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Ethylbenzene Separation from Ethylbenzene/p-xylene Mixture with MFI-type Zeolite Membranes

MFI형 제올라이트 분리막을 이용한 에틸벤젠/파라자일렌 분리에 대한 연구

  • Lee, Gi-Cheon (Department of Chemical and Biomolecular Engineering, Yonsei University) ;
  • Jeon, Yukwon (Department of Chemical and Biomolecular Engineering, Yonsei University) ;
  • Chu, Young Hwan (Department of New Energy, Resource Engineering, College of Science & Engineering, Sangji University) ;
  • Choi, Seonghwan (The 4th Research Team, Daedeok Research Institute, Lotte Chemical Corp.) ;
  • Seo, Young-Jong (The 4th Research Team, Daedeok Research Institute, Lotte Chemical Corp.) ;
  • Shul, Yong-Gun (Department of Chemical and Biomolecular Engineering, Yonsei University)
  • Received : 2013.04.30
  • Accepted : 2013.05.23
  • Published : 2013.08.01

Abstract

Ethylbenzene (EB) which has a similar physical properties with p-xylene (pX) was separated from EB/pX mixture by using MFI-type zeolite (TS-1, ZSM-5, and Silicalite-1) coated membranes. The zeolites were synthesized by microwave method to reduce the synthesis time and uniformly formed zeolite particles were coated on the ${\alpha}$-almina tubular support with a thickness of $3-4{\mu}m$. Separation factor and permeation flux of the synthesized zeolite coated membranes were measured to survey the best performance of ethylbenzene separation from different composition of EB/pX mixtures. When the EB/pX mixture of 5:5 molar ratio applied for the separation experiment, it represented the highest separation factor. We also have studied about the effect of the atomic composition of zeolites on the separation performance within the temperature range from 160 to $220^{\circ}C$. TS-1 showed the highest permeation flux of $1,666mol/m^{2*}s^*Pa$ and Silicate-1 showed the highest separation factor of 1.73 at $200^{\circ}C$ respectively.

본 연구에서는 물리적 특성이 유사한 에틸벤젠과 파라자일렌의 혼합물을 분리하고자 MFI형 제올라이트(TS-1, ZSM-5, Silicalite-1) 분리막을 제조하였으며 이를 이용하여 기상에서 분리 실험을 진행하였다. 제올라이트 입자가 코팅된 분리막을 제조함에 있어서 마이크로웨이브 합성 방법을 사용하여 합성 시간을 단축하였으며, 500 nm 내외의 균일한 입자를 튜브타입의 지지체 막에 안착시켜 제올라이트 입자가 $3{\sim}4{\mu}m$ 두께로 치밀하게 코팅된 분리막을 제조하였다. 제조한 분리막으로 에틸벤젠/파라자일렌 혼합물 원료의 혼합비를 변경하여 투과 분리한 결과 에틸벤젠:파라자일렌=5:5 비율에서 가장 높은 분리도를 가짐을 알 수 있었다. 세 종류의 서로 다른 제올라이트 물질(TS-1, ZSM-5, Silicalite-1)을 각각 코팅하여 제조된 분리막을 이용하여 $160{\sim}220^{\circ}C$의 실험온도에서 에틸벤젠/파라자일렌을 투과 실험을 실시한 결과, TS-1 분리막이 $1,666mol/m^{2*}s^*Pa$의 가장 높은 투과 플럭스를, Silicalite-1 분리막이 1.73의 가장 높은 분리도를 $200^{\circ}C$의 온도에서 각각 보임을 확인할 수 있었다.

