Fundamentals of Reactors

In most industrially relevant reacting systems, one main reaction typically makes the desired products and several side reactions make byproducts. The specific rate of production or consumption of a particular component in such a reaction set depends upon the stoichiometry and the rates. For example, assume that the main reaction for making vinyl acetate, Eq. (4.4.1, proceeds with a rate r< (mol/L s) and that the side reaction, Eq. (4.8), proceeds with rate r2 (mol/L s). Then the net consumption of ethylene is (-l)r1 - (-1 )r2 (mol/L s). Similarly, the net consumption of oxygen is (-0.5)fi + (— 3)r2, and the net production of water is (l)r-, + (2)ra. For a given chemistry (stoichiometry), our ability to control the production or consumption of any one component in the reactor is thus limited to how well we can influence the various rates. This boils down to manipulating the reactor temperature and/ or the concentrations of the dominant components. Occasionally, the reaction volume for liquid-phase reactions or the pressure for gas-phase reactions can also be manipulated for overall production control. These are the fundamentals of reactor control. 

Some of the fundamentals of reactor systems have been presented and discussed in this chapter. This material should assist the reactor engineer in planning appropriate pilot stndies for a new or revised process. Equally important, the concepts reviewed should help the product development personnel in devising reactor systems and operating procedures that will produce satisfactory products. 

The NURESIM (NUclear REactor SIMulation) is a software developed to provide a set of tools for training on fundamentals of reactor theory as well as for performing reactor calculations. 

The package contains a number of sections in the text part with figures, flow diagrams and graphics. The text part explains the fundamentals of reactor physics, including basic calculations on reactor physics and heat generation. 

Since process design starts with the reactor, the first decisions are those which lead to the choice of reactor. These decisions are among the most important in the whole design. Good reactor performance is of paramount importance in determining the economic viability of the overall design and fundamentally important to the environmental impact of the process. In addition to the desired products, reactors produce unwanted byproducts. These unwanted byproducts create environmental problems. As we shall discuss later in Chap. 10, the best solution to environmental problems is not elaborate treatment methods but not to produce waste in the first place. 

The two main principles involved in establishing conditions for performing a reaction are chemical kinetics and thermodynamics. Chemical kinetics is the study of rate and mechanism by which one chemical species is converted to another. The rate is the mass in moles of a product produced or reactant consumed per unit time. The mechanism is the sequence of individual chemical reaction whose overall result yields the observed reaction. Thermodynamics is a fundamental of engineering having many applications to chemical reactor design. 

The name continuous flow-stirred tank reactor is nicely descriptive of a type of reactor that frequently for both production and fundamental kinetic studies. Unfortunately, this name, abbreviated as CSTR, misses the essence of the idealization completely. The ideality arises from the assumption in the analysis that the reactor is perfectly mixed, and that it is homogeneous. A better name for this model might be continuous perfectly mixed reactor (CPMR). 

Catalyst circulation is like blood circulation to the human body. Without proper catalyst circulation, the unit is dead. Troubleshooting circulation problems requires a good understanding of the pressure balance around the reactor-regenerator circuit and the factors affecting catalyst fluidization. The fundamentals of fluidization and catalyst circulation are discussed in Chapter 5. 

A challenge related to the problems of reactor design and engineering is the modehng and study of the fundamental chemistry occtrrring in manufactrrring processes for semiconductors, optical fibers, magnetic media, and interconnection. 

At this stage of presentation a familiarization is provided for the reader with some representative types of reactors which are used for carrying out chemical metallurgical operations. It is also very much in order to indicate at this stage that later chapters contain accounts of different reactors in different fundamental positions. 

Abstract Acoustic cavitation is the formation and collapse of bubbles in liquid irradiated by intense ultrasound. The speed of the bubble collapse sometimes reaches the sound velocity in the liquid. Accordingly, the bubble collapse becomes a quasi-adiabatic process. The temperature and pressure inside a bubble increase to thousands of Kelvin and thousands of bars, respectively. As a result, water vapor and oxygen, if present, are dissociated inside a bubble and oxidants such as OH, O, and H2O2 are produced, which is called sonochemical reactions. The pulsation of active bubbles is intrinsically nonlinear. In the present review, fundamentals of acoustic cavitation, sonochemistry, and acoustic fields in sonochemical reactors have been discussed. 

