Silica membrane formation

Pex, P.P.A.C. and Y.C. van Delft, Silica membranes for hydrogen fuel production by membrane water gas shift reaction and development of a mathematical model for a membrane reactor, in Carbon Dioxide Capture for Storage in Deep Geologic Formations—Results from the C02 Capture Project Capture and Separation of Carbon Dioxide from Combustion Sources, eds., D. Thomas, and B. Sally, Vol. 1, Chapter 17, 2005. 

It should be stressed that this is a very simplified model. For example, the magnitude and size of the electrical charges on the pore wall and particle surface will be important in cases where pore and particle size are not too different. No data are available on initial membrane formation. A similar situation exists to explain the positive effect of some additions (e.g. PVA to boehmite solutions). The trends in experimental observations and the qualitative model discussed above holds also for the formation of other types of mesoporous membranes (titania, zirconia, silica) [6] (Chapter 7). 

Brinker and coworkers [49] reported the synthesis of microporous silica membranes on commercial (membralox) y-alumina supports with pore diameters of 4.0 nm. Ageing of the silica sols was shown to be effective to form discrete membrane layers with an estimated thickness of 35 nm on top of the support and to inhibit pore penetration of the silica. Sols with gyration radii Rg < (radius of support pores) penetrate the support to a depth of about 3 im, which is the thickness of the y-alumina support layer. Minimization of the condensation rate during film formation was considered to decrease the width of the pore size distribution without changing the average pore radius, which was estimated to be 0.35 < Tp < 0.5 nm. The porosity of films deposited on dense supports was about 10% as calculated from refractive index measurements. 

Membrane Formation. In earlier work. 2.) it was found that fumed silica particles could be dispersed in aqueous suspension with the aid of ultrasonic sound. Observations under the electron microscope showed that the dispersion contained disc-like particles, approximately 150-200 1 in diameter and 70-80 1 in height. Filtration experiments carried out in the "dead-end" mode (i.e., zero crossflow velocity) on 0.2 urn membrane support showed typical Class II cake formation kinetics, i.e., the permeation rate decreased according to equation (12). However, as may be seen from Figure 7, the decrease in the permeation rate observed during formation in the crossflow module is only t 1, considerably slower than the t 5 dependence predicted and observed earlier. This difference may be expected due to the presence of lift forces created by turbulence in the crossflow device, and models for the hydrodynamics in such cases have been proposed. 

Foote and coworkers [120] developed a microfabricated system with the ability to electrophoretically preconcentrate fluorescently labeled proteins prior to their separation (see Fig. 6). The authors were able to preconcentrate the proteins using a porous silica membrane situated between adjacent microchannels that allowed for the passage of buffer ions, but excluded larger migrating molecules, such as proteins. Preconcentration factors of 600-fold were achieved using this on-chip format followed by an electrophoretic separation of proteins with SDS-PAGE. Using this chip, fluorescently labeled ovalbumin was detected at concentrations as low as 100 fmol by a combination of field-amplified injection and preconcentration at the membrane prior to microchip electrophoresis. 

A composite ceramic membrane was formed [77] by the graft polymerisation of a hydrophilic polymer, PVP, onto the surface of silica membranes (pore size = 3.0 pm). The flux of an unmodified UF membrane of an oil/water emulsion (4.7%) decreased with time as compared to the flux of the composite membrane. The dechne in flux was caused by fouling and/or the immediate formation of an oil gel layer on the surface of the unmodified membrane. The modified membrane, in contrast, was not only more resistant to adsorption of oil, but also had a higher oil rejection. The performance of the modified ceramic membrane depends upon the configuration of the grafted chains in response to solvent—polymer interactions. Thus, the hydrophific PVP polymer chains tend to expand or extend away from the surface in aqueous solutions, preventing oil adsorption on the membrane surface. Simultaneously, the hydrophific polymer allows the passage of water molecules preferentially over oil. 

Finally, another important characteristic usually evaluated in the composite membranes is the mechanical stability. Thus, an improvement of the mechanical strength (evaluated at 125 °C) with the content of Ti02 and for the case of Ti0S04 was observed in doped PA PBI-based composite membranes. Formation of nanocomposites with silica nanoparticles results in an increase of the... 

In summary, there is significant potential for the utilization of silica membranes in catalytic membrane reactors. To maximize the competitive advantage of catalytic membrane reactors over traditional packed bed reactors, the silica membranes must ideally possess a high Hj permeance and high H2 selectivity. Furthermore, the production rate of Hj from the reaction must be balanced against the permeation performance of the membrane to gain the optimal conversion and H2 yield enhancement. For hydrocarbon feedstocks, additional concerns, such as the formation of coke on both the catalyst and the membrane itself, must be carefully considered. Coke formation on the membrane may serve to hinder H2 flow across the membrane, further reducing H2 permeation and the effectiveness of the membrane reactor system. 

