, Volume 12, Issue 5–6, pp 339–360 | Cite as

MFI zeolite membranes from a- and randomly oriented monolayers

  • Jungkyu Choi
  • Shubhajit Ghosh
  • Lisa King
  • Michael Tsapatsis


c-Oriented columnar MFI films made by secondary growth of randomly oriented seed monolayers, deposited using sonication-assisted covalent attachment, exhibit n-hexane/2,2-dimethylbutane separation factor of up to 104, n-/i-butane separation factor of up to 50, and p-/o-xylene separation factor of up to 2. A MFI film from a-oriented seed layer shows lower separation factors for the linear vs. branched isomers but higher separation factor for p-/o-xylene.


Zeolite MFI Preferred orientation Butane Hexane Xylene Permeation Separation 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Alfaro, S., M. Arruebo, J. Coronas, M. Menendez, and J. Santamaria, “Preparation of MFI Type Tubular Membranes by Steam-assisted Crystallization,” Microporous Mesoporous Mater., 50(2–3), 195 (2001).CrossRefGoogle Scholar
  2. Arruebo, M., J.L. Falconer, and R.D. Noble, “Separation of Binary C5 and C6 Hydrocarbon Mixtures through MFI Zeolite Membranes,” J. Membr. Sci., 269(1–2), 171 (2006).CrossRefGoogle Scholar
  3. Bernal, M.P., J. Coronas, M. Menendez, and J. Santamaria, “On the Effect of Morphological Features on the Properties of MFI Zeolite Membranes,” Microporous Mesoporous Mater., 60(1–3), 99 (2003).CrossRefGoogle Scholar
  4. Bonilla, G., D.G. Vlachos, and M. Tsapatsis, “Simulations and Experiments on the Growth and Microstructure of Zeolite MFI Films and Membranes Made by Secondary Growth,” Microporous Mesoporous Mater., 42(2–3), 191 (2001).CrossRefGoogle Scholar
  5. Bonilla, G., I. Diaz, M. Tsapatsis, H.-K. Jeong, Y. Lee, and D.G. Vlachos, “Zeolite (MFI) Crystal Morphology Control Using Organic Structure-Directing Agents,” Chem. Mater., 16(26), 5697 (2004).CrossRefGoogle Scholar
  6. Bons, A.-J. and P.D. Bons, “The Development of Oblique Preferred Orientations in Zeolite Films and Membranes,” Microporous Mesoporous Mater., 62(1–2), 9 (2003).CrossRefGoogle Scholar
  7. Caro, J., M. Noack, P. Kolsch, and R. Schafer, “Zeolite Membranes—State of their Development and Perspective,” Microporous Mesoporous Mater., 38(1), 3 (2000).CrossRefGoogle Scholar
  8. Caro, J., M. Noack, and P. Koelsch, “Zeolite Membranes: From the Laboratory Scale to Technical Applications,” Adsorption, 11(3/4), 215 (2005).CrossRefGoogle Scholar
  9. Choi, J., S. Ghosh, Z. Lai, and M. Tsapatsis, “Uniformly a-Oriented MFI Zeolite Films by Secondary Growth,” Angew. Chem., Int. Ed., 45(7), 1154 (2006).CrossRefGoogle Scholar
  10. Coronas, J., J.L. Falconer, and R.D. Noble, “Characterization and Permeation Properties of ZSM-5 Tubular Membranes,” AIChE J., 43(7), 1797 (1997).CrossRefGoogle Scholar
  11. Coronas, J., R.D. Noble, and J. L. Falconer, “Separations of C4 and C6 Isomers in ZSM-5 Tubular Membranes,” Ind. Eng. Chem. Res., 37(1), 166 (1998).CrossRefGoogle Scholar
