Nishamol, K; Rahna, K S; Sugunan, S(Elsevier, 2004)
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Abstract:
Various compositions of chromium manganese ferrospinels were tested as catalysts for the vapour phase alkylation of aniline with methanol. The samples were prepared by room temperature co-precipitation technique and characterized by various physico-chemical methods. The acidity–basicity determination revealed that the samples possess greater amount of basic sites than acidic sites. All the ferrite samples proved to be selective and active for N-monoalkylation of aniline leading to N-methyl aniline; Cr0.6Mn0.4Fe2O4, Cr0.8Mn0.2Fe2O4 and CrFe2O4 exhibited cent percent selectivity for N-methyl aniline. Neither C-alkylated products nor any other side products were detected for all catalyst samples. The catalytic activity of the samples studied in this reaction is related to their acid–base properties and also on the cation distribution. Under the optimized reaction conditions all the systems showed constant activity for a long duration.
Ferrospinels of nickel, cobalt and copper and their sulphated analogues were prepared by the room temperature coprecipitation
route to yield samples with high surface areas. The intrinsic acidity among the ferrites was found to decrease in
the order: cobalt> nickel> copper. Sulphation caused an increase in the number of weak and medium strong acid sites,
whereas the strong acid sites were left unaffected. Electron donor studies revealed that copper ferrite has both the highest
proportion of strong sites and the lowest proportion of weak basic sites. All the ferrite samples proved to be good catalysts
for the benzoy lation of toluene with benzoyl chloride. copper and cobalt ferrites being much more active than nickel ferrite.
The catalytic activity for benzoylation was not much influenced by sulphation, but it increased remarkably with calcination
temperature of the catalyst. Surface Lewis acid sites, provided by the octahedral cations on the spinel surface, are suggested
to be responsible for the catalytic activity for the benzoylation reaction.