Multiphase Batch Reactors

A useful classification of lands of reaclors is in terms of their concentration distributions. The concentration profiles of certain limiting cases are illustrated in Fig. 7-3 namely, of batch reactors, continuously stirred tanks, and tubular flow reactors. Basic types of flow reactors are illustrated in Fig. 7-4. Many others, employing granular catalysts and for multiphase reactions, are illustratea throughout Sec. 23. The present material deals with the sizes, performances and heat effects of these ideal types. They afford standards of comparison. 

Example 4.2 used the method of false transients to solve a steady-state reactor design problem. The method can also be used to find the equilibrium concentrations resulting from a set of batch chemical reactions. To do this, formulate the ODEs for a batch reactor and integrate until the concentrations stop changing. This is illustrated in Problem 4.6(b). Section 11.1.1 shows how the method of false transients can be used to determine physical or chemical equilibria in multiphase systems. 

Chemical Kinetics, Tank and Tubular Reactor Fundamentals, Residence Time Distributions, Multiphase Reaction Systems, Basic Reactor Types, Batch Reactor Dynamics, Semi-batch Reactors, Control and Stability of Nonisotheimal Reactors. Complex Reactions with Feeding Strategies, Liquid Phase Tubular Reactors, Gas Phase Tubular Reactors, Axial Dispersion, Unsteady State Tubular Reactor Models... 

Figure 14.3 A temporal superstructure for a multiphase well-mixed batch reactor.

In a batch reactor, the first two terms in equation 12.2-1 are absent. In a semibatch reactor, one of these two terms is usually absent. In a semicontinuous reactor for a multiphase system, both flow terms may be absent for one phase and present for another. In a continuous reactor, the two terms are required to account for the continuous inflow to and outflow from the reactor, whether the system is single-phase or multiphase. 

A semibatch reactor is a variation of a batch reactor in which one reactant may be added intermittently or continuously to another contained as a batch in a vessel, or a product may be removed intermittently or continuously from the vessel as reaction proceeds. The reaction may be single-phase or multiphase. As in a batch reactor, the operation is inherently unsteady-state and usually characterized by a cycle of operation, although in a more complex manner. 

Many chemical reactions are performed on a batch basis, in which a reactor is filled with solvents, substrates, catalysts and anything else required to make the reaction proceed, the reaction is then performed and finally the reactor is emptied and the resultant mixture separated (Figure 11.2). Conceptually, a batch reactor is similar to a scaled up version of a reaction in a round-bottomed flask, although obviously the engineering required to realize a large scale reaction is much more complicated. Batch reactors are suitable for homogeneous reactions, and also for multiphasic reactions provided that efficient mixing between the phases may be achieved so that the reaction occurs at a useful rate. 

Since the overall reaction rate in the loop reactor is limited by mass transport at the phase boundary, one would expect that the Ru concentration has a weaker influence on the rate of reaction than in the batch reactor. We have carried out experiments at a Ru concentration of 0.005 M as well as at 0.01 M and observed nearly a doubling of the overall reaction rate, giving rise to a reaction order of 0.96 with regard to Ru. The result is somehow surprising, since it can be explained only in terms of a kinetic control of the reaction, like in the batch reactor. On the other hand, previous experiments clearly indicate a mass transport limitation at the L/L-interphase. So the question which arises is how it can be possible that a multiphase reaction system is limited by both mass transport and kinetics ... 

The book starts with a review of kinetics and the batch reactor in Chapter 2, and the material becomes progressively more complex until Chapter 12, which describes all the types of multiphase reactors we can think of This is the standard, linear, boring progression followed in essentially all textbooks. 

This last chapter sketches the extension of the methods developed in the previous chapters to real chemical batch reactors, characterized by nonideal fluid dynamics and by the presence of multiphase systems. 

The two extreme hypotheses on mixing produce lumped models for the fluid dynamic behavior, whereas real reactors show complex mixing patterns and thus gradients of composition and temperature. It is worthwhile to stress that the fluid dynamic behavior of real reactors strongly depends on their physical dimensions. Moreover, in ideal reactors the chemical reactions are supposed to occur in a single phase (gaseous or liquid), whereas real reactors are often multiphase systems. Two simple examples are the gas-liquid reactors, used to oxidize a reactant dissolved in a liquid solvent and the fermenters, where reactions take place within a solid biomass dispersed in a liquid phase. Real batch reactors are briefly discussed in Chap. 7, in the context of suggestions for future research work. 

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. 

A more complex behavior is expected when multiphase reacting systems are examined. As an example, consider the gas-liquid reactor sketched in Fig. 7.1(c), which behaves as a batch reactor with respect to the liquid phase and as a continuous reactor with respect to the gaseous phase. A reactant is transferred from the gaseous to the liquid phase, where it reacts with a substrate. 

Knowledge of these types of reactors is important because some industrial reactors approach the idealized types or may be simulated by a number of ideal reactors. In this chapter, we will review the above reactors and their applications in the chemical process industries. Additionally, multiphase reactors such as the fixed and fluidized beds are reviewed. In Chapter 5, the numerical method of analysis will be used to model the concentration-time profiles of various reactions in a batch reactor, and provide sizing of the batch, semi-batch, continuous flow stirred tank, and plug flow reactors for both isothermal and adiabatic conditions. 

Emulsion polymerization is usually carried out isothermally in batch or continuous stirred-tank reactors. Temperature control is much easier than for bulk or solution polymerization because the small ( 0.5 fim) polymer particles, which are the locus of the reaction, are suspended in a continuous aqueous medium. This complex, multiphase reactor also shows multiple steady states under isothermal conditions. In industrial practice, such a reactor often shows sustained oscillations. Solid-catalyzed olefin polymerization in a slurry batch reactor is a classic example of a slurry reactor where the solid particles change size and characteristics with time during the reaction process. 

Laboratory batch reactors can be single-phase (e.g., gas or liquid), multiphase (e.g., gas-liquid or gas-liquid-solid), and catalytic or non-catalytic. In this section we limit the discussion to operation at isothermal conditions. This eliminates the need to consider energy, and due to the uniform composition the component material balances are simple ordinary differential equations with time as the independent variable. 

In fine and specialty chemicals production the process cost is a less relevant aspect on the other hand, the time taken to realize the industrial production is typically the critical factor. This aspect, together with the limited resources dedicated for R D, determine the preference in companies for multipurpose catalysts with respect to optimized, but more specific, catalysts. This applies also to the process itself where simpler, not optimized, batch reactors are preferred to better, but less flexible, more complex operations. This is one of the key aspects to consider in evaluating the use of multiphase operations in the synthesis of this class of chemicals. 

The kinetic modelling of complex multiphase catalytic reactions needs a careful consideration of various complexities of adsorption and desorption of reactants and products. In such cases the kinetic model developed based on the initial rate data may not be adequate to explain the integral batch reactor performance. Hence it was thought appropriate to use mainly the integral rate data for developing a suitable kinetic model. Different rate equations were derived based on various Langumir-Hinshelwood mechanisms and a few of them are given below. 

Different types of reactors are applied in practice (Figure 1.14). Stirred tank reactors (STR), very often applied for homogeneous, enzymatic and multiphase heterogeneous catalytic reactions, can be operated batchwise (batch reactor, BR), semi-batchwise (semibatch reactor, SBR) or continuously (continuous strirred tank reactor, CSTR)... 

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