  12. Coronas, J. and J. Santamaria, “State-of-the-Art in Zeolite Membrane Reactors,” Top. Catal., 29(1–2), 29 (2004).CrossRefGoogle Scholar
  13. Davis, M.E., “Ordered Porous Materials for Emerging Applications,” Nature (London, U. K.), 417(6891), 813 (2002).CrossRefGoogle Scholar
  14. Davis, T.M., T.O. Drews, H. Ramanan, C. He, J. Dong, H. Schnablegger, M.A. Katsoulakis, E. Kokkoli, A.V. McCormick, R.L. Penn, and M. Tsapatsis, “Mechanistic Principles of Nanoparticle Evolution to Zeolite Crystals,” Nature Materials, 5(5), 400 (2006).CrossRefGoogle Scholar
  15. de Vos Burchart, E., J.C. Jansen, B. van de Graaf, and H. van Bekkum, “Molecular Mechanics Studies on MFI-type Zeolites. Part 4. Energetics of Crystal Growth Directing Agents,” Zeolites, 13(3), 216 (1993).CrossRefGoogle Scholar
  16. Deckman, H.W., E.W. Corcoran, Jr., J.A. McHenry, W.F. Lai, L.R. Czarnetzki, and W.E. Wales, “Permselective Compositions Comprising a Substrate, a Zeolite or Zeolitelike Coating, and a Selectivity-enhancing Coating, and Separation and Catalytic Processes using the Compositions,” WO 96/01686, (1996) [Chem. Abstr., 1996, 124,180384p].Google Scholar
  17. Flanders, C.L., V.A. Tuan, R.D. Noble, and J.L. Falconer, “Separation of C6 Isomers by Vapor Permeation and Pervaporation through ZSM-5 Membranes,” J. Membr. Sci., 176(1), 43 (2000).CrossRefGoogle Scholar
  18. Funke, H.H., A.M. Argo, J.L. Falconer, and R.D. Noble, “Separations of Cyclic, Branched, and Linear Hydrocarbon Mixtures through Silicalite Membranes,” Ind. Eng. Chem. Res., 36(1), 137 (1997).CrossRefGoogle Scholar
  19. Gade, S.K., V.A. Tuan, C.J. Gump, R.D. Noble, and J.L. Falconer, “Highly Selective Separation of n-hexane from Branched, Cyclic and Aromatic Hydrocarbons using B-ZSM-5 Membranes,” Chem. Commun., (7), 601–602 (2001).Google Scholar
  20. Gora, L., J.C. Jansen, and T. Maschmeyer, “Controlling the Performance of Silicalite-1 Membranes,” Chem.–Eur. J., 6(14), 2537 (2000).CrossRefGoogle Scholar
  21. Gora, L., N. Nishiyama, J.C. Jansen, F. Kapteijn, V. Teplyakov, and T. Maschmeyer, “Highly Reproducible High-flux Silicalite-1 Membranes: Optimization of Silicalite-1 Membrane Preparation,” Sep. Purif. Methods, 22 and 23(1–3), 223 (2001).Google Scholar
  22. Gora, L. and J. C. Jansen, “Hydroisomerization of C6 with a Zeolite Membrane Reactor,” J. Catal., 230(2), 269 (2005).CrossRefGoogle Scholar
  23. Gouzinis, A., and M. Tsapatsis, “On the Preferred Orientation and Microstructural Manipulation of Molecular Sieve Films Prepared by Secondary Growth,” Chem. Mater., 10(9), 2497 (1998).CrossRefGoogle Scholar
  24. Gump, C.J., R.D. Noble, and J.L. Falconer, “Separation of Hexane Isomers through Nonzeolite Pores in ZSM-5 Zeolite Membranes,” Ind. Eng. Chem. Res., 38(7), 2775 (1999).CrossRefGoogle Scholar
