Catalytic reactor, continuously-stirred

Bubble slurry column reactors (BSCR) and mechanically stirred slurry reactors (MSSR) are particular types of slurry catalytic reactors (Fig. 5.3-1), where the fine particles of solid catalyst are suspended in the liquid phase by a gas dispersed in the form of bubbles or by the agitator. The mixing of the slurry phase (solid and liquid) is also due to the gas flow. BSCR may be operated in batch or continuous modes. In contrast, MSSR are operated batchwise with gas recirculation. 

We have used CO oxidation on Pt to illustrate the evolution of models applied to interpret critical effects in catalytic oxidation reactions. All the above models use concepts concerning the complex detailed mechanism. But, as has been shown previously, critical. effects in oxidation reactions were studied as early as the 1930s. For their interpretation primary attention is paid to the interaction of kinetic dependences with the heat-and-mass transfer law [146], It is likely that in these cases there is still more variety in dynamic behaviour than when we deal with purely kinetic factors. A theory for the non-isothermal continuous stirred tank reactor for first-order reactions was suggested in refs. 152-155. The dynamics of CO oxidation in non-isothermal, in particular adiabatic, reactors has been studied [77-80, 155]. A sufficiently complex dynamic behaviour is also observed in isothermal reactors for CO oxidation by taking into account the diffusion both in pores [71, 147-149] and on the surfaces of catalyst [201, 202]. The simplest model accounting for the combination of kinetic and transport processes is an isothermal continuously stirred tank reactor (CSTR). It was Matsuura and Kato [157] who first showed that if the kinetic curve has a maximum peak (this curve is also obtained for CO oxidation [158]), then the isothermal CSTR can have several steady states (see also ref. 203). Recently several authors [3, 76, 118, 156, 159, 160] have applied CSTR models corresponding to the detailed mechanism of catalytic reactions. 

Tipnis and Carberry (1984) and Carberry et al. (1985) used this concept to design, construct and demonstrate a gradientless gas-liquid-solid catalytic reactor of well-defined interface. With the use of high-speed wipers, a continuously fed liquid film is sustained upon a catalytic wall in the presence of a continuously fed, well-stirred gas phase. This design allows the measurement of intrinsic kinetics of gas-liquid-solid catalytic systems. 

Chapter 7, Reactor Design, discusses continuous and batch stirred-tank reactors and die packed-bed catalytic reactor, which are frequently used. Heat exchangers for stirred-tank reactors described are the simple jacket, simple jacket with a spiral baffle, simple jacket with agitation nozzles, partial pipe-coil jacket, dimple jacket, and the internal pipe coil. The amount of heat removed or added determines what jacket is selected. Other topics discussed are jacket pressure drop and mechanical considerations. Chapter 7 also describes methods for removing or adding heat in packed-bed catalytic reactors. Also considered are flow distribution methods to approach plug flow in packed beds. 

There are numerous reactor types, but in this chapter the objective is to consider only a few common types. These are batch, continuous stirred tank, homogenous plug flow and fixed bed catalytic reactors. To size other reactor types and for a more thorough treatment of reactor design than presented here, the reader can consult books written on reactor design, such as Fogler [16], Smith [23], and Forment and Bischoff [31]. 

The simplicity and general utility of the Madon-Boudart criterion make it one of the most important experimental tests to confirm that kinetic data are free from artifacts. It can be used for heterogeneous catalytic reactions carried out in batch, continuous stirred tank, and tubular plug flow reactors. 

In Table I the high-vacuum (HV) range means a pressure of 10 to 10 Torr entries designated by Torr mean pressures between 0.1 and 10 Torr flow refers to an unspecified steady-state flow pattern. It is apparent from Table I that there is a great diversity in the different oscillation conditions and catalytic systems. The pressures under which oscillations have been observed vary from 10 Torr for the CO/NO reaction on Pt(lOO) 141, 142) to atmospheric pressure for a large number of systems. The reactors used in these studies include ultrahigh-vacuum (UHV) systems, continuous stirred tank reactors (CSTRs), flow reactors, and reactors designed as infrared (IR) cells, calorimeters, and ellipsometric systems. 

The simulations discussed above are focused on the behavior of single catalytic oscillators at fixed reactant pressures. In the full-scale analysis of reactions on nm-supported particles, the reactant pressures should be calculated self-consistently with the reaction kinetics. At present, due to computational limitations, the self-consistent treatment can, however, be done only by using the MF equations (see, e.g., recent simulations [57] of oscillations in CO oxidation in a continuously stirred tank reactor). The MF approach does not, however, make it possible to scrutinize the reaction kinetics on the nm scale. Under such circumstances, the MC and MF treatments are complementary. In particular, the MC results may be employed in order to understand the limits of applicability of the MF approximation. 

To derive the overall kinetics of a gas/liquid-phase reaction it is required to consider a volume element at the gas/liquid interface and to set up mass balances including the mass transport processes and the catalytic reaction. These balances are either differential in time (batch reactor) or in location (continuous operation). By making suitable assumptions on the hydrodynamics and, hence, the interfacial mass transfer rates, in both phases the concentration of the reactants and products can be calculated by integration of the respective differential equations either as a function of reaction time (batch reactor) or of location (continuously operated reactor). In continuous operation, certain simplifications in setting up the balances are possible if one or all of the phases are well mixed, as in continuously stirred tank reactor, hereby the mathematical treatment is significantly simplified. 

Catalytic oxidation of p-xylene with air is the chief commercial method used to produce terephthalic acid. A solution of p-xylene in acetic acid, together with manganese or cobalt derivative and heavy metal bromides, which serve as cocatalysts, is fed to a continuous reactor, vigorously stirred, and heated to 200°C while under about 25 atm pressure. Air is continuously fed into the reactor at the same time as a small stream of partially reacted solution is removed (Eq. 19.66). 

In fact, since the leaving group, methyl carbonate, decomposes (reaction 3), the base is restored and can be used in truly catalytic amounts. This feature allows utihzation of continuous-flow (c-f) procedures (i.e. gas-liquid phase-transfer catalysis, GL PTC, and continuously stirred tank reactor, CSTR ). 

Fig. 12-3 Continuous stirred-tank catalytic reactor from D. G. Tajbl, J. B. Simons, and J. J. Carberry,...

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