[en] The kinetics of selective hydrodechlorination of 1,2-dichloro-ethane into ethylene over a Pd-Ag/SiO2 catalyst is studied. Kinetic data at 573, 596, and 647 K have been obtained by means of experimental designs in the space of the partial pressures of the four components influencing kinetics, that is, 1,2-dichloroethane, hydrogen, ethylene, and hydrogen chloride. One model among the numerous ones examined allows us to represent correctly the experimental data. Ii: corresponds to the following mechanism: dechlorination of 1,2-dichloroethane into ethylene occurs on silver through dissociative adsorption with successive breaking of the two C-Cl bonds and desorption of C2H4. Thanks to its activation power of hydrogen by dissociative chemisorption, palladium present at the surface of the alloy supplies hydrogen atoms for regeneration of the chlorinated silver surface into metallic silver. The presence of hydrogen adsorbed on Pd also causes the undesired ethylene hydrogenation leading to a loss of olefin selectivity. (C) 2001 Academic Press.
Disciplines :
Chemical engineering
Author, co-author :
Heinrichs, Benoît ; Université de Liège - ULiège > Département de chimie appliquée > Génie chimique - Chimie physique appliquée
Schoebrechts, Jean-Paul
Pirard, Jean-Paul ; Université de Liège - ULiège > Département de chimie appliquée > Génie chimique - Chimie physique appliquée
Language :
English
Title :
Palladium-silver sol-gel catalysts for selective hydrodechlorination of 1,2-dichloroethane into ethylene III. Kinetics and reaction mechanism
Publication date :
2001
Journal title :
Journal of Catalysis
ISSN :
0021-9517
eISSN :
1090-2694
Publisher :
Academic Press, San Diego, United States - California
Ainbinder Z., Manzer L.E., Nappa M.J. Handbook of Heterogeneous Catalysis , G. Ertl, H. Knözinger, and J. Weitkamp, Eds. Wiley-VCH, Weinheim; 1997, 4:1677.
Froment G.F., Bischoff K.B. Chemical Reactor Analysis and Design, Wiley, New York; 1990.
Rylander P.N. Catalysis: Science and Technology , J. R. Anderson and M. Boudart, Eds. Springer-Verlag, Berlin; 1983, 4:1.
Heinrichs B. L'hydrodéchloration sélective du 1,2-dichloroéthaneen éthylène sur des catalyseurs Pd-Ag/SiO2, Ph.D. thesis, Université de Liège, Liège; 1999.
Himmelblau D.M. Process Analysis by Statistical Methods, Wiley, New York; 1970.
Press W.H., Flannery B.P., Teukolsky S.A., Vetterling W.T. Numerical Recipes in C - The Art of Scientific Computing, Cambridge Univ. Press, Cambridge; 1990.
Boudart M., Djéga-Mariadassou G. Kinetics of Heterogeneous Catalytic Reactions, Princeton Univ. Press, Princeton; 1984.
Van Santen R.A., Niemantsverdriet J.W. Chemical Kinetics and Catalysis, Plenum, New York; 1995.
Boudart M. Kinetics of Chemical Processes, Prentice-Hall, Englewood Cliffs, NJ; 1968.
Kapteijn F., Moulijn J.A. Handbook of Heterogeneous Catalysis , G. Ertl, H. Knözinger, and J. Weitkamp, Eds. Wiley-VCH, Weinheim; 1997, 3:1189.
Yang M.X. Halogenated Hydrocarbons, Hydrogen Atoms and Metal Surfaces: Isolating Intermediates and Identifying Mechanisms in Catalytic Dehalogenation, Ph. D. thesis, Columbia University, New York; 1995.
Henderson M.A., Mitchell G.E., White J.M. Surf. Sci. 1987, 184.
Anju Y., Mochida I., Yamamoto H., Kato A., Seiyama T. Bull. Chem. Soc. Jpn. 1972, 45:2319.
Wachs I.E., Kelemen S.R. Proceedings, 7th International Congress on Catalysis, Tokyo, 1980, T. Seiyama and K. Tanabe, Eds. Paper A48. Elsevier, Amsterdam; 1981.
Moss R.L., Thomas D.H. J. Catal. 1967, 8:162.
Klugherz P.D., Harriott P. AIChE J. 1971, 17:856.
Metcalf P.L., Harriott P. Ind. Eng. Chem. Process Des. Dev. 1972, 11:478.
Van Santen R.A., Kuipers H.P.C.E. Adv. Catal. 1988, 35:265.
Backx C., De Groot C.P.M., Biloen P. Appl. Surf. Sci. 1980, 6:256.
Kagawa S., Iwamoto M., Mori H., Seiyama T. J. Phys. Chem. 1981, 85:434.
Huang Y.-Y. J. Catal. 1980, 61:461.
Derouane E.G., Pirard J.-P., L'Homme G.A., Fabry-Volders E. Catalysis: Heterogeneous and Homogeneous. Proceedings of the International Symposium on the Relations between Heterogeneous and Homogeneous Catalytic Phenomena, Brussels, Belgium, October 23-25, 1974,. Elsevier, Amsterdam; 1975.
Pirard J.-P., Kalitventzeff B. Ind. Eng. Chem. Fund. 1978, 17:11.
Van Santen R.A. Handbook of Heterogeneous Catalysis , G. Ertl, H. Knözinger, and J. Weitkamp, Eds. Wiley-VCH, Weinheim; 1997, 5:2244.
Backx C., Moolhuysen J., Geenen P., Van Santen R.A. J. Catal. 1981, 72:364.
Bergeret G., Gallezot P. Handbook of Heterogeneous Catalysis , G. Ertl, H. Knözinger, and J. Weitkamp, Eds. Wiley-VCH, Weinheim; 1997, 2:439.
Nieuwenhuys B.E. Stud. Surf. Sci. Catal. 1987, 32:476.
Kok G.A., Noordermeer A., Nieuwenhuys B.E. Surf. Sci. 1985, 152-153:505.
Noordermeer A., Kok G.A., Nieuwenhuys B.E. Surf. Sci. 1986, 165:375.
Knor Z. Catalysis: Science and Technology , J. R. Anderson and M. Boudart, Eds. Springer-Verlag, Berlin; 1982, 3:231.
Pirard J.-P. Approche Multidisciplinaire d'un Problème de Catalyse Hétérogéne - L'Hydrogénation de l'Ethylène par le Cuivre Déposé sur l'Oxyde de Magnésium, Ph.D. thesis, Université de Liège, Liège; 1974.
Pajonk G.M. Handbook of Heterogeneous Catalysis , G. Ertl, H. Knözinger, and J. Weitkamp, Eds. Wiley-VCH, Weinheim; 1997, 3:1064.