation of the polymeric components with one another and with colloidal particles. To combat irreversible fouling of the membranes, treatment options that result in the removal of particles having a size range of 0.2–0.5 μm and in addition remove polymeric impurities, need to be identified. Chemical and microscopic evaluations of the juices and the structural characterisation of individual particles and aggregates identified options to mitigate the fouling of membranes. These include conditioning the feed prior to membrane filtration to break up the network structure formed between the polymers and particles in the feed and the use of surfactants to prevent the aggregation of polymers and particles.

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

Titanium-based perovskite-type mixed conducting ceramic membranes for oxygen permeation

A titanium-based perovskite-type oxide was synthesized by an improved method of combining EDTA acid and citric acid complexes. High structural stability, good sintering ability, and relatively high oxygen permeation flux were obtained simultaneously for disks synthesized from this ceramic oxide. (C) 2002 Elsevier Science B.V All rights reserved.

Research progress and materials selection guidelines on mixed conducting perovskite-type ceramic membranes for oxygen production

Oxygen production by air separation is of great importance in both environmental and industrial processes as most large scale clean energy technologies require oxygen as feed gas. Currently the conventional cryogenic air separation unit is a major economic impediment to the deployment of these clean energy technologies with carbon capture (i.e. oxy-fuel combustion ). Dense ceramic perovskite membranes are envisaged to replace the cryogenics and reduce O2 production costs by 35% or more; which can significantly cut the energy penalty by 50% when integrated in oxy-fuel power plant for CO2 capture. This paper reviews the current progress in the development of dense ceramic membranes for oxygen production. The principles, advantages or disadvantages, and the crucial problems of all kinds of membranes are discussed. Materials development, optimisation guidelines and suggestions for future research direction are also included. Some areas already previously reviewed are treated with less attention.

Effect of operating parameters and cleaning on the performance of ceramic membranes treating partially clarified sugar cane juice

The performance of ceramic membranes with pore sizes of 0.05 and 0.10 mm in purifying limed and partially clarified sugar cane juice was investigated under different operating conditions. From various operating conditions and strategies, switching off the permeate for 5 seconds for every 5 minutes (S5sT5 m) by an automated control valve provided higher flux. From the three pH experiments conducted on the 0.05 mm membrane, the best performance was observed at a pH of 7.5. Amongst the four fouling models tested, the cake filtration model fitted the performance of both membranes with higher accuracy at a transmembrane pressure of 0.5 bar. Filtering the cane juice through the membrane reduced the turbidity by 99.7%, color by 15%, and the starch concentration by 80% as well as increased the purity by 1.4%. The effective cleaning chemical composition from experimental results showed that 1% NaOH and 3000 ppm NaOCl solution performed the best but only for the experiments that were treating limed and partially clarified juice at pH 7.5.

Synthesis and characterization of Fe(III)-doped ceramic membranes of titanium dioxide and its application in photoelectrocatalysis of a textile dye

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanopore size growth and ultrafiltration performance of SnO2 ceramic membranes prepared by sol-gel route

Supported ceramic membranes have been produced by the sol-casting procedure from aqueous colloidal suspensions prepared by the sol-gel route. Coatings on a tubular alumina support have been successfully performed leading to crack free layers. Samples have been sintered at 400, 500 and 600 degreesC, and the effect of heating treatment on the nanostructure and on the ultrafiltration properties are analyzed. The characterization has been done by high resolution scanning electron microscopy, nitrogen adsorption-desorption isotherms, water permeation and cut-off determination using polyethylene glycol standard solutions. The micrographs have revealed that grains and pore size increase with the temperature, whereas their shape remains invariant. This results is in agreements with N-2 adsorption-desorption analyses, which have revealed that the mean pore size diameter increases from 4 to 10 nm as the sintering temperature increases from 400 to 600 degreesC, while the total porosity remains constant. Furthermore, the tortuosity, calculated from water permeability, is essentially invariant with the sintering temperatures. The membranes cut-off, determined with a retention rate equal to 95%, are 3500, 6500 and 9000 g . mol(-1) for 400, 500 and 600 degreesC, respectively, showing that the permeation properties of SnO2 ultrafiltration membranes can easily be controlled by sintering condition.