Keywords

References

  1. Z.-Y. Gu, D.-Q. Jiang, H.-F. Wang, X.-Y. Cui and X.-P. Yan, "Adsorption and Separation of Xylene Isomers and Ethylbenzene on Two Zn-Terephthalate Metal-Organic Frameworks," J. Phys. Chem. C, 114, 311-316(2010). https://doi.org/10.1021/jp9063017
  2. X. Gu, J. Dong, T. M. Nenoff and D. E. Ozokwelu, "Separation of p-xylene From Multicomponent Vapor Mixtures Using Tubular MFI Zeolite Membranes," J. Membrane Sci., 280, 624-633(2006). https://doi.org/10.1016/j.memsci.2006.02.020
  3. B. Lloyd, Separation of Ethyl Benzene from p-xylene by Extractive Distillation, US Patent 5,425,855(1994).
  4. Ana M. Tarditi, Silvia Irusta and E. A. Lombardo, "Xylene Isomerization in a Membrane Reactor Part I: The Synthesis of MFI Membranes for the p-xylene Separation," Chem. Eng. J., 122, 167-174(2006). https://doi.org/10.1016/j.cej.2006.06.009
  5. G. Xomeritakis and M. Tsapatsis, "Permeation of Aromatic Isomer Vapors through Oriented MFI-Type Membranes Made by Secondary Growth," Chem. Mater., 11, 875-878(1999). https://doi.org/10.1021/cm9811343
  6. Z. Lai, M. Tsapatsis and J. P. Nicolich, "Siliceous ZSM-5 Membranes by Secondary Growth of b-Oriented Seed Layers," Adv. Funct. Mater., 14 716-729(2004). https://doi.org/10.1002/adfm.200400040
  7. Y. Hu, C. Liu, Y. Zhang, N. Ren and Y. Tang, "Microwave-assisted Hydrothermal Synthesis of Nanozeolites with Controllable size," Microporous Mesoporous Mater., 119, 306-314(2009). https://doi.org/10.1016/j.micromeso.2008.11.005
  8. S.-E. Park, J.-S. Chang, Y. K. Hwang, D. S. Kim, S. H. Jhung and J. S. Hwang, "Supramolecular Interactions and Morphology Control in Microwave Synthesis of Nanoporous Materials," Catal. Surv. Asia, 8, 91-110(2004). https://doi.org/10.1023/B:CATS.0000026990.25778.a8
  9. Chelsey, D. Baertsch, Hans H. Funke, John L. Falconer and Richard D. Noble, "Permeation of Aromatic Hydrocarbon Vapors through Silicalite-Zeolite Membranes," J. Phys. Chem., 100, 7676-7679(1996). https://doi.org/10.1021/jp960226h
  10. K. Keizer, A. J. Burggraaf, Z. A. E. P. Vroon and H. Verweij, "Two Component Permeation Through Thin Zeolite MFI Membranes," J. Membrane Sci., 147, 159-172(1998). https://doi.org/10.1016/S0376-7388(98)00133-1
  11. Y. Lu, 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 Hexagonalmesoporous Films by Sol-gel Dip-coating", Nature, 389, 364-368(1997). https://doi.org/10.1038/38699
  12. Y. K. Jeon, G.-C. Lee, Y. H. Chu, S. H. Choi, Y. J. Seo and Y. G. Shul, "Microwave-assisted TS-1 Membrane for the Separation of Ethylbenzene from Xylene Mixture," Membrane Journal, 22, 120-127(2012).
  13. K. T. Jung and Y. G. Shul, "Preparation of Transparent TS-1 Zeolite Film by Using Nanosized TS-1 Particles," Chem. Mater., 9, 420-422(1997). https://doi.org/10.1021/cm9603617
  14. K. T. Jung and Y. G. Shul, "Preparation of ZSM-5 Zeolite Film and Its Formation Mechanism," J. Membr. Sci., 191, 189-197(2001). https://doi.org/10.1016/S0376-7388(01)00469-0
  15. M. Taramasso, G. Perego and B. Notari, "Preparation of Porous Crystalline Synthetic Material Comprised of Silicon and Titanium Oxides," US Patent 4,410,501(1983).
  16. B. Sulikowski, J. Rakoczy, H. Hamdan and J. Klinowski, "Structural and Catalytic Consequences of lsomorphous Substitution of Silicon by Aluminium and vice versa in the Framework of Pentasil Zeolites," J. Chem. Soc., Chem. Commun., 1542-1543(1987).
  17. C. Algieri, P. Bernardo, G. Golemme, G. Barbieri and E. Drioli, "Permeation Properties of a Thin Silicalite-1 (MFI) Membrane," J. Membr. Sci., 222, 181-190(2003). https://doi.org/10.1016/S0376-7388(03)00286-2
  18. G. Xomeritakis, Z. Lai and M. Tsapatsis, "Separation of Xylene Isomer Vapors with Oriented MFI Membranes Made by Seeded Growth," Ind. Eng. Chem. Res., 40, 544-552(2001). https://doi.org/10.1021/ie000613k
  19. G. Valerio, J. Plevert, A. Goursot and F. di Renzo, "Modeling of Boron Substitution in Zeolites and Implications on Lattice Parameters," Phys. Chem. Chem. Phys., 2, 1091-1094(2000). https://doi.org/10.1039/a908598j