화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Korean Journal of Chemical Engineering, Vol.17, No.1, 1-11, January, 2000
DOI10.1007/BF02789245  Export Citation
Shape-Selective Alkylation of Biphenyl Catalyzed by H-Mordenites
Yoshihiro Sugi†
  • Department of Chemistry, Faculty of Engineering, Gifu University, Gifu 501-1193, Japan
E-mail:
Liquid phase alkylation of biphenyl was studied over large pore zeolites. Selective formation of the narrowest products, 4,4''-diisopropylbiphenyl (4,4''DIPB), occurred only HM among the zeolites with twelve-membered pore openings. These shape-selective catalyses are ascribed to steric restriction of transition state and to entrance of bulky substrates into the pores. The dealumination of HM enhanced catalytic activity and the selectivity of 4,4''-DIPB because of the decrease of coke-deposition, while the activity and the selectivity were low over HM with the low SiO2/AI2O3 ratio. Non-regioselective catalysis occurs on external acid sites because severe cokedeposition deactivates the acid sites inside the pores by blocking pore opening. The selectivity of DIPB isomers was changes with propylene pressure and/or with reaction temperature. 4,4''-DIPB yielded selectively under high propylene pressure(<0.3MPa) at 250℃, while the selectivity of 4,4''-DIPB decreased under such low propylene pressure as 0.2 MPa. Selective formation of 4,4''DIPB was observed at moderate temperature such as 250℃, whereas the decrease of the selectivity of 4,4''DIPB occurred at higher temperature as 300℃. However, 4,4''-DIPB was almost exclusively isomer in the encapsulated DIPB isomers inside the pores under every pressure and temperature. These decreases of the selectivity of 4,4''-DIPB are due to the isomerization of 4,4''-DIPB on the external acid sites. The deactivation of external acid sites of HM was examined to reduce non-regioselective alkylation and isomerization. External acid sites were deactivated by calcination after impregnation of cerium on HM without the decrease in pore radii. Selectivities of 4,4''-DIPB were improved even at high temperatures in the isopropylation of biphenyl because of the suppression of non-regioselective alkylation and isomerization at the external acid sites. The selectivity of 4.4''-diethylbiphenyl(4,4''-DIPB) in the ethylation of biphenyl was much lower than that in the isopropylation. Among the DIPB isomers, 4,4''-DIPB has the higher reactivity for the ethylation to polyethylbiphenyls inside the pores, whereas the isopropylation of 4,4''-DIPB was negligibly low inside the pores. These differences are ascribed to the difference in steric restriction at the transition state compound of substrate, alkylating agent, and acid sites inside the pores.
Keywords:Alkylation;Biphenyl;Shape-selectivity;Restricted Transition State Mechanism;H-mordenite;Dealumination;External Acid Sites;Ceria Modification
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