Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
권호 표지

Shape-Selective Catalysis over Zeolite. An Attempt in the Alkylation of Biphenyl

  • Sugi, Yoshihiro (Department of Materials Science and Technology, Faculty of Engineering, Gifu University) ;
  • Komura, Kenichi (Department of Materials Science and Technology, Faculty of Engineering, Gifu University) ;
  • Kim, Jong Ho (Department of Applied Chemical Engineering and The Research Institute for Catalysis, Chonnam National University)
  • Received : 2006.05.24
  • Published : 2006.06.10
Download PDF
⟨ Previous Next ⟩

Abstract

Liquid phase alkylation of biphenyl (BP) was studied over large pore zeolites. Selective formation of the least bulky products, 4,4'-diisopropylbiphenyl (4,4'-DIPB) occurred only in the isopropylation of BP over some large pore molecular sieves. H-mordenites (MOR) gave the highest selectivity among them. The dealumination of MOR enhanced catalytic activity and the selectivity of 4,4'-DIPB because of the decrease of coke-deposition. Non-selective catalysis occurs on external acid sites over MOR with the low $SiO_2/Al_2O_3$ ratio because severe coke-deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with reaction temperature. Selective formation of 4,4'-DIPB was observed at moderate temperatures such as $250^{\circ}C$, whereas the decrease of the selectivity of 4,4'-DIPB occurred at higher temperatures as $300^{\circ}C$. However, 4,4'-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores even at high temperatures. These decreases of the selectivity of 4,4'-DIPB are due to the isomerization of 4,4'-DIPB on the external acid sites. Some 12-membered molecular sieves, such as SSZ-24, MAPO-5 (M:Mg, Zn, Si), SSZ-31, and ZSM-12, which have straight channels, gave 4,4'-DIPB with moderate to high selectivity; however; SSZ-55, SSZ-42, and MAPO-36 (M: Mg, Zn) gave lower selectivity because of cages in 12-membered one dimensional channels. Three dimensional H-Y and Beta zeolites also yield 4,4'-DIPB in low yield because of their wide circumstances for the isopropylation of BP. The increasing the size of alkylating agent enhanced the shape-selective alkylaiton even for the zeolites, such as UTD-1. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) over MOR was non-selective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivity of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4'-DEBP was less selective. The least bulky 4-EBP and 4,4'-DEBP have the highest reactivity among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of MOR pores are too loose for shape selective formation of the least bulky isomers, 4-EBP and 4,4'-DEBP in the ethylation of BP, and that MOR pores have enough space for the further ethylation of 4,4'-DEBP.

Keywords

Acknowledgement

Supported by : Japan Society for the Promotion of Science (JSPS)

