Chemical-reaction-engineering approach

In the remainder of this chapter, an overview of the CRE and FM approaches to turbulent reacting flows is provided. Because the description of turbulent flows and turbulent mixing makes liberal use of ideas from probability and statistical theory, the reader may wish to review the appropriate appendices in Pope (2000) before starting on Chapter 2. Further guidance on how to navigate the material in Chapters 2-7 is provided in Section 1.5. 

The CRE approach for modeling chemical reactors is based on mole and energy balances, chemical rate laws, and idealized flow models.2 The latter are usually constructed (Wen and Fan 1975) using some combination of plug-flow reactors (PFRs) and continuous-stirred-tank reactors (CSTRs). (We review both types of reactors below.) The CRE approach thus avoids solving a detailed flow model based on the momentum balance equation. However, this simplification comes at the cost of introducing unknown model parameters to describe the flow rates between various sub-regions inside the reactor. The choice of a particular model is far from unique,3 but can result in very different predictions for product yields with complex chemistry. 

For isothermal, first-order chemical reactions, the mole balances form a system of linear equations. A non-ideal reactor can then be modeled as a collection of Lagrangian fluid elements moving independently through the system. When parameterized by the amount of time it has spent in the system (i.e., its residence time), each fluid element behaves as abatch reactor. The species concentrations for such a system can be completely characterized by the inlet concentrations, the chemical rate constants, and the residence time distribution (RTD) of the reactor. The latter can be found from simple tracer experiments carried out under identical flow conditions. A brief overview of RTD theory is given below. 

2 In CRE textbooks (Hill 1977 Levenspiel 1998 Fogler 1999), the types of reactors considered in this book are referred to as non-ideal. The flow models must take into account fluid-mixing effects on product yields. 

3 It has been described as requiring a certain amount of art (Fogler 1999). 

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Franck, R., David, R., Villenuaux, J. and Klein, J.P., 1988. Crystallization and precipitation engineering - II. A chemical reaction engineering approach to salicylic acid precipitation Modelling of batch kinetics and application to continuous operation. Chemical Engineering Science, 43, 69-11. 

B. Delmon, and G.F. Froment, Remote Control of Catalytic Sites by Spillover Species A Chemical Reaction Engineering Approach, Catal. Rev.-Sci. Eng 38(1), 69-100 (1996). 

Cropley, J. B. Heuristic Approach to Complex Kinetics, pp. 292-302 in Chemical Reaction Engineering—Houston, ACS Symposium Series 65, American Chemical Society, Washington, DC (1978). 

Techniques for approaching optimum temperature profiles for exothermic reaction, (a) Adiabatic operation of reactors with interstage cooling, (b) Countercurrent heat exchange. (Adapted from Chemical Reaction Engineering, Second Edition, by O. Levenspiel. Copyright 1972. Reprinted by permission of John Wiley and Sons, Inc.)... 

Although more fundamental approaches are used in the science of chemical reaction engineering to account for the diffusion/reaction coupling, we rather propose the explanation restricted to rate laws of first order with respect to hydrogen and based on intuition. 

In the remainder of this section, we will review those components of the CRE approach that will be needed to understand the modeling approach described in detail in subsequent chapters. Further details on the CRE approach can be found in introductory textbooks on chemical reaction engineering (e.g., Hill 1977 Levenspiel 1998 Fogler 1999). 

As briefly discussed in Section 1.2, chemical-reaction engineers recognized early on the need to predict the influence of reactant segregation on the yield of complex reactions. Indeed, the competitive-consecutive and parallel reaction systems analyzed in the previous section have been studied experimentally by numerous research groups (Baldyga and Bourne 1999). However, unlike the mechanical-engineering community, who mainly focused on the fluid-dynamics approach to combustion problems, chemical-reaction... 

In summary, computational quantum mechanics has reached such a state that its use in chemical kinetics is possible. However, since these methods still are at various stages of development, their routine and direct use without carefully evaluating the reasonableness of predictions must be avoided. Since ab initio methods presently are far too expensive from the computational point of view, and still require the application of empirical corrections, semiempirical quantum chemical methods represent the most accessible option in chemical reaction engineering today. One productive approach is to use semiempirical methods to build systematically the necessary thermochemical and kinetic-parameter data bases for mechanism development. Following this, the mechanism would be subjected to sensitivity and reaction path analyses for the determination of the rank-order of importance of reactions. Important reactions and species can then be studied with greatest scrutiny using rigorous ab initio calculations, as well as by experiments. 

Lerou J, Ng K. Chemical reaction engineering a multiscale approach to a multiobjective task. Chem. Eng. Sci. 1996 51 1595-1614. 

The scales involved in such a reactor should be defined in a relative manner. For a chemist, the molecule is at the start and catalyst (particle) at the end of the scales. To reveal the reaction mechanism over a catalyst particle, a sequence of network of elementary reactions" will be needed. Accordingly, on the basis of, for example, the molecular collision theory (Turns, 2000), the "global reaction" can be derived in terms of global rate coefficient and reaction order. Here, the resultant reaction mechanism is termed "global" by chemists, because the use of it for a specific problem is normally a "black box" approach, without knowing exactly the underlying networks or structures of chemical routes from reactants to products. On the other hand, for a chemical reaction engineer, the catalyst (particle) is often the start and the reactor is the end. The reaction free of inner-particle and outer-particle diffusions, that is,... 

Renken, A., Microstructured reactors novel approaches for chemical reaction engineering, in Proceedings of the 27th International Exhibition-Congress on Chemical Engineering, Environmental Protection and Biotechnology, ACHEMA (19-24 May 2003), DECHEMA, Frankfurt, 2003, 13. 

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 treatment in this paper has focused on Si derived materials since these are the most widely used materials in the microelectronics industry. However, the modelling approach can be also applied to the new III-V semiconductors. In fact, because of high demands on film thickness and composition uniformity in these systems this promises to be an area where chemical reaction engineering could play a major role. 

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