Polymer production technology involves a diversity of products produced from even a single monomer. Polymerizations are carried out in a variety of reactor types batch, semi-batch and continuous flow stirred tank or tubular reactors. However, very few commercial or fundamental polymer or latex properties can be measured on-line. Therefore, if one aims to develop and apply control strategies to achieve desired polymer (or latex) property trajectories under such a variety of conditions, it is important to have a valid mechanistic model capable of predicting at least the major effects of the process variables. 

One feature that distinguishes the chemical engineer from other types of engineers is the ability to analyze systems in which chemical reactions are occurring and to apply the results of his analysis in a manner that benefits society. Consequently, chemical engineers must be well acquainted with the fundamentals of chemical kinetics and the manner in which they are applied in chemical reactor design. This textbook provides a systematic introduction to these subjects. 

Although the concept of mean residence time is easily visualized in terms of the average time necessary to cover the distance between reactor inlet and outlet, it is not the most fundamental characteristic time parameter for purposes of reactor design. A more useful concept is that of the reactor space time. For continuous flow reactors the space time (t) is defined as the ratio of the reactor volume (VR) to a characteristic volumetric flow rate of fluid (Y). 

The design q>roblem can be approached at various levels of sophistication using different mathematical models of the packed bed. In cases of industrial interest, it is not possible to obtain closed form analytical solutions for any but the simplest of models under isothermal operating conditions. However, numerical procedures can be employed to predict effluent compositions on the basis of the various models. In the subsections that follow, we shall consider first the fundamental equations that must be obeyed by all packed bed reactors under various energy transfer constraints, and then discuss some of the simplest models of reactor behavior. These discussions are limited to pseudo steady-state operating conditions (i.e., the catalyst activity is presumed to be essentially constant for times that are long compared to the fluid residence time in the reactor). 

Hill, CG, An Introduction to Chemical Engineering Kinetics and Reactor Design, Wiley, New York, NY, 1977. Holland, CD, RG Anthony, Fundamentals of Chemical Reaction Engineering, Prentice-Hall, Englewood Cliffs, NJ, 1989. 

Volumes 1, 2 and 3 form an integrated series with the fundamentals of fluid flow, heat transfer and mass transfer in the first volume, the physical operations of chemical engineering in this, the second volume, and in the third volume, the basis of chemical and biochemical reactor design, some of the physical operations which are now gaining in importance and the underlying theory of both process control and computation. The solutions to the problems listed in Volumes 1 and 2 are now available as Volumes 4 and 5 respectively. Furthermore, an additional volume in the series is in course of preparation and will provide an introduction to chemical engineering design and indicate how the principles enunciated in the earlier volumes can be translated into chemical plant. 

The first intent of this text is to update the fundamental principles of the operation of chemical reactors in a brief and logical way. We also intend to keep the text short and cover the fundamentals of reaction engineering as briefly as possible. 

In this chapter we consider the fundamentals of reaction in continuous isothermal reactors. Most industrial reactors are operated in a continuous mode instead of batch because continuous reactors produce more product with smaller equipment, require less labor and maintenance, and frequently produce better quahty control. Continuous processes are more difficult to start and stop than batch reactors, but they make product without stopping to change batches and they require rninimum labor. 

We have frnished our discussions of the fundamentals of catalytic reactions, catalytic reactors, and mass transfer effects. While we noted that most catalytic reactions can be made to exhibit complicated kinetics, we have confined our considerations to the almost trivial reaction r" = k"CA- We did this because the algebra was messy enough with the simplest kinetics. 

In the relevant literature, many definitions of reaction rates can be found, especially in the case of catalytic systems. Depending on the approach followed, a catalytic reaction rate can be based on catalyst volume, surface, or mass. Moreover, in practical applications, rates are often expressed per volume of reactor. Each definition leads to different manipulations and special attention is required when switching from one expression to another, hi the following, the various forms of catalytic reaction rates and their connection is going to be presented. Stalling from the fundamental rate defined per active site, the reader is taken step -by step to the rate based on the volume of the reactor and the concept of the overall rate in two- and three-phase systems. 

Froment G. F. and Bischoff, K. B. Chemical Reactor Analysis and Design, 2nd edn. (Wiley, 1989). Holland, C. D. and Anthony, R. G. Fundamentals of Chemical Reaction Engineering, 2nd edn. (Prentice-Hall, 1992). 

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