Complex reactions CSTRs

Selectivity A significant respect in which CSTRs may differ from batch (or PFR) reaclors is in the product distribution of complex reactions. However, each particular set of reactions must be treated individually to find the superiority. For the consecutive reactions A B C, Fig. 7-5b shows that a higher peak value of B is reached in batch reactors than in CSTRs as the number of stages increases the batch performance is approached. 

When the desirable product of a complex reaction is favored by a high concentration of some reactant, batch or semibatch reactors can Be made superior to CSTRs. 

Neither method will achieve a bumpless startup for complex kinetic schemes such as fermentations. There is a general method, known as constant RTD control, that can minimize the amount of off-specification material produced during the startup of a complex reaction (e.g., a fermentation or polymerization) in a CSTR. It does not require a process model or even a realtime analyzer. We first analyze shutdown strategies, to which it is also applicable. 

Single Isothermal CSTR with complex reaction... 

Graphical Approach to the Analysis of Batteries of Stirred Tank Reactors Operating at Steady State. Even in reaction systems where it is not possible to determine the algebraic form of the reaction rate expression, it is often possible to obtain kinetic data that permit one to express graphically the rate as a function of the concentration of one reactant. Laboratory scale CSTR s are particularly appropriate for generating this type of kinetic data for complex reaction... 

Data of chemical composition 106 Pressure changes 145 Variables related to composition 164 Half iife and initial rate data 177 Temperature variation. Activation energy Homogeneous catalysis 202 Enzyme and solid catalysis 210 Flow reactor data 222 CSTR data 231 Complex reactions 238... 

The cases included are of batch, tubular and CSTR battery reactors in which are conducted simple or complex reactions. 

Isothermal Reactor with Complex Reaction 265 Continuous Stirred-Tanks, Tracer Experiment 273 Deactivating Catalyst in a CSTR 268 Distribution of an Insecticide in an Aquatic Ecosystem 581... 

A further difference between CSTR batteries and PFRs is that of product distributions with complex reactions. In the simple case, A- B- C for example, a higher yield of intermediate product B is obtained in a PFR than in a single CSTR. It is not possible to generalize the results completely, so that the algebra of each individual reacting system must be worked out to find the best mode. 

The same example was solved using MINOPT (Rojnuckarin and Floudas, 1994) by treating the PFR model as a differential model. The required input files are shown in the MINOPT manual. Kokossis and Floudas (1990) applied the presented approach for large-scale systems in which the reactor network superstructure consisted of four CSTRs and four PFR units interconnected in all possible ways. Each PFR unit was approximated by a cascade of equal volume CSTRs (up to 200-300 CSTRs in testing the approximation). Complex reactions taking place in continuous and semibatch reactors were studied. It is important to emphasize that despite the complexity of the postulated superstructure, relatively simple structure solutions were obtained with the proposed algorithmic strategy. 

Equation (19-22) indicates that, for a nominal 90 percent conversion, an ideal CSTR will need nearly 4 times the residence time (or volume) of a PFR. This result is also worth bearing in mind when batch reactor experiments are converted to a battery of ideal CSTRs in series in the field. The performance of a completely mixed batch reactor and a steady-state PFR having the same residence time is the same [Eqs. (19-5) and (19-19)]. At a given residence time, if a batch reactor provides a nominal 90 percent conversion for a first-order reaction, a single ideal CSTR will only provide a conversion of 70 percent. The above discussion addresses conversion. Product selectivity in complex reaction networks may be profoundly affected by dispersion. This aspect has been addressed from the standpoint of parallel and consecutive reaction networks in Sec. 7. 

There have been many hybrid multiscale simulations published recently in other diverse areas. It appears that the first onion-type hybrid multiscale simulation that dynamically coupled a spatially distributed 2D KMC for a surface reaction with a deterministic, continuum ODE CSTR model for the fluid phase was presented in Vlachos et al. (1990). Extension to 2D KMC coupled with ID PDE flow model was described in Vlachos (1997) and for complex reaction networks studied using 2D KMC coupled with a CSTR ODEs model in Raimondeau and Vlachos (2002a, b, 2003). Other examples from catalytic applications include Tammaro et al. (1995), Kissel-Osterrieder et al. (1998), Qin et al. (1998), and Monine et al. (2004). For reviews, see Raimondeau and Vlachos (2002a) on surface-fluid interactions and chemical reactions, and Li et al. (2004) for chemical reactors. 

For complex reactions and with multistage CSTRs, more than three steady states can exist (as in Fig. 23-17c). Most of the work on multiplicities and instabilities has been done only on paper. No plant studies and a very few laboratory studies are mentioned in the comprehensive reviews of Razon and Schmitz Chem. Eng. Set, 42, 1,005-1,047 [1987]) and Morbidelli et al. (in Carberry and Varma, Chemical Reaction and Reactor Engineering, Dekker, 1987, pp. 973-1,054). 

Multiple steady states as discussed in the previous subsection are related to the nonisothermicity of the CSTR. However, even in the isothermal case, a CSTR is known to be able to exhibit multiple steady states, periodic orbits, and chaotic behavior for sufficiently complex reaction network structures (see, e.g.. Gray and Scott, 1990). When the number of reactions is very large, the problem becomes a formidable one. In a series of papers (Feinberg 1987, 1988, and the literature quoted therein), Feinberg and his coworkers have developed a procedure for CSTRs that can be applied to systems with arbitrarily large numbers of reactants and reactions. The procedure is based on the deficiency concept discussed in Appendix C. 

Petroleum refinery flowsketch, 26 PER (plug flow reactor), 55,558 comparison with CSTR, complex reactions, 569 volume ratio to CSTR, 571 Phase diagrams nitrotoluene isomers, 544 salt solutions, 526 use of example, 528 Phenol bv the chlorbenzene process, 34 Phosgene synthesis, 594 PhthMic anhydride synthesis, 593 PID (proportional-integral-derivative) controllers, 41, 42... 

Thermal stability of chemical reactors is a classic yet active area within chemical engineering science. Considerable research has focused on determining safe operating criteria for batch, CSTR, and tubular reactors. Current work has been directed towards understanding thermal stability in the presence of multiple phases (fluid/solid and gas/liquid) and multiple reactions with realistic, complex reaction rates expressions. The advent of computational methods has allowed for this field to continue to thrive. A sound understanding of these principles may help improve industrial reactor performance by reducing waste and costly separation operations and help maintain a clean environment. 

Chapter 2 treated multiple and complex reactions in an ideal batch reactor. The reactor is ideal in the sense that mixing is assumed to be instantaneous and complete throughout the vessel. Real batch reactors will approximate ideal behavior when the characteristic time for mixing is short compared to the reaction half-life. Industrial batch reactors have inlet and outlet ports, pumps, and an agitation system. The same hardware is easily converted to continuous operation. Just feed and discharge continuously. If the reactor is well mixed in the batch mode, it is likely to remain well mixed in the continuous mode, at least for the same reaction. The assumption of instantaneous and perfect mixing remains a reasonable approximation, but the batch reactor has become a CSTR. 

---