Multiple operating states

CONTROL AND STARTUP OF A 3-STAGE CSTR CASCADE MULTIPLE OPERATING STATES AND COUNTERCURRENT COOLING... 

Volumetric heat generation increases with temperature as a single or multiple S-shaped curves, whereas surface heat removal increases linearly. The shapes of these heat-generation curves and the slopes of the heat-removal lines depend on reaction kinetics, activation energies, reactant concentrations, flow rates, and the initial temperatures of reactants and coolants (70). The intersections of the heat-generation curves and heat-removal lines represent possible steady-state operations called stationary states (Fig. 15). Multiple stationary states are possible. Control is introduced to estabHsh the desired steady-state operation, produce products at targeted rates, and provide safe start-up and shutdown. Control methods can affect overall performance by their way of adjusting temperature and concentration variations and upsets, and by the closeness to which critical variables are operated near their limits. 

Fig. 15. Temperature vs heat generation or removal in estabHshing stationary states. The heavy line (—) shows the effect of reaction temperature on heat-generation rates for an exothermic first-order reaction. Curve A represents a high rate of heat removal resulting in the reactor operating at a low temperature with low conversion, ie, stationary state at a B represents a low rate of heat removal and consequently both a high temperature and high conversion at its stationary state, b and at intermediate heat removal rates, ie, C, multiple stationary states are attainable, c and The stationary state at c ...

FIG. 23-17 Multiple steady states of CSTRs, stable and unstable, adiabatic except the last item, (a) First-order reaction, A and C stable, B unstable, A is no good for a reactor, the dashed line is of a reversible reaction, (h) One, two, or three steady states depending on the combination Cj, Ty). (c) The reactions A B C, with five steady states, points 1, 3, and 5 stable, (d) Isothermal operation with the rate equation = 0 /(1 -I- C y = (C o Cy/t. 

Linear control theory will be of limited use for operational transitions from one batch regime to the next and for the control of batch plants. Too many of the processes are unstable and exhibit nonlinear behavior, such as multiple steady states or limit cycles. Such problems often arise in the batch production of polymers. The feasibility of precisely controlling many batch processes will depend on the development of an appropriate nonlinear control theory with a high level of robustness. 

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. 

For the parameters used in the program, the system is characterised by multiple steady-state operating conditions. For example, four of them are as follows... 

The problem of ignition and extinction of reactions is basic to that of controlling the process. It is interesting to consider this problem in terms of the variables used in the earlier discussion of stability. When multiple steady-state solutions exist, the transitions between the various stable operating points are essentially discontinuous, and hysteresis effects can be observed in these situations. 

On the other hand, lanthanides with 100% isotopical purity such as terbium or holmium are preferred to simplify the operation and minimize decoherence in spin qubits. In this respect, the existence, for some lanthanides, of a manifold of electronuclear states can provide additional resources for the implementation of multiple qubit states within the same molecule [31]. All atoms in the first coordination sphere should be oxygen, and the sample should be deuter-ated if the compound contains hydrogen, to avoid interaction with other nuclei spins. Again, POM chemistry has been shown to provide ideal examples of this kind. 

An unusual feature of a CSTR is the possibility of multiple stationary states for a reaction with certain nonlinear kinetics (rate law) in operation at a specified T, or for an exothermic reaction which produces a difference in temperature between the inlet and outlet of the reactor, including adiabatic operation. We treat these in turn in the next two sections. 

A reaction which follows power-law kinetics generally leads to a single, unique steady state, provided that there are no temperature effects upon the system. However, for certain reactions, such as gas-phase reactions involving competition for surface active sites on a catalyst, or for some enzyme reactions, the design equations may indicate several potential steady-state operating conditions. A reaction for which the rate law includes concentrations in both the numerator and denominator may lead to multiple steady states. The following example (Lynch, 1986) illustrates the multiple steady states... 

If feed at a specified rate and T0 enters a CSTR, the steady-state values of the operating temperature T and the fractional conversion fA (for A —> products) are not known a priori. In such a case, the material and energy balances must be solved simultaneously for T and fA. This can give rise to multiple stationary states for an exothermic reaction, but not for an endothermic reaction. 

The existence of possible multiple stationary-states, as illustrated in Example 14-8, raises further questions (for adiabatic operation) ... 

Figure 14.6 Illustration of range of feed temperatures (T 0 to T ) for multiple stationary-states in CSTR for adiabatic operation (autothermal behavior occurs for T0 > T )...

For an endothermic reaction, whether the operation is adiabatic or nonadiabatic, there is no possibility of multiple stationary-states because of the negative slope of the /A versus T relation in the energy balance (see equation 14.3-11). This is illustrated schematically in Figure 14.8. 

It is suspected that this nonlinear rate form, which has a maximum value, may cause certain regions of unstable operation with multiple steady states. How should the operation be conducted to ensure unique steady conditions ... 

COMMUTATIVE PROPERTY states that when performing a string of addition operations, or a string of multiplication operations, the order does not matter. In other words, a + b = b + a. 

ASSOCIATIVE PROPERTY is used when grouping symbols are present. This property states that when you perform a string of addition operations, or all multiplication operations, you can change the grouping. In other words, (axb)xc = ax(bxc). 

Finally, we note that Dudukovic has shown that, for isothermal reactors, the degree of micromixing can significantly influence the appearance of multiple steady-state operating conditions, this being particularly likely for kinetic mechanisms which display maximum reaction rates at intermediate concentration levels [38, 39]. 

Whenever multiple steady states in a reactor are possible, we must be very concerned that we are operating on the desired steady-state branch. This requires a proper startup procedure to attain the desired steady state and suitable operation limits to make sure that we never exhibit a sufficiently large transient to cause the system to fall off the desired conversion branch. We will consider transients in the CSTR in the next section. 

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 ... 

Sincic and Bailey (1977) relaxed the assumption of only one stable attractor for a given set of operating conditions and showed examples of some possible exotic responses in a CSTR with periodically forced coolant temperature. They also probed the way in which multiple steady states or sustained oscillations in the dynamics of the unforced system affect its response to periodic forcing. Several theoretical and experimental papers have since extended these ideas (Hamer and Cormack, 1978 Cutlip, 1979 Stephanopoulos et al., 1979 Hegedus et al., 1980 Abdul-Kareem et al., 1980 Bennett, 1982 Goodman et al., 1981, 1982 Cutlip et al., 1983 Taylor and Geiseler, 1986 Mankin and Hudson, 1984 Kevrekidis et al., 1984). 

It is of some note that many of the models may be (and often were) obtained by-passing the derivational approach here. Basically each model may be viewed as represented by the first terms in a graph-theoretic cluster expansion [80]. Once the space on which the model to be represented is specified, the interactions in the orthogonal-basis cases are just the simplest additive few-site operators possible. For the nonorthogonal bases the overlaps are just the simplest multiplicative operators possible, while the associated Hamiltonian operators are the simplest associated derivative operators. These ideas lead [80] to proper size-consistency and size extensivity. Similar sorts of ideas apply in developing wavefunction Ansatze or ground-state energy expansions for the various models. 

The area of reactor design has been widely studied, and there are many excellent textbooks that cover this subject. Most of the emphasis in these books is on steady-state operation. Dynamics are also considered, but mostly from the mathematical standpoint (openloop instability, multiple steady states, and bifurcation analysis). The subject of developing effective stable closedloop control systems for chemical reactors is treated only very lightly in these textbooks. The important practical issues involved in providing reactor control systems that achieve safe, economic, and consistent operation of these complex units are seldom understood by both students and practicing chemical engineers. 

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