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The ellipse and hyperbola types are shown in Fig 42(a) and (b), respectively The PSPS goes through all-pure component vertices and the stoichiometric pole of x = (1, 1) since T = 1 For the ellipse type (example 1; Fig 42(a)), the PSPS does not move into the triangle but rather intersects with the chemical equilibrium surface only at the pure components A and B Consequently, there exists no reactive azeotrope, and all azeotropes are located outside the triangle A reactive azeotrope (RA = a non-pure component intersection of the PSPS with the chemical equilibrium surface) is located, if C is the highest boiler (example 2; Fig 42(b)) This is in agreement with the general conclusion reached by Barbosa and Doherty [16] that reactive azeotropes can exist only if the volatilities of the reactants are either all higher or all lower than the volatilities of the products.

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For example 1, the singular points of the considered reactive condenser are collected in one diagram in Fig 43(a), while Fig 43(b) shows analogous singular points for the reactive reboiler In both systems, as mentioned earlier, all singular points are located on the same ellipse-shaped PSPS In general, the location and stability of the singular points of the reboiler and condenser are different for the same Damk hler number For process design purposes the stable nodes at positive Damk hler numbers are of major interest These points are collected and depicted in a feasibility diagram (Fig 43(c)), which illustrates the changing of possible column products with respect to the Damk hler number For the here-considered system, pure A can be the only top product and pure B can be the only bottom product For example 2, Figs 4.

45 8

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4(a) and (b) show the bifurcations of all singular points with respect to the Damk hler numbers of the reactive condenser and the reactive reboiler, respectively As can be seen from the feasibility diagram in Fig 44(c), at Damk hler numbers Dac > 0830, two possible condenser products that is, the top products of a fully reactive distillation column, are predicted The kinetic azeotrope in the reactive reboiler is always the possible bottom product of a column..

In adsorptive reactors an adsorbent is employed as a regenerative source or sink for one or more of the reacting species, thus enabling a modification of the concentration conditions within the reactor to enhance its performance. In a simple reversible reaction, for instance, the local adsorption of a reaction (by)product in a fixed bed comprised of catalyst and adsorbent serves to displace the equilibrium composition to higher conversions than would otherwise be attained (Fig. 7.1). Due to the progressive exhaustion of the adsorbent capacity, one observes two distinct reaction fronts: (i) a stationary equilibrium-limited purely catalytic reaction zone in the vicinity of the reactor inlet; and (ii) a dynamic downstream zone corresponding to the location of the adsorptive breakthrough front. It can be appreciated that neither of these fronts is especially sharp due to the decelerating reaction kinetics when approaching equilibrium on one hand and the protracted interaction between adsorption and reaction on the other hand. The almost quantitative conversions which can thus be achieved are of course of limited duration sooner or later the propagating adsorptive reaction zone reaches the end of the reactor necessitating regeneration of the adsorbent after which the adsorptive reaction cycle can be commenced anew. Although most attention has been devoted to the task of equilibrium displacement through the (by)product removal just described [1], the incorporation of adsorption in chemical reactors can also be used to enrich reactants, either as an alternative technique to shift equilibria or to ensure complete conversion in irreversible reactions by providing local excess of one reactant [2]. In addition, adsorption can be exploited to sequester labile intermediates [3], thus avoiding unwanted consecutive reactions, or to intensify heat and mass transfer processes by enhancing local gradients [4], through acting as a local heat source for endothermic reactions, for example (Fig. 7.2).