화학공학소재연구정보센터
Applied Catalysis A: General, Vol.146, No.2, 269-284, 1996
Selective Hydrogenation of Acetylene in Ethylene Feedstocks on Pd Catalysts
Pumice supported palladium catalysts were compared with Pd/SiO2 and Pd/Al2O3 in the hydrogenation of acetylene using typical industrial ethylene feedstocks : front-end and tail-end cuts. Pd/pumice catalysts exhibit good activity and excellent selectivity and stability in the title reaction. Their activity/selectivity pattern is controlled by the composition of the reaction mixture. The turnover frequency (TOF) increases, and the apparent activation energy (E(a)) decreases, with the H-2/C2H2 ratio, but they are not affected by the C2H2/C2H4 ratio. The selectivity to ethane (S-E) does not change with acetylene conversion at low H-2/C2H2 ratio (tail-end cut) and increases at high H-2/C2H2 ratio (front-end cut). No dependence of S-E with acetylene conversion was found, at any H-2/C2H2 ratio, on varying the metal dispersion. TOF and S-E change with metal loading depending on the reaction mixtures; low metal loaded catalysts gave the best activity/selectivity pattern. Pd/pumice catalysts do not show aging phenomena even when used in drastic conditions (high space velocities and front-end cuts). The catalytic behavior of Pd/pumice catalysts, as a function of the composition of reaction mixture, elucidated by using the isokinetic relationship (IKR) approach shows that the relative amount of hydrogen in the feedstocks plays an important role in activation/deactivation processes which occurs on the metal surface. By considering the presence of different centers on the catalyst and by performing data analysis with a suitable mathematical model, the microscopical mechanism and the role of surface deposits can be explained. A similar reaction mechanism is applicable to the other palladium catalysts, at least in the case of tail-end mixtures.