References

  1. P. T. Anastas and T. C. Williamson, (eds.), in 'Green Chemistry. Frontiers in Benign Chemical Synthesis and Processes,' Oxford University Press, Oxford (1998)
  2. S. M. Csicsery, Zeolite, 4, 202 (1984) https://doi.org/10.1016/0144-2449(84)90024-1
  3. P. B. Venuto, Micropor. Mater., 2, 297 (1994) https://doi.org/10.1016/0927-6513(94)00002-6
  4. Y. Sugi, Korean J. Chem. Eng., 17, 1 (2001)
  5. Y. Sugi, Y. Kubota, T. Hanaoka, and T. Matsuzaki, Catal. Survey Jpn., 5, 43 (2001) https://doi.org/10.1023/A:1012394525091
  6. Y. Sugi, Catal. (Shokubai), 47, 213 (2005)
  7. T. Matsuzaki, Y. Sugi, T. Hanaoka, K. Takeuchi, H. Arakawa, T. Tokoro, and G. Takeuchi, Chem. Express, 4, 413 (1989)
  8. Y. Sugi, T. Matsuzaki, T. Hanaoka, K. Takeuchi, T. Tokoro, and G. Takeuchi, Stud. Surf. Sci, Catal., 60, 303 (1991) https://doi.org/10.1016/S0167-2991(08)61907-2
  9. Y. Sugi and T. Hanaoka, Sekiyu Gakkaishi, 41, 193 (1998) https://doi.org/10.1627/jpi1958.41.193
  10. Y. Sugi, S. Tawada, T. Sugimura, Y. Kubota, T. Hanaoka, T. Matsuzaki, K. Nakajima, and K. Kunimori, Appl. Catal. A: Gen., 189, 251 (1999) https://doi.org/10.1016/S0926-860X(99)00282-3
  11. Y. Sugi, S. Tawada, T. Sugimura, and Y. Kubota, Catal. Lett., 77, 159 (2001) https://doi.org/10.1023/A:1012730910613
  12. S. Tawada, Y. Sugi, Y. Kubota, Y. Imada, T. Hanaoka, T. Matsuzaki, K. Nakajima, K. Kunimori, and J.-H. Kim, Catal. Today, 60, 243 (2000) https://doi.org/10.1016/S0920-5861(00)00341-2
  13. J.-H. Kim, Y. Sugi, T. Matsuzaki, T. Hanaoka, Y. Kubota, X. Tu, M. Matsumoto, A. Kato, G. Seo, and C. Pak, Appl. Catal., A: Gen., 131, 15 (1995) https://doi.org/10.1016/0926-860X(95)00101-8
  14. Y. Sugi, Y. Kubota, S. Tawada, S. Noda, I. Toyama, H. Ito, K. Sakakibara, S. Watanabe, T. Matsuzaki, and T. Hanaoka, Shokubai, 43, 113 (2002)
  15. G. S. Lee, J. J. Maj, S. C. Rocke, and J. M. Garces, Catal. Lett., 2, 243 (1989) https://doi.org/10.1007/BF00766213
  16. T. Matsuda and E. Kikuchi, Stud. Surf. Sci. Catal., 83, 295 (1994) https://doi.org/10.1016/S0167-2991(08)63269-3
  17. A. Katayama, M. Toba, G. Takeuchi, F. Mizukami, S. Niwa, and S. Mitamura, J. Chem. Soc., Chem. Commun., 39 (1991)
  18. C. Song and A. D. Schmitz, Sekiyu Gakkaishi, 42, 275 (1999) https://doi.org/10.1627/jpi1958.42.275
  19. P. Dejaifve, A. Auroux, P. C. Gravelle, J. C. Vedrine, Z. Gabelica, and E. G. Derouane, J. Catal., 70, 123 (1981) https://doi.org/10.1016/0021-9517(81)90322-5
  20. M. Guisnet and P. Magnoux, Appl. Catal., 54, 1 (1989) https://doi.org/10.1016/S0166-9834(00)82350-7
  21. S. Bhatia, J. Beltramini, and D. D. Do, Catal. Rev. Sci. Eng., 31, 431 (1989-90) https://doi.org/10.1080/01614948909349937
  22. H. G. Karge and J. Weitkamp, Chem. Ind. Tech., 58, 946 (1986) https://doi.org/10.1002/cite.330581206
  23. L. Meyers, T. H. Fleisch, G. J. Ray, J. T. Miller, and J. B. Hall, J. Catal., 110, 82 (1988) https://doi.org/10.1016/0021-9517(88)90299-0
