Continuous-stirred-tank reactor, mass transfer model

Over 25 years ago the coking factor of the radiant coil was empirically correlated to operating conditions (48). It has been assumed that the mass transfer of coke precursors from the bulk of the gas to the walls was controlling the rate of deposition (39). Kinetic models (24,49,50) were developed based on the chemical reaction at the wall as a controlling step. Bench-scale data (51—53) appear to indicate that a chemical reaction controls. However, flow regimes of bench-scale reactors are so different from the commercial furnaces that scale-up of bench-scale results caimot be confidently appHed to commercial furnaces. For example. Figure 3 shows the coke deposited on a controlled cylindrical specimen in a continuous stirred tank reactor (CSTR) and the rate of coke deposition. The deposition rate decreases with time and attains a pseudo steady value. Though this is achieved in a matter of rninutes in bench-scale reactors, it takes a few days in a commercial furnace. 

One of the simplest models for convective mass transfer is the stirred tank model, also called the continuously stirred tank reactor (CSTR) or the mixing tank. The model is shown schematically in Figure 2. As shown in the figure, a fluid stream enters a filled vessel that is stirred with an impeller, then exits the vessel through an outlet port. The stirred tank represents an idealization of mixing behavior in convective systems, in which incoming fluid streams are instantly and completely mixed with the system contents. To illustrate this, consider the case in which the inlet stream contains a water-miscible blue dye and the tank is initially filled with pure water. At time zero, the inlet valve is opened, allowing the dye to enter the... 

Both the mass-transfer approach as well as the diffusion approach are required to describe the influence of mass transport on the overall polycondensation rate in industrial reactors. For the modelling of continuous stirred tank reactors, the mass-transfer concept can be applied successfully. For the modelling of finishers used for polycondensation at medium to high melt viscosities, the diffusion approach is necessary to describe the mass transport of EG and water in the polymer film on the surface area of the stirrer. Those tube-type reactors, which operate close to plug-flow conditions, allow the mass-transfer model to be applied successfully to describe the mass transport of volatile compounds from the polymer bulk at the bottom of the reactor to the high-vacuum gas phase. 

We have used CO oxidation on Pt to illustrate the evolution of models applied to interpret critical effects in catalytic oxidation reactions. All the above models use concepts concerning the complex detailed mechanism. But, as has been shown previously, critical. effects in oxidation reactions were studied as early as the 1930s. For their interpretation primary attention is paid to the interaction of kinetic dependences with the heat-and-mass transfer law [146], It is likely that in these cases there is still more variety in dynamic behaviour than when we deal with purely kinetic factors. A theory for the non-isothermal continuous stirred tank reactor for first-order reactions was suggested in refs. 152-155. The dynamics of CO oxidation in non-isothermal, in particular adiabatic, reactors has been studied [77-80, 155]. A sufficiently complex dynamic behaviour is also observed in isothermal reactors for CO oxidation by taking into account the diffusion both in pores [71, 147-149] and on the surfaces of catalyst [201, 202]. The simplest model accounting for the combination of kinetic and transport processes is an isothermal continuously stirred tank reactor (CSTR). It was Matsuura and Kato [157] who first showed that if the kinetic curve has a maximum peak (this curve is also obtained for CO oxidation [158]), then the isothermal CSTR can have several steady states (see also ref. 203). Recently several authors [3, 76, 118, 156, 159, 160] have applied CSTR models corresponding to the detailed mechanism of catalytic reactions. 

While vinyl acetate is normally polymerized in batch or continuous stirred tank reactors, continuous reactors offer the possibility of better heat transfer and more uniform quality. Tubular reactors have been used to produce polystyrene by a mass process (1, 2), and to produce emulsion polymers from styrene and styrene-butadiene (3 -6). The use of mixed emulsifiers to produce mono-disperse latexes has been applied to polyvinyl toluene (5). Dunn and Taylor have proposed that nucleation in seeded vinyl acetate emulsion is prevented by entrapment of oligomeric radicals by the seed particles (6j. Because of the solubility of vinyl acetate in water, Smith -Ewart kinetics (case 2) does not seem to apply, but the kinetic models developed by Ugelstad (7J and Friis (8 ) seem to be more appropriate. 

