Sreekumar, K; Raja, T; Kiran, B P; Sugunan, S; Rao, B S(Elsevier, 1999)
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Abstract:
The reaction of aniline with methanol was carried out over Zn1-xNixFe2O4 (x= 0, 0.2, 0.5, 0.8 and 1) type systems in a
fixed-bed down-flow reactor. It was observed that systems possessing low ``x'' values are highly selective and active for mono
N-alkylation of aniline leading to N-methyl aniline. Selectivity for N-methyl aniline over ZnFe2O4 was more than 99% under
the optimized reaction conditions. Even at methanol to aniline molar ratio of 2, the yield of N-methyl aniline was nearly
55.5%, whereas its yield exceeded 67% at the molar ratio of 7. The Lewis acid sites of the catalysts are mainly responsible for
the good catalytic performance. Cation distribution in the spinel lattice influences their acido-basic properties, and hence,
these factors have been considered as helpful to evaluate the activity and stability of the systems.
Sreekumar, K; Jyothi, T M; Talawar, M B; Kiran, B P; Rao, B S(Elsevier, 2000)
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Abstract:
A series of ferrites having the general formula Zn1-xCoxFe2O4 (x=0, 0.2, 0.5, 0.8 and 1.0)were prepared by soft
chemical route. The materials were characterized by adopting various physico-chemical methods. The reaction of aniline
with methanol was studied in a fixed-bed reactor system as a potential source for the production of various methyl anilines.
It was observed that systems possessing low ‘ x’ values are highly selective and active for N-monoalkylation of aniline
leading to N-methylaniline. Reaction parameters were properly varied to optimize the reaction conditions for obtaining
N-methylaniline selectively and in better yield. Among the systems Zn0.8Co0.2Fe2O4 is remarkable due to its very high
activity and excellent stability. Under the optimized conditions N-methylaniline selectivity exceeded 98%. Even at a
methanol to aniline molar ratio of 2, the yield of N-methylaniline was nearly 50%, whereas its yield exceeded 71% at the
molar ratio of 5. ZnFe2O4, though executed better conversion than Zn0.8Co0.2Fe2O4 in the initial period of the run,
deactivates quickly as the reaction proceeds. The Lewis acidity of the catalysts is mainly responsible for the good
performance. Cation distribution in the spinel lattice influences their acido-basic properties and, hence, these factors have
been considered as helpful parameters to evaluate the activity of the systems.