As an example of the selective removal of products, Foley et al. [36] anticipated a selective formation of dimethylamine over a catalyst coated with a carbon molecular sieve layer. Nishiyama et al. [37] demonstrated the concept of the selective removal of products. A silica-alumina catalyst coated with a silicalite membrane was used for disproportionation and alkylation of toluene to produce p-xylene. The product fraction of p-xylene in xylene isomers (para-selectivity) for the silicalite-coated catalyst largely exceeded the equilibrium value of about 22%. 

Controlled formation of three-dimensional functional devices in silica makes the hybrid membrane materials presented here of interest for the development of a new supramolecular approach to nanoscience and nanotechnology through self-organization, towards systems of increasing behavioral and functional addressabilities (catalysis, optical and electronic applications, etc.). 

Siloxane compounds, in vitreous silica manufacture, 22 414 Siloxane materials, 20 240 Siloxane oligomers, in silicone polymerization, 22 555-556 Siloxanols, silylation and, 22 703 Silsesquioxane hybrids, 13 549 Silsesquioxanes, 15 188, 22 589-590 SilvaGas process, 3 696, 697 Silver (Ag), 22 636-667. See also Silver compounds. See Ag entries Argentothiosulfate complexes Batch desilverizing Lead-silver alloys Palladium-silver alloy membranes analytical methods for, 22 650-651 applications of, 22 636-637, 657-662 as bactericide, 22 656, 657, 660 barium alloys with, 3 344 in bimetallic monetary system, 22 647-648 in cast dental gold alloys, 8 307t coke formation on, 5 266 colloidal precipitation color, 7 343t colloidal suspensions, 7 275 color, 7 334, 335... 

Monoglyceride (MG) is one of the most important emulsifiers in food and pharmaceutical industries [280], MG is industrially produced by trans-esterification of fats and oils at high temperature with alkaline catalyst. The synthesis of MG by hydrolysis or glycerolysis of triglyceride (TG) with immobilized lipase attracted attention recently, because it has mild reaction conditions and avoids formation of side products. Silica and celite are often used as immobilization carriers [281], But the immobilized lipase particles are difficult to reuse due to adsorption of glycerol on this carriers [282], PVA/chitosan composite membrane reactor can be used for enzymatic processing of fats and oils. The immobilized activity of lipase was 2.64 IU/cm2 with a recovery of 24%. The membrane reactor was used in a two-phase system reaction to synthesize monoglyceride (MG) by hydrolysis of palm oil, which was reused for at least nine batches with yield of 32-50%. 

The chemical composihons of the zeolites such as Si/Al ratio and the type of cation can significantly affect the performance of the zeolite/polymer mixed-matrix membranes. MiUer and coworkers discovered that low silica-to-alumina molar ratio non-zeolitic smaU-pore molecular sieves could be properly dispersed within a continuous polymer phase to form a mixed-matrix membrane without defects. The resulting mixed-matrix membranes exhibited more than 10% increase in selectivity relative to the corresponding pure polymer membranes for CO2/CH4, O2/N2 and CO2/N2 separations [48]. Recently, Li and coworkers proposed a new ion exchange treatment approach to change the physical and chemical adsorption properties of the penetrants in the zeolites that are used as the dispersed phase in the mixed-matrix membranes [56]. It was demonstrated that mixed-matrix membranes prepared from the AgA or CuA zeolite and polyethersulfone showed increased CO2/CH4 selectivity compared to the neat polyethersulfone membrane. They proposed that the selectivity enhancement is due to the reversible reaction between CO2 and the noble metal ions in zeolite A and the formation of a 7i-bonded complex. 

The porous membrane templates described above do exhibit three-dimensionality, but with limited interconnectedness between the discrete tubelike structures. Porous structures with more integrated pore—solid architectures can be designed using templates assembled from discrete solid objects or su-pramolecular structures. One class of such structures are three-dimensionally ordered macroporous (or 3-DOM) solids, which are a class of inverse opal structures. The design of 3-DOM structures is based on the initial formation of a colloidal crystal composed of monodisperse polymer or silica spheres assembled in a close-packed arrangement. The interconnected void spaces of the template, 26 vol % for a face-centered-cubic array, are subsequently infiltrated with the desired material. 

Silica-alumina particles coated with a permselective silicalite membrane is almost completely selective in the formation of p-xylene in the disproportionation of toluene.402 Friedel-Crafts alkylations were performed in ionic liquids. The strong polarity and high electrostatic fields of these materials usually bring about enhanced activity.403 404 Easy recycling is an additional benefit. Good characteristics in the alkylation of benzene with dodecene were reported for catalysts immobilized on silica or MCM-41 405... 

Abstract Molecular imprinting has grown considerably over the last decade with more and more applications being developed. The use of this approach for the generation of enzyme-mimics is here reviewed with a particular focus on the most recent achievements using different polymer formats such as microgels and nanogels, beads, membranes and also silica nanoparticles. 

---