Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
권호 표지

Transmethylation of Methylnaphthalene Over Beta, USY and Mordenite Zeolite Catalysts

제올라이트 Beta, USY, Mordenite 촉매를 이용한 Methylnaphthalene의 트랜스메틸화 반응

  • Park, Jung-Nam (Advanced Chemical Technology Division, Korea Research Institute of Chemical Technology (KRICT)) ;
  • Park, Yong-Ki (Advanced Chemical Technology Division, Korea Research Institute of Chemical Technology (KRICT)) ;
  • Baeg, Jin-Ook (Advanced Chemical Technology Division, Korea Research Institute of Chemical Technology (KRICT)) ;
  • Hong, Suk-In (Department of Chemical & Biological Engineering, Korea University) ;
  • Lee, Chul Wee (Advanced Chemical Technology Division, Korea Research Institute of Chemical Technology (KRICT))
  • 박중남 (한국화학연구원 화학기술부) ;
  • 박용기 (한국화학연구원 화학기술부) ;
  • 백진욱 (한국화학연구원 화학기술부) ;
  • 홍석인 (고려대학교 화공생명공학과) ;
  • 이철위 (한국화학연구원 화학기술부)
  • Received : 2005.08.10
  • Accepted : 2005.09.20
  • Published : 2005.10.31
Download PDF
⟨ Previous Next ⟩

Abstract

Catalytic performances of zeolite catalysts such as H-mordenite(HM), H-Beta$(H{\beta})$, H-USY(HUSY) for the transmethylation between 1-methylnaphthalene(1-MN) and 2-methylnaphthalene(2-MN) were investigated in a fixed-bed flow reactor. $H{\beta}$ showed higher and more stable conversion than others to exhibit a high and stable 2-MN/1-MN ratio of 2.3 and 2,6-DMN/2,7-DMN ratio of 1.3 at the $1^{st}$ hour of time on stream under the reaction conditions as follows: reaction temperature of $350^{\circ}C$, reaction pressure of 1.5 MPa, WHSV of $2.7g_{feed}/g_{cat}{\cdot}h$ and the molar ratio of 1-MN and 2-MN of 1:1. The catalytic behavior has been discussed in relation with the catalyst pore structure and acidity.

1-methylnaphthalene(1-MN)과 2-methylnaphthalene(2-MN) 사이에서의 트랜스메틸화 반응을 제올라이트, H-mordenite(HM), H-Beta$(H{\beta})$, H-USY(HUSY) 촉매를 이용한 고정층 반응기에서 수행하였다. $H{\beta}_{25}(SiO_2/Al_2O_3=25)$ 촉매는 다음과 같은 조건, 반응온도 $350^{\circ}C$, 반응압력 1.5 Mpa, 전체 액상 반응물의 WHSV $2.7g_{feed}/g_{cat}{\cdot}h$, 반응물 1-MN과 2-MN의 몰비 1:1, 반응 1시간에서 2-MN/1-MN 비=2.3와 2,6-DMN/2,7-DMN 비=1.3을 보이면서 다른 촉매보다 높은 전환율과 안정성을 나타내었다. 촉매의 세공구조, 산성도와 관련하여 촉매성능을 해석하였다.