However, each set of factors entering in to the rate expression is also a potential source of scaleup error. For this, and other reasons, a fundamental requirement when scaling a process is that the model and prototype be similar to each other with respect to reactor type and design. For example, a cleaning process model of a continuous-stirred tank reactor (CSTR) cannot be scaled to a prototype with a tubular reactor design. Process conditions such as fluid flow and heat and mass transfer are totally different for the two types of reactors. However, results from rate-of-reaction experiments using a batch reactor can be used to design either a CSTR or a tubular reactor based solely on a function of conversion, -r ... 

Many wastewater flows in industry can not be treated by standard aerobic or anaerobic treatment methods due to the presence of relatively low concentration of toxic pollutants. Ozone can be used as a pretreatment step for the selective oxidation of these toxic pollutants. Due to the high costs of ozone it is important to minimise the loss of ozone due to reaction of ozone with non-toxic easily biodegradable compounds, ozone decay and discharge of ozone with the effluent from the ozone reactor. By means of a mathematical model, set up for a plug flow reactor and a continuos flow stirred tank reactor, it is possible to calculate more quantitatively the efficiency of the ozone use, independent of reaction kinetics, mass transfer rates of ozone and reactor type. The model predicts that the oxidation process is most efficiently realised by application of a plug flow reactor instead of a continuous flow stirred tank reactor. 

For the semi-batch stirred tank reactor, the model was based on the following assumptions the reactor is well agitated, so no concentration differences appear in the bulk of the liquid gas-liquid and liquid-solid mass transfer resistances can prevail and finally, the liquid phase is in batch, while hydrogen is continuously fed into the reactor. The hydrogen pressure is maintained constant. The liquid and gas volumes inside the reactor vessel can be regarded as constant, since the changes of the fluid properties due to reaction are minor. The total pressure of the gas phase (P) as well as the reactor temperature were continuously monitored and stored on a PC. The partial pressure of hydrogen (pnz) was calculated from the vapour pressure of the solvent (pvp) obtained from Antoine s equation (pvpo) and Raoult s law ... 

A semi-batch reactor is more difficult to analyze mathematically because at least one of the reactant or product species enters or leaves the system boundaries, thus specific applications should be modeled [1,5]. However, the most typical application for a semi-batch reactor is the presence of one reactant initially contained in a stirred tank reactor and a second reactant continuously added to the reactor, with no flow out of the reactor. The addition of a gas to participate in a liquid-phase reaction is one of the more common situations involving a semi-batch reactor, especially because the rate of addition of the gas can be controlled to keep its partial pressure essentially constant as well as providing quantitative information about the rate of reaction. In addition, there is frequently little or no change in the volume of the liquid phase. Well-mixed autoclave reactors coupled with gas pressure controllers, mass flow meters and computers can nicely provide continuous, real-time rate data related to heterogeneous catalysts used in such gas/liquid systems [6-8]. Again, it must be emphasized that experiments must be performed and/or calculations made to verify that no heat or mass transfer limitations exist. 

The principle of the perfectly-mixed stirred tank has been discussed previously in Sec. 1.2.2, and this provides essential building block for modelling applications. In this section, the concept is applied to tank type reactor systems and stagewise mass transfer applications, such that the resulting model equations often appear in the form of linked sets of first-order difference differential equations. Solution by digital simulation works well for small problems, in which the number of equations are relatively small and where the problem is not compounded by stiffness or by the need for iterative procedures. For these reasons, the dynamic modelling of the continuous distillation columns in this section is intended only as a demonstration of method, rather than as a realistic attempt at solution. For the solution of complex distillation problems, the reader is referred to commercial dynamic simulation packages. 

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