  25. Ha, K., Y.-J. Lee, H.J. Lee, and K.B. Yoon, “Facile Assembly of Zeolite monolayers on Glass, Silica, Alumina, and other Zeolites using 3-Halopropylsilyl Reagents as Covalent Linkers,” Adv. Mater. (Weinheim, Ger.), 12(15), 1114 (2000).CrossRefGoogle Scholar
  26. Hedlund, J., J. Sterte, M. Anthonis, A.-J. Bons, B. Carstensen, N. Corcoran, D. Cox, H. Deckman, W. De Gijnst, P.-P. de Moor, F. Lai, J. McHenry, W. Mortier, J. Reinoso, and J. Peters, “High-flux MFI Membranes,” Microporous Mesoporous Mater., 52(3), 179 (2002).CrossRefGoogle Scholar
  27. Hedlund, J., F. Jareman, A.-J. Bons, and M. Anthonis, “A Masking Technique for High Quality MFI Membranes,” J. Membr. Sci., 222(1–2), 163 (2003).CrossRefGoogle Scholar
  28. Jareman, F., J. Hedlund, and J. Sterte, “Effects of Aluminum Content on the Separation Properties of MFI Membranes,” Sep. Purif. Methods, 32(1–3), 159 (2003).Google Scholar
  29. Jeong, H.-K., Z. Lai, M. Tsapatsis, and J.C. Hanson, “Strain of MFI Crystals in Membranes. An in Situ Synchrotron x-ray Study,” Microporous and Mesoporous Materials, 84(1–3), 332 (2005).CrossRefGoogle Scholar
  30. Jiang, H., B. Zhang, Y.S. Lin, and Y. Li, “Synthesis of Zeolite Membranes,” Chin. Sci. Bull., 49(24), 2547 (2004).CrossRefGoogle Scholar
  31. Kalipcilar, H., S.K. Gade, R.D. Noble, and J.L. Falconer, “Synthesis and Separation Properties of B-ZSM-5 Zeolite Membranes on Monolith Supports,” J. Membr. Sci., 210(1), 113 (2002).CrossRefGoogle Scholar
  32. Keizer, K., A.J. Burggraaf, Z.A.E.P. Vroon, and H. Verweij, “Two Component Permeation through Thin Zeolite MFI Membranes,” J. Membr. Sci., 147(2), 159 (1998).CrossRefGoogle Scholar
  33. Lai, Z., G. Bonilla, I. Diaz, J.G. Nery, K. Sujaoti, M.A. Amat, E. Kokkoli, O. Terasaki, R.W. Thompson, M. Tsapatsis, and D.G. Vlachos, “Microstructural Optimization of a Zeolite Membrane for Organic Vapor Separation,” Science (Washington, DC, U. S.), 300(5618), 456 (2003).Google Scholar
  34. Lai, Z. and M. Tsapatsis, “Gas and Organic Vapor Permeation through b-Oriented MFI Membranes,” Ind. Eng. Chem. Res., 43(12), 3000 (2004).CrossRefGoogle Scholar
  35. Lai, Z., M. Tsapatsis, and J.P. Nicolich, “Siliceous ZSM-5 Membranes by Secondary Growth of b-oriented Seed Layers,” Adv. Funct. Mater., 14(7), 716 (2004).CrossRefGoogle Scholar
  36. Lassinantti, M., F. Jareman, J. Hedlund, D. Creaser, and J. Sterte, “Preparation and Evaluation of thin ZSM-5 Membranes Synthesized in the Absence of Organic Template Molecules,” Catal. Today, 67(1–3), 109 (2001).CrossRefGoogle Scholar
  37. Lee, J.S., K. Ha, Y.-J. Lee, and K.B. Yoon, “Ultrasound-aided Remarkably Fast Assembly of Monolayers of Zeolite Crystals on Glass with a Very High Degree of Lateral Close Packing,” Adv. Mater. (Weinheim, Ger.), 17(7), 837 (2005).CrossRefGoogle Scholar
  38. Li, G., E. Kikuchi, and M. Matsukata, “ZSM-5 Zeolite Membranes Prepared from a Clear Template-Free solution,” Microporous Mesoporous Mater., 60(1–3), 225 (2003).CrossRefGoogle Scholar
