Complex Catalytic Processes by C.H. Bamford and C.F.H. Tipper (Eds.)

By C.H. Bamford and C.F.H. Tipper (Eds.)

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11. Distribution of (a) deuteroethylene yields and (b) deuteroethane yields as a function of conversion observed in the reaction of ethylene with deuterium over a nickel wire at 90°C [91]. may give misleading values of the specific activities. One of the earliest studies of the reaction of C2H4with D2,in which a full mass spectrometric analysis of the products was performed, used a nickel wire as catalyst [115,116]. Some typical results are shown in Fig. 11. These results showed that ethylene exchange was rapid and the deuteroethylenes are probably formed in a stepwise process in which only one deuterium atom is introduced during each residence of the ethylene molecule on the surface, that is there is a high probability of ethylene desorption from the surface.

Distribution of the n-butenes as a function of extent of hydrogenation of butl e n e over palladiumalumina at 37OC [ 1241. 0, But-1-ene; @, trans-but-2-ene; @, cis-but-2ene. Dotted lines indicate thermodynamic equilibrium yields. 41 -0 20 40 600 n-Butane (%) 20 40 0 n-Butane (%) 20 n-Butane 40 (n) Fig. 15. Distribution of t h e n-butenes as a function of t h e extent of hydrogenation of ( a ) but-1-ene a t 33'C, ( b ) trans-but-2ene a t 33'C and ( c) cis-but-2-ene a t 49OC over r u t h e n i u m a l u m i n a catalysts [ 1231.

6). 5 Similar results have been obtained using silica-supported metals [ 53,641, although the shape of the isotherm and the extent of retention appear t o be dependent upon the physical nature of the catalyst (Fig. 7). With alumina-supported palladium, platinum and rhodium and silicasupported platinum [65,66] in the temperature range 20-200"C, no molecular exchange between adsorbed 14C-ethyleneand gaseous ethylene is observed, whilst with hydrogen, small quantities of methane are formed at 100°C and above with platinum and rhodium and at 200°C with palladReferences PP.

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