Synthesis of quinolines from aniline and propanol over modified USY zeolite: catalytic performance and mechanism evaluated by in situ Fourier transform infrared spectroscopy

Abstract

The reaction of aniline and propanol to quinolines was conducted in a fixed-bed flow-type reactor, using a series of modified USY zeolite catalysts. The structural, textural and acidic properties of the catalyst were characterized by XRD, N₂-physisorption, ²⁷Al MAS NMR, NH₃-TPD and pyridine-FTIR, while the mechanism for the reaction of aniline and propanol was investigated by in situ FTIR. It was identified that the reaction of aniline and propanol generated predominantly quinolines, including 2-ethyl-3-methylquinoline and other alkyl quinoline, N-alkyl aniline and other byproducts. Among others, the ZnCl₂/Ni-USY catalyst exhibited the best performance, providing a 96.4% conversion of aniline and a 78.3% total yield of quinolines with 81.2% total selectivity to quinolines and 60.1% selectivity to 2-ethyl-3-methylquinoline at 683 K. This was attributed to the larger concentration ratio of Lewis acid sites to Bronsted acid sites over the ZnCl₂/Ni-USY catalyst, relative to other catalysts. There were predominantly two possible routes for the formation of quinolines, which required predominantly Lewis acid sites and Bronsted acid sites, respectively. In both the routes, N-phenylpropan-1-imine was proposed as the key intermediate. Relative to that based on Bronsted acid sites, the route based on Lewis acid sites appeared to contribute much more in the generation of quinolines from the reaction of aniline and propanol.