  39. Li, Y., X. Zhang, and J. Wang, “Preparation for ZSM-5 Membranes by a Two-stage Varying-Temperature Synthesis,” Sep. Purif. Methods, 25(1–3), 459 (2001).Google Scholar
  40. Lin, Y.S., I. Kumakiri, B.N. Nair, and H. Alsyouri, “Microporous Inorganic Membranes,” Sep. Purif. Methods, 31(2), 229 (2002).CrossRefGoogle Scholar
  41. Lovallo, M.C. and M. Tsapatsis, “Preferentially Oriented Submicron Silicalite Membranes,” AIChE J., 42(11), 3020 (1996).CrossRefGoogle Scholar
  42. Lovallo, M.C., A. Gouzinis, and M. Tsapatsis, “Synthesis and Characterization of Oriented MFI Membranes Prepared by Secondary Growth,” AIChE J., 44(8), 1903 (1998).CrossRefGoogle Scholar
  43. Lu, Y., R. Ganguli, C.A. Drewien, M.T. Anderson, C.J. Brinker, W. Gong, Y. Guo, H. Soyez, B. Dunn, M.H. Huang, and J.I. Zink, “Continuous Formation of Supported Cubic and Hexagonal Mesoporous Films by Sol-gel Dip-coating,” Nature (London, U. K.), 389(6649), 364 (1997).CrossRefGoogle Scholar
  44. Mabande, G.T.P., S. Ghosh, Z. Lai, W. Schwieger, and M. Tsapatsis, “Preparation of b-oriented MFI Films on Porous Stainless Steel Substrates,” Ind. Eng. Chem. Res., 44(24), 9086 (2005).CrossRefGoogle Scholar
  45. Matsufuji, T., N. Nishiyama, M. Matsukata, and K. Ueyama, “Separation of Butane and Xylene Isomers with MFI-type Zeolitic Membrane Synthesized by a Vapor-phase Transport Method,” J. Membr. Sci., 178(1–2), 25 (2000a).CrossRefGoogle Scholar
  46. Matsufuji, T., N. Nishiyama, K. Ueyama, and M. Matsukata, “Permeation Characteristics of Butane Isomers through MFI-type Zeolitic Membranes,” Catal. Today, 56(1–3), 265 (2000b).CrossRefGoogle Scholar
  47. Matsufuji, T., K. Watanabe, N. Nishiyama, Y. Egashira, M. Matsukata, and K. Ueyama, “Permeation of Hexane Isomers through an MFI Membrane,” Ind. Eng. Chem. Res., 39(7), 2434 (2000c).CrossRefGoogle Scholar
  48. McLeary, E.E. and J.C. Jansen, “Basic Views on the Preparation of Porous Ceramic Membrane Layers: A Comparison Between Amorphous and Crystalline Layers, Leading to a New Method for the Preparation of Microporous Continuous Layers,” Top. Catal., 29(1–2), 85 (2004).CrossRefGoogle Scholar
  49. McLeary, E.E., J.C. Jansen, and F. Kapteijn, “Zeolite Based Films, Membranes and Membrane Reactors: Progress and Prospects,” Microporous Mesoporous Mater., 90(1–3), 198 (2006).CrossRefGoogle Scholar
  50. Meindersma, G.W. and A.B. de Haan, “Economical Feasibility of Zeolite Membranes for Industrial Scale Separations of Aromatic Hydrocarbons,” Desalination, 149(1–3), 29 (2002).CrossRefGoogle Scholar
  51. Nishiyama, N., L. Gora, V. Teplyakov, F. Kapteijn, and J.A. Moulijn, “Evaluation of Reproducible High Flux Silicalite-1 Membranes: Gas Permeation and Separation Characterization,” Sep. Purif. Technol., 22 and 23(1–3), 295 (2001).CrossRefGoogle Scholar
  52. Noack, M., P. Kolsch, R. Schafer, P. Toussaint, and J. Caro, “Molecular Sieve Membranes for Industrial Application: Problems, Progress, Solutions,” Chem. Eng. Technol., 25(3), 221 (2002).CrossRefGoogle Scholar