  24. M. Sawa, M. Niwa, and Y. Murakami, Appl. Catal., 53, 169 (1989) https://doi.org/10.1016/S0166-9834(00)80019-6
  25. Y. Sugi, Y. Kubota, A. Ito, H. Maekawa, R. K. Ahedi, S. Watanabe, C. Asaoka, H.-S. Lee, J.-H. Kim, and G. Seo, Shokubai, 45, 114 (2003)
  26. Y. Sugi, Y. Kubota, A. Ito, H. Maekawa, R. K. Ahedi, S. Tawada, S. Watanabe, I. Toyama, C. Asaoka, H.-S. Lee, J.-H. Kim, and G. Seo, Stud. Surf. Sci. Catal., 154, 2228 (2005)
  27. H. Maekawa, A. Ito, H. Kawagoe, K. Komura, Y. Kubota, and Y. Sugi, Submitted to Micropor. Mesopor. Mater.
  28. S. K. Saha, S. B. Waghmode, H. H. Maekawa, K. Komura, Y. Kubota, Y. Sugi, Y. Oumi, and T. Sano, Micropor. Mesopor. Mater., 81, 289 (2005) https://doi.org/10.1016/j.micromeso.2005.02.009
  29. M. Bandyopadhyay, R. Bandyopadhyay, S. K. Tawada, Y. Kubota, and Y. Sugi, Appl. Catal. A: Gen., 225, 51 (2002) https://doi.org/10.1016/S0926-860X(01)00738-4
  30. S. K. Saha, S. B. Waghmode, H. Maekawa, R. Kawase, K. Komura, Y. Kubota, and Y. Sugi, Micropor. Mesopor. Mater., 81, 277 (2005) https://doi.org/10.1016/j.micromeso.2005.02.008
  31. H. Maekawa, S. K. Saha, S. A. R. Mulla, S. B. Waghmode, K. Komura, Y. Kubota, and Y. Sugi, Submitted to Appl. Catal. A: Gen
  32. R. Ahedi, K. Tawada, S. Kubota, Y. Sugi, and J.-H. Kim, J. Mol. Catal., A: Chem., 197, 133 (2003) https://doi.org/10.1016/S1381-1169(02)00627-1
  33. Manuscript in preparation
  34. Y. Kubota, S. Tawada, C. Naitoh, K. Nakagawa, N. Sugimoto, Y. Fukushima, and Y. Sugi, Shokubai, 41, 380 (1999)
  35. A. Maekawa, C. Naitoh, K. Nakagawa, K. Komura, Y. Kubota, Y. Sugi, D.-H. Choi, J.-H. Kim, and G. Seo, Submitted to Catal. Lett.
  36. G. Takeuchi, H. Okazaki, T. Kito, Y. Sugi, and T. Matsuzaki, Sekiyu Gakkaishi, 34, 242 (1991) https://doi.org/10.1627/jpi1958.34.242
  37. J. Horniakov, D. Mravec, M. Krlik, J. Leko, P. Graffin, and P. Moreau, Appl. Catal. A: Gen., 215, 235 (2001) https://doi.org/10.1016/S0926-860X(01)00538-5
  38. J. Horniakova, D. Mravec, J. Joffre, and P. Moreau, J. Mol. Catal. A: Chem., 185, 249 (2002) https://doi.org/10.1016/S1381-1169(02)00055-9
  39. D. L. Dorset, S. C. Weston, and S. S. Dhingra, J. Phys. Chem. B, 110, 2045 (2006) https://doi.org/10.1021/jp0565352
  40. M. Matsumoto, X. Tu, Y. Sugi, T. Matsuzaki, T. Hanaoka, Y. Kubota, J.-H. Kim, K. Nakajima, A. Igarashi, and K. Kunimori, Stud. Surf. Sci. Catal., 105, 1317 (1997) https://doi.org/10.1016/S0167-2991(97)80772-0
  41. K. Nakajima, T. Hanaoka, Y. Sugi, T. Matsuzaki, Y. Kubota, A. Igarashi, and K. Kunimori, ACS Symp. Ser., 738, 260 (1999)
  42. S. A. R. Mulla, S. B. Waghmode, S. Watanabe, Maekawa, K. Komura, Y. Kubota, Y. Sugi, J.-H. Kim, and G. Seo, Bull. Chem. Soc. Jpn., in press
  43. Y. Sugi, Y. Kubota, S. Tawada, S. Noda, I. Toyama, H. Ito, K. Sakakibara, S. Watanebe, T. Matsuzaki, T. Hanaoka, and J.-H. Kim, Shokubai, 43, 113 (2002)