KINETICS AND IDEAL REACTOR MODELS

In this chapter, we describe several ideal types of reactors based on two modes of operation (batch and continuous), and ideal flow patterns (backmix and tubular) for the continuous mode. From a kinetics point of view, these reactor types illustrate different ways in which rate of reaction can be measured experimentally and interpreted operationally. From a reactor point of view, the treatment also serves to introduce important concepts and terminology of CRE (developed further in Chapters 12 to 18). Such ideal reactor models serve as points of departure or first approximations for actual reactors. For illustration at this stage, we use only simple systems. 

In this chapter, we thus focus on four types of ideal reactors  

We describe each of these in more detail in turn, with particular emphasis on the material-balance equation in each of the first three cases, since this provides an interpretation of rate of reaction for the last case, LFR, we consider only the general features at this stage. Before doing this, we first consider various ways in which time is represented. 

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Chapter 2 Kinetics and Ideal Reactor Models 2.8 PROBLEMS FOR CHAPTER 2... 

Ideal flow is introduced in Chapter 2 in connection with the investigation of kinetics in certain types of ideal reactor models, and in Chapter 11 in connection with chemical reactors as a contrast to nonideal flow. As its name implies, ideal flow is a model of flow which, in one of its various forms, may be closely approached, but is not actually achieved. In Chapter 2, three forms are described backmix flow (BMF), plug flow (PF), and laminar flow (LF). 

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. 

As discussed in Section 17.2.3.1, reactor performance in general depends on (1) the kinetics of reaction, (2) the flow pattern as represented by the RTD, and (3) mixing characteristics within the vessel. The performance predicted by ideal reactor models (CSTR, PFR, and LFR) is determined entirely by (1) and (2), and they do not take (3)... 

Often the kinetics of the chemical reaction and whether or not the reaction rate is affected by transport limitation are not known a priori. Lab-scale experimental reactors are structured such that they are operated isothermally and can be described by one of three ideal reactor models (ideal batch, CSTR, and plug flow). Isothermal operation is achieved by providing a large beat-transfer surface and maintaing the reactor in a constant-temperature bath. Experiments are conducted at different initial (or inlet) reactant proportions (to determine the form of the rate expression) and at different temperatures (to determine the activation energy). 

Computer simulation of the reactor kinetic hydrodynamic and transport characteristics reduces dependence on phenomenological representations and idealized models and provides visual representations of reactor performance. Modem quantitative representations of laminar and turbulent flows are combined with finite difference algorithms and other advanced mathematical methods to solve coupled nonlinear differential equations. The speed and reduced cost of computation, and the increased cost of laboratory experimentation, make the former increasingly usehil. 

In Chaps. 5 and 6 model-based control and early diagnosis of faults for ideal batch reactors have been considered. A detailed kinetic network and a correspondingly complex rate of heat production have been included in the mathematical model, in order to simulate a realistic application however, the reactor was described by simple ideal mathematical models, as developed in Chap. 2. In fact, real chemical reactors differ from ideal ones because of two main causes of nonideal behavior, namely the nonideal mixing of the reactor contents and the presence of multiphase systems. 

It may be seen that components of the model discussed thus far are generally applicable to any two phase ideal back-mixed reactor. Chemical kinetics and phase equilibrium are the two components which make the model unique. 

Ideal reactors work under very simple limiting conditions, mainly concerning the residence time distribution. The operation of an ideal reactor is essentially controlled by chemical kinetics and thus the kinetic analysis of a chemical reaction is facilitated by the use of such a reactor. Furthermore, most laboratory and industrial reactors operate under conditions very near to ideality or may be modelled by simple combinations of ideal reactors. There are three main types of ideal reactors ... 

The state of mixing in a given reactor can be evaluated by RTD experiments by means of inert tracers, by temperature measurements, by flow visualization and, finally, by studying in the reactor under consideration the kinetics of an otherwise well-known reaction (because its mechanism has been carefully elucidated from experiments carried out in an ideal reactor, the batch reactor being generally chosen as a reference for this purpose). From these experimental results, a reactor model may be deduced. Very often, in the laboratory but also even in industrial practice, the real reactor is not far from ideal or can be modelled successfully by simple combinations of ideal reactors this last approach is of frequent use in chemical reaction engineering. But... 

The evaluation of catalyst effectiveness requires a knowledge of the intrinsic chemical reaction rates at various reaction conditions and compositions. These data have to be used for catalyst improvement and for the design and operation of many reactors. The determination of the real reaction rates presents many problems because of the speed, complexity and high exo- or endothermicity of the reactions involved. The measured conversion rate may not represent the true reaction kinetics due to interface and intraparticle heat and mass transfer resistances and nonuniformities in the temperature and concentration profiles in the fluid and catalyst phases in the experimental reactor. Therefore, for the interpretation of experimental data the experiments should preferably be done under reaction conditions, where transport effects can be either eliminated or easily taken into account. In particular, the concentration and temperature distributions in the experimental reactor should preferably be described by plug flow or ideal mixing models. 

A qualified question is then whether or not the multicomponent models are really worthwhile in reactor simulations, considering the accuracy reflected by the flow, kinetics and equilibrium model parts involved. For the present multiphase flow simulations, the accuracy reflected by the flow part of the model is still limited so an extended binary approach like the Wilke model sufEce in many practical cases. This is most likely the case for most single phase simulations as well. However, for diffusion dominated problems multicomponent diffusion of concentrated ideal gases, i.e., for the cases where we cannot confidently designate one of the species as a solvent, the accuracy of the diffusive fluxes may be significantly improved using the Maxwell-Stefan approach compared to the approximate binary Fickian fluxes. The Wilke model might still be an option and is frequently used for catalyst pellet analysis. 

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