Reactions nonisothermal

In fact, we usually want to operate exothemic reactions nonisothermally to take advantage of the heat release in the reaction to heat the reactor to a temperature where the rates are higher and reactor volumes can be smaller. However, if the temperature is too high, equilibrium limitations can limit the conversion, as we saw previously for NH3 and CH3OH synthesis reactions. 

In this and the previous chapters we considered the effects of nonisothermal operation on reactor behavior. The effects of nonisothermal operation can be dramatic, especially for exothermic reactions, often leading to reactor volumes many times smaller than if isothermal and often leading to the possibility of multiple steady states. Further, in nonisothermal operation, the CSTR can require a smaller volume for a given conversion than a PFTR. In this section we summarize some of these characteristics and modes of operation. For endothermic reactions, nonisothermal operation cools the reactor, and this reduces the rate, so that these reactors are inherently stable. The modes of operation can be classified as follows ... 

It is expected that, for more complex reactions and conditions (e.g., multiple reactions, nonisothermal conditions, etc.), step distributions of a relatively narrow width (approaching a Dirac delta type) placed at a specific location within the membrane pore... 

Example 7.7 Multiple-reaction, nonisothermal fixed-bed reactor... 

For the single-reaction, nonisothermal problem, we solved the so-called Weisz-Hicks problem, and determined the temperature and concentration profiles within the pellet. We showed the effectiveness factor can be greater than unity for this case. Multiple steady-state solutions also are possible for this problem, but for realistic values of the... 

Computing Data under Reaction Nonisothermal Conditions and Their Graphic Presentation... 

This development has been generalized. Results for zero- and second-order irreversible reactions are shown in Figure 10. Results are given elsewhere (48) for more complex kinetics, nonisothermal reactions, and particle shapes other than spheres. For nonspherical particles, the equivalent spherical radius, three times the particle volume/surface area, can be used for R to a good approximation. 

Computational fluid dynamics (CFD) emerged in the 1980s as a significant tool for fluid dynamics both in research and in practice, enabled by rapid development in computer hardware and software. Commercial CFD software is widely available. Computational fluid dynamics is the numerical solution of the equations or continuity and momentum (Navier-Stokes equations for incompressible Newtonian fluids) along with additional conseiwation equations for energy and material species in order to solve problems of nonisothermal flow, mixing, and chemical reaction. 

Nonisothermal reaction in a batch reactor Acetylated Castor Oil Hydrolysis... 

Omoleye, J. A., Adesina, A. A., and Udegbunam, E. O., Optimal design of nonisothermal reactors Derivation of equations for the rate-temperature conversion profile and the optimum temperature progression for a general class of reversible reactions, Chem. Eng. Comm., Vol. 79, pp. 95-107, 1989. 

The heat transfer problem which must be solved in order to calculate the temperature profiles has been posed by Lee and Macosko(lO) as a coupled unsteady state heat conduction problem in the adjoining domains of the reaction mixture and of the nonadiabatic, nonisothermal mold wall. Figure 5 shows the geometry of interest. The following assumptions were made 1) no flow in the reaction mixture (typical molds fill in <2 sec.) ... 

In order to get a quantitative idea of the magnitude of the effects of these temperature variations on molecular structure and morphology an experimental study was undertaken. Two types of polymerizations were conducted. One type was isothermal polymerization at fixed reaction time at a series of temperatures. The other type was a nonisothermal polymerization in the geometry of a RIM mold. Intrinsic viscosities, size exclusion chromotograms (gpc) and differential scanning calorimetry traces (dsc) were obtained for the various isothermal products and from spatially different sections of the nonisothermal products. Complete experimental details are given below. 

Chapter 1 treated single, elementary reactions in ideal reactors. Chapter 2 broadens the kinetics to include multiple and nonelementary reactions. Attention is restricted to batch reactors, but the method for formulating the kinetics of complex reactions will also be used for the flow reactors of Chapters 3 and 4 and for the nonisothermal reactors of Chapter 5. 

Table 3.1 suggests that scaling in series could make sense for an adiabatic, gas-phase reaction with no change in the number of moles upon reaction. It would also make sense when the number of moles decreases upon reaction, since the high pressures caused by this form of scaleup will favor the forward reaction. Chapter 5 gives the design equations for nonisothermal reactions and discusses the thermal aspects of scaleup. 

This set of first-order ODEs is easier to solve than the algebraic equations where all the time derivatives are zero. The initial conditions are that a ut = no, bout = bo,... at t = 0. The long-time solution to these ODEs will satisfy Equations (4.1) provided that a steady-state solution exists and is accessible from the assumed initial conditions. There may be no steady state. Recall the chemical oscillators of Chapter 2. Stirred tank reactors can also exhibit oscillations or more complex behavior known as chaos. It is also possible that the reactor has multiple steady states, some of which are unstable. Multiple steady states are fairly common in stirred tank reactors when the reaction exotherm is large. The method of false transients will go to a steady state that is stable but may not be desirable. Stirred tank reactors sometimes have one steady state where there is no reaction and another steady state where the reaction runs away. Think of the reaction A B —> C. The stable steady states may give all A or all C, and a control system is needed to stabilize operation at a middle steady state that gives reasonable amounts of B. This situation arises mainly in nonisothermal systems and is discussed in Chapter 5. 