Preparation of ceramic membranes from surface modified tin oxide nanoparticles

The preparation of crack-free SnO2 supported membranes requires the development of new strategies of synthesis capable to allow controlled changes of surface chemistry and to improve the processability of supported layers. In this way, the controlled modification of the SnO2 nanoparticle surface by adding capping molecules like Tiron(R) ((OH)(2)C6H2(SO3Na)(2)) during the sol-gel process was studied, aiming to obtain high performance membranes. Colloidal suspensions were prepared by hydrolyzing SnCl4.5H(2)O aqueous solution with NH4OH in presence of Tiron(R). The effect of the amount of Tiro(R) (from I to 20 wt.%) on the structural features of nanoparticles, powder redispersability and particle-solution interface properties was investigated by X-ray powder diffraction (XRPD), extended X-ray absorption fine structure (EXAFS), quasi-elastic light scattering and electrophoretic mobility measurements. XRPD and EXAFS results showed that the addition of Tiron(R) up to 20 wt.% to colloidal suspensions does not affect the crystallite size of SnO2 primary particles, determined around 2-3 nm. This value is comparable to the hydrodynamic size measured after redispersion of powder prepared with amount of Tiro(R) higher than 7.5 wt.%, indicating the absence of condensation reactions between primary particles after the initial precipitation step. As a consequence the powder with amount of Tiron(R) > 7.5 wt.%, can be fully redispersed in aqueous solution at pH greater than or equal to I I until a nanoparticle concentration of 6 vol.%. The electrophoresis measurements showed a decrease of the isoelectric point by increasing the amount of grafted Tiron(R) at the SnO2 nanoparticle surface, resulting in negatively charged particle-solution interface in all the studied pH range (2-11). These features govern the gelation process favoring the preparation of crack-free SnO2 supported membranes. The control exercised by Tiron(R) modifying agent in the aggregation process allows the fine-tuning of the porosity, from 0.124 to 0.065 cm(3) g(-1), and mean pore size, from 6.4 to 1.9 nm, as the amount of grafted molecules increases from 0 to 10 wt.%. In consequence, the membrane cut-off determined by filtration of polyethylene glycol standard solutions can be screened from 1500 to 3500 g mol(-1). (C) 2002 Elsevier B.V. B.V. All rights reserved.

Comparison of the performance of ceramic microfiltration and ultrafiltration membranes in the reclamation and reuse of secondary wastewater

Advanced treatment of secondary wastewater generally has been achieved using polymeric microfiltration and ultrafiltration membranes. Newly developed ceramic membranes offer distinctive advantages over the currently employed membranes and were recently introduced for the purpose. This paper presents results of a pilot study designed to investigate the application of ceramic microfiltration (MF) and ultrafiltration (UF) membranes in the recovery of water from secondary wastewater. Synthetic wastewater similar to the quality of secondary treated wastewater was fed to ceramic MF and UF system in a cross-flow mode. The filtration experiments revealed that the flux recovery through tubular ceramic MF membrane was more sensitive to the variation in TMP compared with the tubular ceramic UF membrane over the range of TMP studied. The resistance in series model was used for the evaluation of the resistance to the permeate flux. The results revealed that for ceramic UF membrane, the contribution to the total resistance of fouling was higher than the inherent of the clean membrane resistance. However, both the clean membrane resistance and the fouling resistance contribute equally in the case of MF membrane. Various wastewater indices were measured to evaluate the effectiveness of the filtration treatment. The ceramic UF membrane consistently met water quality in the permeate in terms of colour, turbidity, chemical oxygen demand and absorbance, suggesting that the permeate water could be made to be reused or recycled for suitable purposes. However, MF membrane appeared to be incompetent with respect to the removal of colour. The unified membrane fouling index (UMFI) was used to measure the fouling potential of both the membranes. The result showed that for UF membrane, the value of UMFI is one order of magnitude higher than MF membrane. The overall results suggest that there were significant differences in the performance of both the ceramic UF and MF membranes that are likely to impact on the operation and maintenance of the membrane system.