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Abstract

The vapour phase hydrogenation of 1,3-cyclo-octadiene (COD) over Pd on alumina has been studied in the gas phase, using a recycle reactor. The dependences of COD hydrogenation rates and those of the consecutive cyclo-octene (COE) hydrogenation on the reaction conditions are well described by a model which takes into account mass transfer in the porous layer of palladium. The kinetics of the COE hydrogenation is of a Langmuir-Hinshelwood type. The hydrogenation of COD is of first order with respect to hydrogen. The reaction order with respect to COD is −0.15. If the catalyst surface is completely covered by COD, the hydrogenation of COE is totally suppressed. This indicates a much stronger adsorption of COD than of COE. Hydrogenation of COE can only occur in the innermost part of the pores when the transport of COD by diffusion is insufficient to supply the entire active surface of the catalyst. This happens if the ratio Pmath image/PCOD exceeds 2/φ2 with φ being the Thiele's modulus. This relationship permits a simple evaluation of the effective diffusion coefficient in the porous Pd-layer.