The design equations for a nonisothermal batch reactor include A-fl DDEs, one for each component and one for energy. These DDEs are coupled by the temperature and compositional dependence of 91/. They may also be weakly coupled through the temperature and compositional dependence of physical properties such as density and heat capacity, but the strong coupling is through the reaction rate. 

The examples that follow assume constant physical properties and use Equation (5.28). Their purpose is to explore nonisothermal reaction phenomena rather than to present detailed design calculations. 

Most kinetic experiments are run in batch reactors for the simple reason that they are the easiest reactor to operate on a small, laboratory scale. Piston flow reactors are essentially equivalent and are implicitly included in the present treatment. This treatment is confined to constant-density, isothermal reactions, with nonisothermal and other more complicated cases being treated in Section 7.1.4. The batch equation for component A is... 

This technique should give reasonable results for isothermal, first-order reactions. It and other modeling approaches are largely untested for complex and nonisothermal reactions. 

Correlations for E are not widely available. The more accurate model given in Section 9.1 is preferred for nonisothermal reactions in packed-beds. However, as discussed previously, this model degenerates to piston flow for an adiabatic reaction. The nonisothermal axial dispersion model is a conservative design methodology available for adiabatic reactions in packed beds and for nonisothermal reactions in turbulent pipeline flows. The fact that E >D provides some basis for estimating E. Recognize that the axial dispersion model is a correction to what would otherwise be treated as piston flow. Thus, even setting E=D should improve the accuracy of the predictions. 

Example 9.6 Compare the nonisothermal axial dispersion model with piston flow for a first-order reaction in turbulent pipeline flow with Re= 10,000. Pick the reaction parameters so that the reactor is at or near a region of thermal runaway. 

What models should be used, either for scaleup or to correlate pilot-plant data Section 9.1 gives the preferred models for nonisothermal reactions in packed beds. These models have a reasonable experimental basis even though... 

FIGURE 10.3 Nonisothermal effectiveness factors for first-order reactions in spherical pellets. (Adapted from Weisz, P. B. and Hicks, J. S., Chem. Eng. Sci., 17, 265 (1962).)... 

The steady-state design equations (i.e., Equations (14.1)-(14.3) with the accumulation terms zero) can be solved to find one or more steady states. However, the solution provides no direct information about stability. On the other hand, if a transient solution reaches a steady state, then that steady state is stable and physically achievable from the initial composition used in the calculations. If the same steady state is found for all possible initial compositions, then that steady state is unique and globally stable. This is the usual case for isothermal reactions in a CSTR. Example 14.2 and Problem 14.6 show that isothermal systems can have multiple steady states or may never achieve a steady state, but the chemistry of these examples is contrived. Multiple steady states are more common in nonisothermal reactors, although at least one steady state is usually stable. Systems with stable steady states may oscillate or be chaotic for some initial conditions. Example 14.9 gives an experimentally verified example. 

Nonisothermal stirred tanks are governed by an enthalpy balance that contains the heat of reaction as a significant term. If the heat of reaction is unimportant, so that a desired Tout can be imposed on the system regardless of the extent of reaction, then the reactor d5mamics can be analyzed by the methods of the previous section. 

Equation (15.46) is applicable to nonisothermal systems since there is no chemical reaction. 

The analog of the residence time for a nonisothermal reaction is the thermal time ... 

This is an integral along a molecule s path that weighs time and temperature in the manner appropriate to homogeneous but nonisothermal reactions. For a first-order reaction,... 

It was felt that a nonisothermal policy might have considerable advantages in minimizing the reaction time compared to die optimal isothermal policy. Modem optimal control theory (Sage and White (1977)), was employed to minimize the reaction time. The mathematical development is presented below. 

In this paper we formulated and solved the time optimal problem for a batch reactor in its final stage for isothermal and nonisothermal policies. The effect of initiator concentration, initiator half-life and activation energy on optimum temperature and optimum time was studied. It was shown that the optimum isothermal policy was influenced by two factors the equilibrium monomer concentration, and the dead end polymerization caused by the depletion of the initiator. When values determine optimum temperature, a faster initiator or higher initiator concentration should be used to reduce reaction time. 

A dynamic differential equation energy balance was written taking into account enthalpy accumulation, inflow, outflow, heats of reaction, and removal through the cooling jacket. This balance can be used to calculate the reactor temperature in a nonisothermal operation. 

Nonisothermal reactors with adiabatic beds. Optimization of the temperature profile described above assumes that heat can be added or removed wherever required and at whatever rate required so that the optimal temperature profile can be achieved. A superstructure can be set up to examine design options involving adiabatic reaction sections. Figure 7.12 shows a superstructure for a reactor with adiabatic sections912 that allows heat to be transferred indirectly or directly through intermediate feed injection. 

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