  53. Piera, E., M.P. Bernal, M.A. Salomon, J. Coronas, M. Menendez, and J. Santamaria, “Preparation and Permeation Properties of Different Zeolite Tubular Membranes,” Stud. Surf. Sci. Catal., 125(Porous Materials in Environmentally Friendly Processes), 189 (1999).Google Scholar
  54. Tuan, V.A., J.L. Falconer, and R.D. Noble, “Alkali-Free ZSM-5 Membranes: Preparation Conditions and Separation Performance,” Ind. Eng. Chem. Res., 38(10), 3635 (1999).CrossRefGoogle Scholar
  55. Tuan, V.A., R.D. Noble, and J.L. Falconer, “Boron-substituted ZSM-5 Membranes: Preparation and Separation Performance,” AIChE J., 46(6), 1201 (2000).CrossRefGoogle Scholar
  56. van de Graaf, J.M., E. van der Bijl, A. Stol, F. Kapteijn, and J.A. Moulijn, “Effect of Operating Conditions and Membrane Quality on the Separation Performance of Composite Silicalite-1 Membranes,” Ind. Eng. Chem. Res., 37(10), 4071 (1998).Google Scholar
  57. Verduijn, J.P., A.-J. Bons, M.H.C. Anthonis, and L.R. Czarnetzki, “Structures Comprising a Support, an Intermediate Layer, and an Upper Layer, Process for Forming a Molecular Sieve Layer on Supports, the Products Obtained, and Process for Separating Fluid Mixtures and Catalyzing Chemical Reactions with the Resulting Zeolite Membranes,” WO 96/01683, (1996) [Chem. Abstr., 1996, 124:236420s].Google Scholar
  58. Vroon, Z.A.E.P., K. Keizer, M.J. Gilde, H. Verweij, and A.J. Burggraaf, “Transport Properties of Alkanes through Ceramic Thin Zeolite MFI Membranes,” J. Membr. Sci., 113(2), 293 (1996).Google Scholar
  59. Vroon, Z.A.E.P., K. Keizer, A.J. Burggraaf, and H. Verweij, “Preparation and Characterization of Thin Zeolite MFI Membranes on Porous Supports,” J. Membr. Sci., 144(1–2), 65 (1998).Google Scholar
  60. Xomeritakis, G., A. Gouzinis, S. Nair, T. Okubo, M. He, R.M. Overney, and M. Tsapatsis, “Growth, Microstructure, and Permeation Properties of Supported Zeolite (MFI) Films and Membranes Prepared by Secondary Growth,” Chem. Eng. Sci., 54(15–16), 3521 (1999).CrossRefGoogle Scholar
  61. Xomeritakis, G., S. Nair, and M. Tsapatsis, “Transport Properties of Alumina-supported MFI Membranes Made by Secondary (Seeded) Growth,” Microporous Mesoporous Mater., 38(1), 61 (2000).CrossRefGoogle Scholar
  62. Xomeritakis, G., Z. Lai, and M. Tsapatsis, “Separation of Xylene Isomer Vapors with Oriented MFI Membranes Made by Seeded Growth,” Ind. Eng. Chem. Res., 40(2), 544 (2001).CrossRefGoogle Scholar

Copyright information

© Springer Science + Business Media, LLC 2006

Authors and Affiliations

  • Jungkyu Choi
    • 1
  • Shubhajit Ghosh
    • 1
  • Lisa King
    • 2
  • Michael Tsapatsis
    • 1
  1. 1.Department of Chemical Engineering and Materials ScienceUniversity of Minnesota, 151 Amundson HallMinneapolisUSA
  2. 2.UOP LLCDes Plaines

Personalised recommendations