Shape-selective alkylation of biphenyl over mordenites: effects of dealumination on shape-selectivity and coke deposition

Abstract

To understand the relationships between shape-selectivity and coke deposition in the alkylation of biphenyl over H-mordenite (HM), thermogravimetric analyses were examined for the catalyst after the reaction. The coke deposition during the catalysis was very severe over HM with low SiO/Al₂O₃ ratio, however, dealumination enhanced the decrease of coke deposition. Over highly dealuminated HM, volatile organic compounds, mainly biphenyl derivatives, were observed in addition to carbonaceous deposits. The deposits are produced from biphenyl derivatives on acid sites in the HM pore, and the ease of their formation is governed by acid site density and acid strength. The decrease of carbonaceous deposits and the increase of encapsulated biphenyl derivatives are related with the increase of both selectivity and yield of 4,4′-diisopropylbiphenyl (4,4′-DIPB). The increase of reaction temperature up to 250°C enhanced the catalysis over highly dealuminated HM, however, further increase of the temperature resulted in extensive decrease of the selectivity of 4,4′-DIPB. Coke deposition also increased with the temperature although its level was low. The composition of 4,4′-DIPB in encapsulated DIPB isomers remained as high as 80% in spite of a change of the distribution of bulk products.