Dense metallic membrane dehydrogenation reactions

The effect of reactant loss on membrane reactor performance was explained nicely in a study by Harold et al [5.25], who compared conversion during the cyclohexane dehydrogenation reaction in a PBMR equipped with different types of membranes. The results are shown in Fig. 5.4, which shows the cyclohexane conversion in the reactor as a function of the ratio of permeation to reaction rates (proportional to the ratio of a characteristic time for reaction in the packed bed to a characteristic time for transport through the membrane). Curves 1 and 2 correspond to mesoporous membranes with a Knudsen (H2/cyclohexane) separation factor. Curves 3 and 4 are for microporous membranes with a separation factor of 100, and curves 5 and 6 correspond to dense metal membranes with an infinite separation factor. The odd numbered curves correspond to using an inert sweep gas flow rate equal to the cyclohexane flow, whereas for the even numbered curves the sweep to cyclohexane flow ratio is 10. 

A large number of hydrogenation and dehydrogenation reactions were tested in the early studies of dense-metal membrane reactors (see listing in Shu et al. [34], Hsieh [35], and Gryaznov and Orekhova [36]). Many works tested the dehydrogenation of cyclohexane to benzene as a model reaction since it can be carried out at low temperature with no side reactions and no deactivation a conversion of 99.5% was achieved with a palladium membrane, compared with 18.7% at equilibrium, at 200°C [31]. 

Enhancement in conversion by the usage of a membrane reactor has been demonstrated for many dehydrogenation reactions. Product selectivity of some hydrogenation and other reactions arc found to improve with a permselective membrane as part of the reactor. Several dense metal as well as solid elecu olyte membranes and porous metal as well as various oxide membranes have been discovered to be effective for the reaction performance. 

Light alkane (C2-C4) dehydrogenation was the reaction studied by Gryaznov and coworkers in their pioneering studies [2.1, 2.2]. In their dehydrogenation reaction studies, they used Pd or Pd-alloy dense membranes, which were 100 % selective towards hydrogen permeation. The choice of these membranes in many of the early studies is because they were commercially available at that time in a variety of compositions, and their metallic nature allows the construction of multitubular and other complex-shaped membrane reactor systems. Comprehensive review papers on Pd membrane reactors have been published by the same group [2.1, 2.2], and also by Shu et al [2.3]. 

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