Pseudohomogeneous kinetics

Strictly gas-phase CSTRs are rare. Two-phase, gas-liquid CSTRs are common and are treated in Chapter 11. Two-phase, gas-solid CSTRs are fairly common. When the solid is a catalyst, the use of pseudohomogeneous kinetics allows these two-phase systems to be treated as though only the fluid phase were present. All concentration measurements are made in the gas phase, and the rate expression is fitted to the gas-phase concentrations. This section outlines the method for fitting pseudo-homogeneous kinetics using measurements made in a CSTR. A more general treatment is given in Chapter 10. 

The initial and boundary conditions are given in Chapter 9. The present treatment does not change the results of Chapter 9 but instead provides a rational basis for using pseudohomogeneous kinetics for a solid-catalyzed reaction. The axial dispersion model in Chapter 9, again with pseudohomogeneous kinetics, is an alternative to Equation 10.1 that can be used when the radial temperature and concentration gradients are small. 

The first eight chapters of this book treat homogeneous reactions. Chapter 9 provides models for packed-bed reactors, but the reaction kinetics are pseudohomogeneous so that the rate expressions are based on fluid-phase concentrations. There is a good reason for this. Fluid-phase concentrations are what can be measured. The fluid-phase concentrations at the outlet are what can be sold. 

Chapter 10 begins a more detailed treatment of heterogeneous reactors. This chapter continues the use of pseudohomogeneous models for steady-state, packed-bed reactors, but derives expressions for the reaction rate that reflect the underlying kinetics of surface-catalyzed reactions. The kinetic models are site-competition models that apply to a variety of catalytic systems, including the enzymatic reactions treated in Chapter 12. Here in Chapter 10, the example system is a solid-catalyzed gas reaction that is typical of the traditional chemical industry. A few important examples are listed here ... 

Deduce the functional form for the pseudohomogeneous, intrinsic kinetics. 

Determine the form of the pseudohomogeneous, intrinsic kinetics for each of these cases. Assume that the surface reaction step, as shown above, is rate limiting. 

The packed-bed reactors discussed in Chapters 9 and 10 are multiphase reactors, but the solid phase is stationary, and convective flow occurs only through the fluid phase. The reaction kinetics are pseudohomogeneous, and components balances are written only for the fluid phase. 

The pseudohomogeneous reaction term in Equation (11.42) is analogous to that in Equation (9.1). We have explicitly included the effectiveness factor rj to emphasis the heterogeneous nature of the catalytic reaction. The discussion in Section 10.5 on the measurement of intrinsic kinetics remains applicable, but it is now necessary to ensure that the liquid phase is saturated with the gas when the measurements are made. The void fraction s is based on relative areas occupied by the liquid and soUd phases. Thus,... 

In previous chapters, we deal with simple systems in which the stoichiometry and kinetics can each be represented by a single equation. In this chapter we deal with complex systems, which require more than one equation, and this introduces the additional features of product distribution and reaction network. Product distribution is not uniquely determined by a single stoichiometric equation, but depends on the reactor type, as well as on the relative rates of two or more simultaneous processes, which form a reaction network. From the point of view of kinetics, we must follow the course of reaction with respect to more than one species in order to determine values of more than one rate constant. We continue to consider only systems in which reaction occurs in a single phase. This includes some catalytic reactions, which, for our purpose in this chapter, may be treated as pseudohomogeneous. Some development is done with those famous fictitious species A, B, C, etc. to illustrate some features as simply as possible, but real systems are introduced to explore details of product distribution and reaction networks involving more than one reaction step. 

In this chapter, we develop some guidelines regarding choice of reactor and operating conditions for reaction networks of the types introduced in Chapter 5. These involve features of reversible, parallel, and series reactions. We first consider these features separately in turn, and then in some combinations. The necessary aspects of reaction kinetics for these systems are developed in Chapter 5, together with stoichiometric analysis and variables, such as yield and fractional yield or selectivity, describing product distribution. We continue to consider only ideal reactor models and homogeneous or pseudohomogeneous systems. 

Note that the results of our simulation via the pseudohomogeneous model tracks the actual plant very closely. However, since the effectiveness factors r]i were included in a lumped empirical fashion in the kinetic parameters, this model is not suitable for other reactors. A heterogeneous model, using intrinsic kinetics and a rigorous description of the diffusion and conduction, as well as the reactions in the catalyst pellet will be more reliable in general and can be used to extract intrinsic kinetic parameters from the industrial data. 

A one-dimensional pseudohomogeneous plug flow reactor model assuming isothermality was used to simulate experimental results. The continuity and kinetic expressions used were as follows ... 

In most investigations concerning the reactor modelling, simple pseudohomogeneous (t = 1) reactor models were used. The effect of external and internal mass and heat transfer resistances on the effectiveness factors using realistic complex reaction network has not been widely investigated. The simple linear kinetics proposed by... 

Tables 6.30, 6.31 show, respectively, the industrial and pseudohomogeneous model results given by Sheel and Crowe (1969) after introducing the corrections given by Crowe (1992). Table 6.32 gives the results of the pseudo-homogeneous model using the kinetic parameters of Sheel and Crowe (1969) without the corrections of the kinetic parameters provided by Crowe (1989). It is clear from Table...

Suppose that adsorption is much slower than surface reaction or desorption for the heterogeneously catalyzed reaction A P. Deduce the functional form of the pseudohomogeneous, intrinsic kinetics. 

The process is described by an one-dimensional, pseudohomogeneous, non-steady state dispersion model for an adiabatic fixed bed reactor. The kinetics are modelled by a re-versibll reaction system where each reaction step follows a power law with a reaction order of one in the gas and in the solid component. The temperature dependency of the reaction rate constant follows the Arrhenius law. The equilibrium constant is set to be independent of temperature. 

Low-pressure polymerizations were initiated by ultraviolet radiation in the presence of di-iert-butyl peroxide in bulk, dimethyl sulfoxide, or /ert-butanol solution at — 20°C to -I- 30°C. While the polymer precipitated out of solution at low conversion, in dimethyl sulfoxide, this precipitate was a gel which was partially transparent to light. At low conversions, the reaetion kinetics were treated as pseudohomogeneous processes [15]. 

The kinetics of octanoic acid esterification by t-butanol catalyzed by the macroretic-ular, sulfonylated ion-exchange resin, Amberlite-15, in a batch reactor was measured [37]. The effect of the catalyst amount, temperature and concentration of alcohol, water and butyl octanoate was investigated. Experimental data suggested that the solvated sulfo groups are bonded with the alcohol-water matrix. It was assumed that the examined reaction system included the heterogeneous reaction catalyzed by nonionized sulfo groups as well as the pseudohomogeneous reaction catalyzed by solvated protons. 

If this reaction were to occur only in the aqueous bulk, the film has no role to play, the entire system is pseudohomogeneous, and a true kinetic analysis as outlined earlier is possible. If mass transfer effects are present between the pseudophases, the analysis outlined before for such systems would apply. However, if reaction occurs in the film, two situations can arise (1) reaction occurs only in the micelles present in the film and not in the rest of the film, and (2) reaction occurs in both the micellar and aqueous phases in the film. The analysis of both the situations is very similar to that for microphase action described in Chapter 23. 

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