skip to main content

Activity of Aniline Methylation over Fe-Cu-Cr Ternary Spinel Systems

Reni George  -  Department of Applied Chemistry, Cochin University of Science and Technology, Kochi-682022, Kerala, India
Kochurani George  -  Department of Applied Chemistry, Cochin University of Science and Technology, Kochi-682022, Kerala, India
*Sankaran Sugunan  -  Department of Applied Chemistry, Cochin University of Science and Technology, Kochi-682022, Kerala, India

Citation Format:
Abstract

A series of spinels having thegeneral formula CuCr2-xFexO4 with x=0.25,0.75, 1.25, 1.75 were prepared by co-precipitation method. The catalysts werecharacterized by various physico-chemical methods like XRD, BET, UV-DRS, SEM,EDX, TPD etc. The reaction of aniline with methanol was studied in a fixed-bedreactor system as a potential source for the production of various methylanilines. It was observed that systems possessing low ‘x’ values are highlyselective and active for N-monoalkylation of aniline leading toN-methylaniline. Reaction parameters were properly varied to optimize thereaction conditions for obtaining N-methylaniline selectively and in betteryield. Among the systems CuCr1.75Fe0.25O4 isremarkable due to its very high activity and excellent stability. Under theoptimized conditions N-methylaniline selectivity exceeded 91%. CuCr1.25Fe0.75O4gives better conversion than CuCr1.75Fe0.25O4in CuCr2-xFexO4 series. The Lewis acid sitesof the catalysts are mainly responsible for the good catalytic performance. © 2014 BCREC UNDIP. All rights reserved

Submitted: 18th July 2013; Revised: 5th November 2013; Accepted: 1st December 2013

[How to Cite: George, R., George, K., Sugunan, S. (2014). Activity of Aniline Methylation over Fe-Cu-Cr Ternary Spinel Systems. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (1): 39-44. (doi:10.9767/bcrec.9.1.5169.39-44)]


[Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.1.5169.39-44]

 

Fulltext View|Download
Keywords: aniline methylation; spinels system; Fe-Cu-Cr; co-precipitation; alkylation
Funding: CUSAT

Article Metrics:

  1. Landolt-Bronstein, Magnetic oxides and related compounds, Springer Berlin, 3 (1970)
  2. Goodenough, J.B. (1971). Metallic oxides, Progress in Solid State Chemistry. 5: 145-399
  3. Bragg, W.H. (1915). The structure of the spinel group of crystal. Philosophical Magazine, 30: 305-315
  4. Hill, R.J., Caig, J.R., Gibbs, G.V. (1979). Systematics of the spinel structure type. Physics and Chemistry of Minerals. 4: 317-339
  5. Navrotsky, A., Kleppa, O.J, (1967). The thermodynamics of cation distributions in simple Spinels. Journal of Inorganic and Nuclear Chemistry. 29: 2701-2714
  6. Dunitz, J.D., Orgel, L.E. (1957). Electronic properties of transition-metal oxides-I: Distortions from cubic symmetry. Journal of Physics and Chemistry of Solids. 3: 20-29
  7. Rennard, R.J., Kehi, W.L. (1971). Oxidative dehydrogenation of butenes over ferrite Catalysts. Journal of Catalysis. 21: 282-293
  8. Ghorpad
  9. e, S.P.(1998). Liquid-phase Friedel-Crafts alkylation using CuCr2-xFexO4 spinel catalys. Applied Catalysis A: General. 166: 135-142
  10. Sharpe, P.K., Vickerman, J.C., Stanay, M.H. in Proceedings of the sixth International Congress on Catalysis, London, 1976
  11. Dube, G.R., Darshane, V.S. (1991). X-ray, Electrical and catalytic studies of the system CoFe2O4-Co2TiO4. Bulletin of Chemical Society of Japan. 64: 2449-2453
  12. Nayak, H., Bhatta, D. (2002). Catalytic effects of magnesium chromite spinel on the decomposition of lanthanum oxalate. Thermochimica Acta 389: 109-119
  13. Haralambous, K.J., Loizos, Z., Spyrellius, N. (1991). Catalytic properties of some mixed transition-metal oxides. Material Letters. 11: 133-141
  14. Shimokawabe, M., Furuichi, R., Ishii, T. (1977). Effect of Metal-Oxide Additives on Thermal- Decomposition of Perchlorates, Oxalates and Hydroxides. Thermochimica Acta. 20: 347-361
  15. Said, A.A., Hassan, E.A., Abd EI.-Salaam, K.M. (1983). Electrical conductivity and thermogravimetric studies of the thermal decomposition of doped cobalt carbonate. Surface Technology. 20:123-130
  16. Ko, A.N., Yang, C.L., Zhu, W.D., Lin, H.E. (1996). Selective N-alkylation of aniline with methanol over γ-alumina. Applied Catalysis. A: General. 134: 53-66
  17. Narayanan, S., Deshpande K. (1998). Acid activation of montmorillonite : Effect on structural and catalytic properties. Studies in Surface Science and Catalysis. 113: 773–778
  18. Elangovan, S.P., Kannan, C., Arabindoo B., Murugesan, V. (1998). Applied Catalysis A: General 174: 213-219
  19. Chen, P.Y., Chen, M.C., Chen, H.Y., Chang, N.S., Chung, T. K., (1986). New developments in Zeolite Science and Technology. (Y. Murakami, A. Iijima, and J.W. Ward, Eds) Studies in Surface Science and Catalysis, Elsevier Amsterdam 28: 279
  20. Lian Su, B., Barthomeuf, D., (1995) Alkylation of aniline with methanol: change in selectivity with acido-basicity of faujasite catalysts. Applied Catalysis A: General 24: 73-80
  21. Ivanova, I.I., Pomakhina, E.B., Rebrov, A.I., Hunger, M., Kolyagin, Y.G. Jens, W. (2001). Surface Species Formed during Aniline Methylation on Zeolite HY Investigated by in Situ MAS NMR Spectroscopy. Journal of Catalysis. 203 : 375-381
  22. Bautista, F.M., Campelo, J.M., Garcisa, A., Luna, J.D., Marinas, M., Romero, A.A. (1997). Heterogeneous catalysis and Fine chemicals IV, Studies in Surface Science and Catalysis, Elsevier, Amsterdam, 108: 123
  23. Sreekumar, K., Jyothy, T., Sugunan, S. (2000). Kinetics of N-monomethylation of aniline with methanol over Zn1-xCoxFe2O4 (x=0,0.2,0.8,1.0) type systems. Reaction Kinetics and Catalysis Letters.70: 161-167
  24. Sreekumar, K., Sugunan, S. (2002). Ferro-spinels based on Co and Ni prepared via a low temperature route as efficient catalysts for the selective synthesis of o-cresol and 2, 6-xylenol from phenol and methanol. Journal of Molecular Catalysis A: Chemical. 185: 259-262
  25. Rahna, K.S., Nisha, K., Sugunan, S. (2003). Acidity and aniline alkylation of Mixed Fe-Al Pillared Montmorillonites. Reaction Kinetics and Catalysis Letters. 79: 19-26
  26. Nisha, K., Rahna, K.S., Sugunan, S. (2003) . Selective Alkylation of Aniline to N-methyl aniline using chromium Manganese Ferro-spinels, Journal of Molecular Catalysis A: Chemical. 209: 89-96

Last update:

No citation recorded.

Last update:

No citation recorded.