Vapor Phase Transesterification of Dimethyl Malonate with Phenol over Cordierite Honeycomb Coated with Zirconia and Its Modified Forms
The transesterification of dimethyl malonate (DMM)
with phenol has been studied in vapour phase over cordierite
honeycomb coated with solid acid catalysts such as ZrO2,
Mo(VI)/ZrO2 and SO42-/ZrO2. The catalytic materials were prepared
honeycomb coated, powder forms, and characterized for their total
surface acidity by NH3-TPD and crystalinity by powder XRD
methods. Phenyl methyl malonate (PMM) and diphenyl malonate
(DPM) were obtained as the reaction products. A good conversion of
DMM (up to 82%) of MPM with 95% selectivity was observed when
the reactions were carried out at a catalyst bed temperature of 200 °C
and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst.
However, over SO4^2-/ZrO2 catalyst, the yield of DPM was found to be
higher. The results have been interpreted based on the variation of
acidic properties and powder XRD phases of zirconia on
incorporation of Mo(VI) or SO42– ions. Transesterification reactions
were also carried out over powder forms of the catalytic materials
and the yield of the desired phenyl ester products were compared
with that of the HC coated catalytic materials. The solid acids were
found to be reusable when used for at least 5 reaction cycles.
[1] T. A. Nijhuis, M. T. Kreutzer, A. C. J. Romijn, F. Kapteijn, J. Moulijn,
Chem. Eng. Sci. 56, 2001, pp. 823.
[2] Sudhanshu Sharma, PhD Thesis, Gas phase and electro catalytic
reaction over Pt, Pd ions substituted CeO2, TiO2 catalysts and electronic
Interaction between noble metal ions and the reducible oxide, 2009.
[3] A. Corma, Chem. Rev. 95, 1995, pp. 559.
[4] K. Tanabe, W. F. Holderich, Appl. Catal. A. 81(2), 1999, pp. 399.
[5] G. D. Yadav, J. J. Nair, Micropor. Mesopor. Mater, 33, 1999, pp. 1.
[6] J. Otera, Chem. Rev. 93, 1993, pp. 1449.
[7] A. Corma, S. Iborra, S. Miquel, J. Primo, 1998 J. Catal,173 1998, pp.
315.
[8] P. Ilankumaran, J. G. Verkade, 1999 J. Org. Chem. 64, 1999, pp. 3086.
[9] S. Y. Park, H. Morimoto, S. Matsunaga, M. Shibasaki, Tetrahedon
Letters, 48 (16), 2007, pp. 1035.
[10] S. E. Sen, M. Smith, K. A. Sulivan, 1998 Tetrahedron 55, 1998, pp.
12657.
[11] K. C. Patil, M. S. Hegde, T. Rattan, H. T. Aruna, Chemistry of Nano
Crystalline Oxide Materials, Combustion Synthesis, Properties and
Applications, World Scientific Publishing Pvt. Ltd, Singapore, 2008.
[12] N. Nagaraju, S. Z. Mohamed Shamshuddin, Catal. Commun. 7(3) 2006,
pp. 593.
[13] S. Z. Mohamed Shamshuddin, M. Shyamsundar, N. Thimmaraju,
Venkatesh, G. Vatsalya, M. Senthilkumar, Comptes Rendus Chemie, 15,
2012, pp. 799.
[1] T. A. Nijhuis, M. T. Kreutzer, A. C. J. Romijn, F. Kapteijn, J. Moulijn,
Chem. Eng. Sci. 56, 2001, pp. 823.
[2] Sudhanshu Sharma, PhD Thesis, Gas phase and electro catalytic
reaction over Pt, Pd ions substituted CeO2, TiO2 catalysts and electronic
Interaction between noble metal ions and the reducible oxide, 2009.
[3] A. Corma, Chem. Rev. 95, 1995, pp. 559.
[4] K. Tanabe, W. F. Holderich, Appl. Catal. A. 81(2), 1999, pp. 399.
[5] G. D. Yadav, J. J. Nair, Micropor. Mesopor. Mater, 33, 1999, pp. 1.
[6] J. Otera, Chem. Rev. 93, 1993, pp. 1449.
[7] A. Corma, S. Iborra, S. Miquel, J. Primo, 1998 J. Catal,173 1998, pp.
315.
[8] P. Ilankumaran, J. G. Verkade, 1999 J. Org. Chem. 64, 1999, pp. 3086.
[9] S. Y. Park, H. Morimoto, S. Matsunaga, M. Shibasaki, Tetrahedon
Letters, 48 (16), 2007, pp. 1035.
[10] S. E. Sen, M. Smith, K. A. Sulivan, 1998 Tetrahedron 55, 1998, pp.
12657.
[11] K. C. Patil, M. S. Hegde, T. Rattan, H. T. Aruna, Chemistry of Nano
Crystalline Oxide Materials, Combustion Synthesis, Properties and
Applications, World Scientific Publishing Pvt. Ltd, Singapore, 2008.
[12] N. Nagaraju, S. Z. Mohamed Shamshuddin, Catal. Commun. 7(3) 2006,
pp. 593.
[13] S. Z. Mohamed Shamshuddin, M. Shyamsundar, N. Thimmaraju,
Venkatesh, G. Vatsalya, M. Senthilkumar, Comptes Rendus Chemie, 15,
2012, pp. 799.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:71556", author = "Prathap S. Raghavendra and Mohamed S. Z. Shamshuddin and Thimmaraju N. and Venkatesh", title = "Vapor Phase Transesterification of Dimethyl Malonate with Phenol over Cordierite Honeycomb Coated with Zirconia and Its Modified Forms", abstract = "The transesterification of dimethyl malonate (DMM)
with phenol has been studied in vapour phase over cordierite
honeycomb coated with solid acid catalysts such as ZrO2,
Mo(VI)/ZrO2 and SO42-/ZrO2. The catalytic materials were prepared
honeycomb coated, powder forms, and characterized for their total
surface acidity by NH3-TPD and crystalinity by powder XRD
methods. Phenyl methyl malonate (PMM) and diphenyl malonate
(DPM) were obtained as the reaction products. A good conversion of
DMM (up to 82%) of MPM with 95% selectivity was observed when
the reactions were carried out at a catalyst bed temperature of 200 °C
and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst.
However, over SO4^2-/ZrO2 catalyst, the yield of DPM was found to be
higher. The results have been interpreted based on the variation of
acidic properties and powder XRD phases of zirconia on
incorporation of Mo(VI) or SO42– ions. Transesterification reactions
were also carried out over powder forms of the catalytic materials
and the yield of the desired phenyl ester products were compared
with that of the HC coated catalytic materials. The solid acids were
found to be reusable when used for at least 5 reaction cycles.", keywords = "Cordierite honeycomb, methyl phenyl malonate,
vapour phase transesterification, zirconia.", volume = "9", number = "12", pages = "1383-4", }