I. Ivanova, E. Pomakhina, A. I. Rebrov
Oct 25, 2001
Citations
1
Influential Citations
54
Citations
Journal
Journal of Catalysis
Abstract
Abstract Aniline alkylation with methanol on zeolite H–Y has been studied using in situ 13 C MAS NMR spectroscopy under batch conditions. To clarify the main reaction pathways, the conversion of methanol as well as the interaction of aniline with surface methoxy groups were investigated under similar conditions. Methanol- 13 C and methyl iodide- 13 C were used as labeled reactants. Co -adsorption of aniline and methanol- 13 C on zeolite H–Y led to strongly adsorbed aniline molecules, assigned to aniline H-bonded to zeolite Bronsted acid sites, and three types of methanol species of different mobility: mobile methanol molecules with a liquid-like characteristics and two types of rigid methanol species with solid-like characteristics attributed to a methanol adsorption complex with aniline and surface methoxy groups, respectively. Among all the methanol species observed, only surface methoxy groups were shown to be responsible for aniline alkylation which takes place at temperatures from 373 to 523 K. The formation of surface methoxy groups was found to be a limiting step of the overall reaction. The primary alkylation product is N -methylaniline. Toluidines and N -methyltoluidines are formed at temperatures from 523 to 623 K after complete conversion of methanol to N -methylaniline. Therefore, isomerization or disproportionation of N -methylaniline was proposed to account for their formation.