Formation and characterization of supported microporous ceramic membranes prepared by sol-gel modification techniques

The formation is described of supported microporous membranes (by IUPAC definition rpore < 1 nm), prepared by modification of mesoporous γ-alumina membranes with polymeric sols. The mesoporous γ-alumina membranes, with a top-layer thickness in the order of 7–10 μm, and with pore radii of 2–2.5 nm, have a very high surface finish (mean roughness 40 nm). The amorphous microporous top-layer thickness is in the order of 60–100 nm. Gas transport properties are effectively improved as is shown by activated permeation and molecular sieve-like separation factors in the order of 50–200 for H2/CH4. These microporous top-layers can be prepared from a relatively wide range of sol structures; from inorganic oligomers which are too small to result in significant scattering with SAXS, to polymeric structures with fractal dimensions in the range: 1

[1]  M. D. Exter,et al.  Synthesis and characterization of zeolite (MFI) membranes on porous ceramic supports , 1992 .

[2]  S. J. Gregg,et al.  Adsorption Surface Area and Porosity , 1967 .

[3]  A. Burggraaf,et al.  Polymeric-silica-based sols for membrane modification applications: sol-gel synthesis and characterization with SAXS , 1995 .

[4]  A. Burggraaf,et al.  The preparation and characterization of alumina membranes with ultra-fine pores , 1984 .

[5]  A. Burggraaf,et al.  Synthesis of ceramic membranes , 1992 .

[6]  Yuehe Lin,et al.  Experimental studies on pore size change of porous ceramic membranes after modification , 1993 .

[7]  Donald W. Breck,et al.  Zeolite Molecular Sieves: Structure, Chemistry, and Use , 1974 .

[8]  R. Bhave,et al.  Inorganic membranes : synthesis, characteristics, and applications , 1991 .

[9]  A. Burggraaf,et al.  Microporous SiO2 and SiO2/MOx (M=Ti, Zr, Al) for ceramic membrane applications: A microstructural study of the sol-stage and the consolidated state , 1994 .

[10]  D. Vaughan Zeolites and Other Microporous Materials , 1989 .

[11]  H. Strathmann Inorganic membranes — synthesis, characteristics and applications , 1992 .

[12]  C. E. Megiris,et al.  Synthesis of hydrogen-permselective membranes by modified chemical vapor deposition. Microstructure and permselectivity of silica/carbon/Vycor membranes , 1992 .

[13]  E. Barrett,et al.  The Determination of Pore Volume and Area Distributions in Porous Substances. II. Comparison between Nitrogen Isotherm and Mercury Porosimeter Methods , 1951 .

[14]  G. Gavalas,et al.  Catalytic isobutane dehydrogenation in a dense silica membrane reactor , 1993 .

[15]  A. Burggraaf,et al.  Analysis and theory of gas transport in microporous sol-gel derived ceramic membranes , 1995 .

[16]  A. Burggraaf,et al.  Permeation and separation studies on microporous sol-gel modified ceramic membranes , 1995 .

[17]  Y. S. Lin,et al.  CVD of solid oxides in porous substrates for ceramic membrane modification , 1992 .

[18]  E. Barrett,et al.  (CONTRIBUTION FROM THE MULTIPLE FELLOWSHIP OF BAUGH AND SONS COMPANY, MELLOX INSTITUTE) The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms , 1951 .

[19]  S. J. Martin,et al.  Characterization of the surface area and porosity of sol-gel films using saw devices. [Silicates; surface acoustic wave (SAW)] , 1988 .

[20]  H. Nagamoto,et al.  Synthesis and textural properties of unsupported and supported rutile (TiO2) membranes , 1993 .

[21]  F. Kapteijn,et al.  Single and Multi-Component Transport through Metal-Supported MFI Zeolite Membranes , 1993 .

[22]  D. Briggs,et al.  Practical surface analysis: By auger and x-ray photoelectron spectroscopy , 1983 .

[23]  T. Okubo,et al.  Single gas permeation through porous glass modified with tetraethoxysilane , 1989 .

[24]  Anthony G. Dixon,et al.  Adsorption, permeation, and diffusion of gases in microporous membranes. II: Permeation of gases in microporous glass membranes , 1992 .

[25]  A. Burggraaf,et al.  Permporometry study on the size distribution of active pores in porous ceramic membranes , 1993 .

[26]  C. Brinker,et al.  “Ultramicroporous” silica-based supported inorganic membranes , 1993 .

[27]  S. Kitao,et al.  Gas Separation Performance of Thin Porous Silica Membrane Prepared by Sol-Gel and CVD Methods , 1992 .

[28]  A. Burggraaf,et al.  Growth of thin dense gas-tight (Tb,Y)-ZrO2 films by electrochemical vapour deposition , 1993 .

[29]  Alan J. Hurd,et al.  Review of sol-gel thin film formation , 1992 .

[30]  K. Peinemann,et al.  Ceramic zeolite composite membranes.: Preparation, characterization and gas permeation , 1993 .

[31]  S. Kitao,et al.  Gas separation by thin porous silica membrane of ultra fine pores at high temperature. , 1990 .

[32]  C. Guizard,et al.  The sol-gel approach to prepare candidate microporous inorganic membranes for membrane reactors , 1993 .

[33]  Benoit B. Mandelbrot,et al.  Fractal Geometry of Nature , 1984 .

[34]  R. D. Lange,et al.  Microporous sol-gel derived ceramic membranes for gas separation , 1993 .

[35]  G. Gavalas,et al.  Deposition of H2-permselective SiO2 films , 1989 .

[36]  G. Gavalas,et al.  Synthesis of hydrogen permselective silicon dioxide, titanium dioxide, aluminum oxide, and boron oxide membranes from the chloride precursors , 1991 .

[37]  D. Ulrich Better Ceramics Through Chemistry , 1988 .

[38]  E. Geus Preparation and characterization of composite inorganic zeolite membranes with molecular sieve properties , 1993 .

[39]  R. Lee Diffusion of Hydrogen in Natural and Synthetic Fused Quartz , 1963 .

[40]  M. P. C. Weijnen,et al.  Precision process technology : perspectives for pollution prevention , 1993 .

[41]  Y. S. Lin,et al.  Preparation and Characterization of High‐Temperature Thermally Stable Alumina Composite Membrane. , 1991 .

[42]  K. Sing Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984) , 1985 .

[43]  K. Keizer,et al.  Microstructural properties of non-supported microporous ceramic membrane top-layers obtained by the sol-gel process , 1996 .

[44]  A. Soffer,et al.  Study of molecular sieve carbons. Part 1.—Pore structure, gradual pore opening and mechanism of molecular sieving , 1980 .

[45]  C. A. Smolders,et al.  Permporometry: the determination of the size distribution of active pores in UF membranes , 1992 .

[46]  A. J. Burggraaf,et al.  The preparation and characterization of alumina membranes with ultrafine pores: 2. The formation of supported membranes , 1985 .

[47]  Y. S. Lin Chemical and electrochemical vapour deposition of zirconia-yttria solid solutions in porous ceramic media , 1992 .

[48]  A. Burggraaf,et al.  CERAMIC MEMBRANES FOR SEPARATIONS AND REACTIONS , 1993 .

[49]  A. Burggraaf,et al.  Gas transport and separation with ceramic membranes. Part II: Synthesis and separation properties of microporous membranes , 1992 .