Reaction mechanisms reactor types

A typical computation such as the ones described here used about 100 adaptively placed mesh points and required about 5 minutes on a Cray 1-S. Of course, larger reaction mechanisms take more time. Also, simpler transport models can be used to reduce computation time. Since the solution methods are iterative, the computer time for a certain simulation can be reduced by starting it from the solution of a related problem. For example, it may be efficient to determine the solution to a problem with a susceptor temperature of 900 K starting from a converged solution for a reactor with a susceptor temperature of 1000 K. In fact, it is typical to compute families of solutions by this type of continuation procedure. 

For toluene fluorination, the impact of micro-reactor processing on the ratio of ortho-, meta- and para-isomers for monofluorinated toluene could be deduced and explained by a change in the type of reaction mechanism. The ortho-, meta- and para-isomer ratio was 5 1 3 for fluorination in a falling film micro reactor and a micro bubble column at a temperature of-16 °C [164,167]. This ratio is in accordance with an electrophilic substitution pathway. In contrast, radical mechanisms are strongly favored for conventional laboratory-scale processing, resulting in much more meta-substitution accompanied by imcontroUed multi-fluorination, addition and polymerization reactions. 

The trickle-bed reactor (TBR) and slurry reactor (SR) are the most commonly used for multiphase reactions in the chemical industries. A new reactor type, the monolithic reactor (MR), offers many advantages. Therefore, these three types of reactors are discussed below in more detail. Their general characteristics are given in Table 5.4-44. With respect to slurry reactors, the focus will be on mechanically agitated slurry reactors (MASR) because these are more widely used in fine chemicals manufacture than column slurry reactors. 

Identify the predominant rate-controlling mechanism kinetic, mass or heat transfer. Choose a suitable reactor type, based on experience with similar reactions, or from the laboratory and pilot plant work. 

The reaction mechanism of SCR of NOx with decane on acid and iron-exchanged MFI-type zeolite was also investigated by operando FTIR spectroscopy and a special reactor cell enabling the use of water-containing gas mixtures. Brosius et al. found that water has a dramatic influence on the reaction pathway, while the formation of organic nitro and nitrite compounds does not proceed via chemisorbed states of NO, as observed in SCR with dry gases [174],... 

The solution procedure to this equation is the same as described for the temporal isothermal species equations described above. In addition, the associated temperature sensitivity equation can be simply obtained by taking the derivative of Eq. (2.87) with respect to each of the input parameters to the model. The governing equations for similar types of homogeneous reaction systems can be developed for constant volume systems, and stirred and plug flow reactors as described in Chapters 3 and 4 and elsewhere [31-37], The solution to homogeneous systems described by Eq. (2.81) and Eq. (2.87) are often used to study reaction mechanisms in the absence of mass diffusion. These equations (or very similar ones) can approximate the chemical kinetics in flow reactor and shock tube experiments, which are frequently used for developing hydrocarbon combustion reaction mechanisms. 

The air oxidation of 2-methylpropene to methacrolein was investigated at atmospheric pressure and temperatures ranging between 200° and 460°C. over pumice-supported copper oxide catalyst in the presence of selenium dioxide in an integral isothermal flow reactor. The reaction products were analyzed quantitatively by gas chromatography, and the effects of several process variables on conversion and yield were determined. The experimental results are explained by the electron theory of catalysis on semiconductors, and a reaction mechanism is proposed. It is postulated that while at low selenium-copper ratios, the rate-determining step in the oxidation of 2-methylpropene to methacrolein is a p-type, it is n-type at higher ratios. 

Mechanisms of reactions are important for industry because they provide information useful for optimizing catalyst and reactor conditions. The study of reaction mechanisms in industry cannot stand alone as it can in academia. Mechanistic studies are funded to solve plant problems, to decrease operating costs, and to improve product quality. There is a wide variation in industry in the amount and type of mechanistic research funded and the timing for such research. Mechanistic research on chemical reactions is most easily justified when it is focused on the development of commercial products for a company. Often the results of mechanistic studies are not published but used instead in reactor modeling. The second reason is that competitors would obtain the information at no cost. 

Chemical reactors are the most important features of a chemical process. A reactor is a piece of equipment in which the feedstock is converted to the desired product. Various factors are considered in selecting chemical reactors for specific tasks. In addition to economic costs, the chemical engineer is required to choose the right reactor that will give the highest yields and purity, minimize pollution, and maximize profit. Generally, reactors are chosen that will meet the requirements imposed by the reaction mechanisms, rate expressions, and the required production capacity. Other pertinent parameters that must be determined to choose the correct type of reactor are reaction heat, reaction rate constant, heat transfer coefficient, and reactor size. Reaction conditions must also be determined including temperature of the heat transfer medium, temperature of the inlet reaction mixture, inlet composition, and instantaneous temperature of the reaction mixture. 