Keywords

Acknowledgement

Supported by : 한국과학재단

References

  1. Song, C. and Schobert, H. H., 'Opportunities for Developing Specialty Chemicals and Advanced Materials from Coals,' Fuel Proc. Technol., 34(2), 157-196(1993)
  2. Inui, T. and Pu, S. B., 'Separation of 2,6-Dimethylnaphthalene from a Mixture of its Isomers using Lithium-incorporated Zeolite Y Synthesized by Rapid Crystallization Method,' Separations Technol., 5(4), 229-237(1995) https://doi.org/10.1016/0956-9618(95)00127-1
  3. Tanabe, K. and Hölderich, W. F., 'Industrial Application of Solid Acid-base Catalysts,' Appl. Catal. A, 181(2), 399-434(1999) https://doi.org/10.1016/S0926-860X(98)00397-4
  4. Hagen, G. P. and Hung, D. T., 'Selective Production of 2,6-dimethylnaphthalene,' U.S. Patent No. 5,670,704(1997)
  5. Pu, S.-B. and Inui, T., 'Synthesis of 2,6-dimethylnaphthalene by Methylation of Methylnaphthalene on Various Medium and Large-Pore Zeolite Catalysts,' Appl.Catal. A, 146(2), 305-316(1996) https://doi.org/10.1016/S0926-860X(96)00182-2
  6. Fraenkel, D., Cherniavsky, M., Ittah, B. and Levy, M., 'Shapeselective Alkylation of Naphthalene and Methylnaphthalene with Methanol over H-ZSM-5 Zeolite Catalysts,' J. Catal., 101(2), 273- 283(1986) https://doi.org/10.1016/0021-9517(86)90254-X
  7. Komatsu, T., Araki, Y., Namba, S. and Yashima, T., 'Selective Formation of 2,6-dimethylnaphthalene from 2-methylnaphthalene on ZSM-5 and Metallosilicates with MFI Structure,' Stud. Surf. Sci. Catal., 84(1), 1821-1828(1994) https://doi.org/10.1016/S0167-2991(08)63737-4
  8. Inui, T., Pu, S.-B. and Kugai, J.-I., 'Selective Neutralization of Acid Sites on the External Surface of H-ZSM-5 Crystallites by a Mechanochemical Method for Methylation of Methylnaphthalene,' Appl. Catal. A, 146(2), 285-296(1996) https://doi.org/10.1016/S0926-860X(96)00185-8
  9. Park, J.-N., Wang, J., Lee, C. W. and Park, S.-E., 'Methylation of Naphthalene with Methanol over Beta, Mordenite, ZSM-12 and MCM-22 Zeolite Catalysts,' Bull. Korean Chem. Soc., 23(7), 1011-1013(2002) https://doi.org/10.5012/bkcs.2002.23.7.1011
  10. Pazzuconi, G., Terzoni, G., Perego, C. and Bellussi, G., 'Selective Alkylation of Naphthalene to 2,6-dimethylnaphthalene Catalyzed by MTW Zeolite,' Stud. Surf. Sci. Catal., 135(1), 25-O-03 (2001)
  11. Tsutsui, T., Ijichi, K., Inomata, T., Setiadi, Kojima, T. and Sato, K., 'Enhancement of Conversion and Selectivity by Temperature- swing Unsteady-state Reaction Method in Shape-selective Methylation of Methylnaphthalene with ZSM-5,' Chem. Engin. Science, 59(19), 3993-3999(2004) https://doi.org/10.1016/j.ces.2004.05.030
  12. Weitkamp, J. and Neuber, M., 'Shape Selective Reaction of Alkylnaphthalenes in Zeolite Catalysts,' Stud. Surf. Sci. Catal., 60(1), 291-301(1991) https://doi.org/10.1016/S0167-2991(08)61906-0
  13. Park, J.-N., Wang, J., Kim, H. Y., Lee, J. K. and Lee, C. W., 'Gas Phase Methylation of 2-Methylnaphthalene by 1,2,4- Trimethylbenzene/Methanol Over Various Zeolitic Catalysts,' Prog. Catal. Res., Chapter 3, Nova Science Publisher (2005)
  14. Park, J.-N., Wang, J., Hong, S.-I. and Lee, C.W., 'Effect of Dealumination of Zeolite Catalysts on Methylation of 2-methylnaphthalene in a High-pressure Fixed-bed Flow Reactor,' Appl. Catal. A, 292(1), 68-75(2005) https://doi.org/10.1016/j.apcata.2005.05.039
  15. Santilli, D. S. and Chen, C.-Y., 'Method of Making 2,6-dimethylnaphthalene from Other Dimethylnaphthalene Isomers and from Dimethyltetralins/Dimethyldecalins with a Methyl Group on Each Ring,' U.S. patent No. 6,015,930(2000)
  16. Chen, T., Kang, N. Y., Lee, C. W., Kim, H. Y., Hong, S. B., Roh, H. D. and Park, Y.-K., 'Three-step Reactions for Selective Production of 2,6-rich Dimethylnaphthalene from 2,7-rich Dimethylnaphthalene,' Catal. Today, 93(1), 371-376(2004) https://doi.org/10.1016/j.cattod.2004.06.028
  17. Motoyuki, M., Yamamoto, K., Sapre, A. V., Williams, J. P. M. and Donnelly, S. P., 'Process for Preparing 2,6-dialkylnaphthalene,' U.S. Patent No. 6,121,501(2000)