Zeolite-based supports for inorganic membranes intended for gas separation have the potential to increase the resistance to thermal shock-induced cracking compared with ceramic or metallic substrates. We have studied the effect of exposure at 90 °C of hierarchically porous silicalite-I substrates to aqueous solutions at pH 2.0, 10.6, and 13.0 for periods up to 168 h. Silicalite-I supports were produced in binder-free form by pulsed current processing and using clay-binders by conventional thermal treatment. Long-term (168 h) acid and alkali treatment of the silicalite-I substrates results in a slight removal of silicon (in acid) and aluminum (in alkali) and does not affect the specific surface area and the crystalline microporous structural features but broadens the size distribution of the macropores. The mechanical strength remains unchanged after exposure to both alkaline and acidic solutions and the binder-free substrates display more than 20 times higher strength than the binder-containing materials.
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O. Camus, S. Perera, B. Crittenden, Y.C. van Delft, D.F. Meyer, P.P.A.C. Pex, I. Kumakiri, S. Miachon, J-A. Dalmon, S. Tennison, P. Chanaud, E. Groensmit, and W. Nobel: Ceramic membranes for ammonia recovery. AIChE J. 52(6), 2055 (2006).
J. Caro, M. Noack, and P. Kölsch: Zeolite membranes: From the laboratory scale to technical applications. Adsorption 11(3–4), 215 (2005).
M. Noack, P. Kölsch, R. Schäfer, P. Toussaint, and J. Caro: Molecular sieve membranes for industrial application: Problems, progress, solutions. J. Chem. Eng. Technol. 25(3), 221 (2002).
E.E. McLeary, J.C. Jansen, and F. Kapteijn: Zeolite based films, membranes and membrane reactors: Progress and prospects. Microporous Mesoporous Mater. 90(1–3), 198 (2006).
E. Piera, A. Giroir-fendler, J.A. Dalmon, H. Moueddeb, J. Coronas, M. Menéndez, and J. Santamaria: Separation of alcohols and alcohols/O2 mixtures using zeolite MFI membranes. J. Mem. Sci. 142, 97 (1998).
E. Piera, C. Téllez, J. Coronas, M. Menéndez, and J. Santamaria: Use of zeolite membrane reactors for selectivity enhancement: Application to the liquid-phase oligomerization of i-butene. Catal. Today 67(1–3), 127 (2001).
W.C. Wong, L.T.Y. Au, C.T. Ariso, and K.L. Yeung: Effects of synthesis parameters on the zeolite membrane growth. J. Mem. Sci. 191(1–2), 143 (2001).
Á. Berenguer-Murcia, J. Garcia-Martinez, D. Cazorla-Amorós, Á. Linares-Solano, and A.B. Fuertes: Silicalite-1 membranes supported on porous carbon discs. Microporous Mesoporous Mater. 59(2–3), 147 (2003).
F. Akhtar, A. Ojuva, S.K. Wirawan, J. Hedlund, and L. Bergström: Hierarchically porous binder-free silicalite-1 discs: A novel support for all-zeolite membranes. J. Mater. Chem. 21(24), 8822 (2011).
R. Lai and G.R. Gavalas: Surface seeding in ZSM-5 membrane preparation. Ind. Eng. Chem. Res. 37(11), 4275 (1998).
H-Z. Jeannette-Mareike: Chemical and thermal stability of mesoporous ceramic membranes, Ph.D. Thesis. Proefschrift Universiteit Twente, Enschede, The Netherlands, 1995.
M. Mallada Reyes and M. Menédez: Inorganic Membranes, Synthesis, Characterization and Applications, 13 serie (Elsevier B.V., England, 2008), p. 7.
T. Van Gestel, C. Vandecasteele, A. Buekenhoudt, C. Dotremont, J. Luyten, R. Leysen, B. Van der Bruggen, and G. Maes: Alumina and titania multilayer membranes for nanofiltration: Preparation, characterization and chemical stability. J. Membr. Sci. 207(1), 73 (2002).