Civilian applications are numerous, but most funding of SCWO technology has stemmed from the military s need to find a safe and effective alternative to incineration of their wastes, as well as the need to clean up mixed wastes (radioactive and hazardous organic materials) at DOE weapons facilities. For better utilization of SCWO for its application to a wide range of waste types, a better fundamental understanding of reaction media, including reaction rates, reaction mechanisms, and phase behavior of multicomponent systems is required. Such an understanding would help optimize the process conditions to minimize reactor corrosion and salt... 

If a chemical reaction is operated in a flow reactor under fixed external conditions (temperature, partial pressures, flow rate etc.), usually also a steady-state (i.e., time-independent) rate of reaction will result. Quite frequently, however, a different response may result The rate varies more or less periodically with time. Oscillatory kinetics have been reported for quite different types of reactions, such as with the famous Belousov-Zha-botinsky reaction in homogeneous solutions (/) or with a series of electrochemical reactions (2). In heterogeneous catalysis, phenomena of this type were observed for the first time about 20 years ago by Wicke and coworkers (3, 4) with the oxidation of carbon monoxide at supported platinum catalysts, and have since then been investigated quite extensively with various reactions and catalysts (5-7). Parallel to these experimental studies, a number of mathematical models were also developed these were intended to describe the kinetics of the underlying elementary processes and their solutions revealed indeed quite often oscillatory behavior. In view of the fact that these models usually consist of a set of coupled nonlinear differential equations, this result is, however, by no means surprising, as will become evident later, and in particular it cannot be considered as a proof for the assumed underlying reaction mechanism. 

Some authors [120—122] have collected simple kinetic systems and attempted to solve the corresponding characteristic equations explicitly in the case of an isothermal, constant volume batch reactor. In view of the fact that most reaction mechanisms are not simple ones or are not considered in these collections or are not amenable to an explicit solution and that types of reactors other than the isothermal batch reactor are used in kinetics, this approach (involving, furthermore, standard mathematics) will not be discussed further here. 

Other types of discontinuous flow reactors may be used for transient kinetic studies in which, for example, isotopically labelled reactants are widely used in kinetic studies. This kind of investigation has been particularly developed in the case of discontinuous flow reactors. A different instrument called TAP (for Temporal Analysis of Products) permits extremely sensitive detection of intermediates or products. The results obtained with these various instruments can provide information about reaction mechanisms. 

The rational design of a reaction system to produce a desired polymer is more feasible today by virtue of mathematical tools which permit one to predict product distribution as affected by reactor type and conditions. New analytical tools such as gel permeation chromatography are beginning to be used to check technical predictions and to aid in defining molecular parameters as they affect product properties. The vast majority of work concerns bulk or solution polymerization in isothermal batch or continuous stirred tank reactors. There is a clear need to develop techniques to permit fuller application of reaction engineering to realistic nonisothermal systems, emulsion systems, and systems at high conversion found industrially. A mathematical framework is also needed which will start with carefully planned experimental data and efficiently indicate a polymerization mechanism and statistical estimates of kinetic constants rather than vice-versa. 

Plasma polymerization is a very complicated process, and the overall growth rate is a function of several independent factors such as the type of discharge, reactor geometry, properties and temperature of the substrate, pressure, type and composition of the feed gas and so on. As a result, formulation of a generalized reaction mechanism is not easy. However, attempts were made to formulate the overall mechanisms of plasma polymerization, and can be applied to many cases. 

Tank reactors for solid-catalyzed gaseous or liquid reactions are seen much less frequently than tubular reactors because of the difficulty in separating the phases and in agitating a fluid phase in the presence of solid particles. One type of CSTR used to study catalytic reactions is the spinning basket reactor, which has the catalyst embedded in the blades of the spinning agitator. Another is the Berty reactor, which uses an internal recycle stream to achieve perfectly mixed behavior." These reactors (see Chapter 5) are frequently used in industry to evaluate reaction mechanisms and determine reaction kinetics. 

Reactions occur in reactors, and in addition to the intrinsic kinetics, observed reaction rates depend on the reactor type, scale, geometry, mode of operation, and operating conditions. Similarly, understanding of the reactor system used in the kinetic experiments is required to determine the reaction mechanism and intrinsic kinetics. In this section we address the effect of reactor type on observed rates. In Sec. 19 the effect of reactor type on performance (rates, selectivity, yield) is discussed in greater detail. 

This entry on free-radical polymerization discusses relevant aspects from a chemical processing perspective. It briefly discusses the chemistry and mechanism, the types of reactors and processes typically used in the industry, and other relevant reaction engineering and processing aspects. This should provide an introduction to the process with more detailed information included in the references herein. 

---