R.K. Iler: The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties and Biochemistry of Silica (Wiley Interscience, New York, 1979).
C. Andersson and J. Hedlund: Effects of exposure to water and ethanol on silicalite-1 membranes. J. Membr. Sci. 313(41), 120 (2008).
M.R. Apelian, A.S. Fung, G.J. Kennedy, and T.F. Degnan: Dealumination of zeolite β via dicarboxylic acid treatment. J. Phys. Chem. 100(41), 16577 (1996).
M. Ogura, S. Shinomiya, J. Tateno, Y. Nara, M. Nomura, E. Kikuchi, and M. Matsukata: Alkali-treatment technique: New method for modification of structural and acid-catalytic properties of ZSM-5 zeolites. J. Appl. Catal. 219(1–2), 33 (2001).
A. Čimek, B. Subotić, I. Šmit, A. Tonejc, R. Aiello, F. Crea, and A. Nastro: Dissolution of high-silica zeolites in alkaline solutions II: Dissolution of ‘activated’ silicalite-1 and ZSM-5 with different aluminum content. Microporous Mater. 8(3–4), 159 (1997).
S. Werner: Formation of silicic acid in aqueous suspensions of different silica modifications: In equilibrium concepts in natural water systems. J. Am. Chem. Soc. 67, 161 (1967).
H. Beyer: Dealumination techniques for zeolites. Molecular Seive 3, 203 (2002).
Y.Y. Li, S.P. Perera, B.D. Crittenden, and J. Bridgwater: The effect of the binder on the manufacture of a 5A zeolite monolith. Powder Technol. 116(1), 85 (2001).
R. van Mao, E. Rutinduka, C. Detellier, P. Gougay, V. Hascoet, S. Tavakoliyan, S. V Hoa, and T. Matsuura: Mechanical and pore characteristics of zeolite composite membranes. J. Mater. Chem. 9(3), 783 (1999).
E.H. Oelkers, J. Schott, and J-L. Devidal: The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta 58(9), 2011 (1994).
W.H. Casey, H.R. Westrich, and G.W. Arnold: Surface chemistry of labradorite feldspar reacted with aqueous solutions at pH = 2, 3, and 12. Geochim. Cosmochim. Acta 52(12), 2795 (1988).
ASTM standard F394-78: Test Method for Biaxial Flexure Strength (Modulus of Rupture) of Ceramic Substrates (ASTM international, West conshohocken, PS, DOI: 10-1520/F0394-78R96, 1996).
Z. Xie and J.V. Walther: Incongruent dissolution and surface area of kaolinite. Geochim. Cosmochim. Acta 56(9), 3357 (1992).
H.M. May, D.G. Klnniburgh, P.A. Helmke, and M.L. Jackson: Aqueous dissolution, solubilities and thermodynamic stabilities of common aluminosilicate clay minerals: Kaolinite and smectites. Geochim. Cosmochim. Acta 50(8), 1667 (1986).
R.L. Hartman and H.S. Fogler: Understanding the dissolution of zeolites. J. Am. Chem. Soc. 23(10), 5477 (2007).
G. Jozefaciuk and G. Bowanko: Effect of acid and alkali treatments on surface areas and adsorption energies of selected minerals. Clays Clay Miner. 50(6), 771 (2002).
F. Shi: Ceramic Material-Progress in Modern Ceramics (Intech, Rijeka, Croatia, 2012).
The authors would like to thank Swedish Foundation for Scientific Research (SSF) and Berzelii center EXSELENT on porous material at Stockholm University for financing this work. We like to acknowledge Dr. Kjell Jansson for his help with the electron microscopy.
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Keshavarzi, N., Akhtar, F. & Bergström, L. Chemical durability of hierarchically porous silicalite-I membrane substrates in aqueous media. Journal of Materials Research 28, 2253–2259 (2013). https://doi.org/10.1557/jmr.2013.177