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FIGURE 3.8 Dynamic flash drum.

A more workable dynamic model can be developed if we ignore the dynamics of the vapor phase (as we did in case B of Sec. 3.7). The vapor is assumed to be always in equilibrium with the liquid. The conservation equations are written for the liquid phase only.
C. PRACTICAL MODEL.

Total continuity :
dt

Component continuity :
d dt
PO

(3.58)

Energy :
dt
=

The NC vapor-liquid equilibrium equations [Eqs. the three enthalpy relationships [Eqs. the two density equations [Eqs. (3.48) and the two molecular-weight equations [Eq. and the feedback controller equaare all needed. The total number of equations is 2NC + 9, tions [Eqs. which equals the total number of variables: .. Keep in mind that all the feed properties, or forcing functions, are given:
PO,

3.9 BATCH REACT& Batch processes offer some of the most interesting and challenging problems in modeling and control because of their inherent dynamic nature. Although most

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Reactants charged initially Temperature transmitter

Steam , V-l water outlet sensor

, v-2 3

Cooling water inlet

Condensate FIGURE 3.9 Batch reactor.

A
Products withdrawn finally

large-scale chemical engineering processes have traditionally been operated in a continuous fashion, many batch processes are still used in the production of smaller-volume specialty chemicals and pharmaceuticals. The batch chemical reactor has inherent kinetic advantages over continuous reactors for some reactions (primarily those with slow rate constants). The wide use of digital process control computers has permitted automation and optimization of batch processes and made them more efficient and less labor intensive. Let us consider the batch reactor sketched in Fig. 3.9. Reactant is charged into the vessel. Steam is fed into the jacket to bring the reaction mass up to a desired temperature. Then cooling water must be added to the jacket to remove the exothermic heat of reaction and to make the reactor temperature follow the prescribed temperature-time curve. This temperature profile is fed into the temperature controller as a signal. The varies with time. First-order consecutive reactions take place in the reactor as time proceeds.

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The product that we want to make is component B. If we let the reaction go on too long, too much of B will react to form undesired C; that is, the yield will be low. If we stop the reaction too early, too little A will have reacted; i.e., the conversion and yield will be low. Therefore there is an optimum batch time when we should stop the reaction. This is often done by quenching it, i.e., cooling it down quickly. There may also be an optimum temperature profile. If the of the specific reaction rates and are the same (if their activation energies are equal), the reaction should be run at the highest possible temperature to minimize the batch time. This maximum temperature would be a limit imposed by some constraint: maximum working temperature or pressure of the equipment, further undesirable degradation or polymerization of products or reactants at very high temperatures, etc. If is more temperature-dependent than k,, we again want to run at the highest possible temperature to favor the reaction to B. In both cases we must be sure to stop the reaction at the right time so that the maximum amount of B is recovered. If is less temperature-dependent that the optimum temperature profile is one that starts off at a high temperature to get the first reaction going but then drops to prevent the loss of too much B. Figure 3.10 sketches typical optimum temperature and concentration profiles. Also shown in Fig. 3.10 as the dashed line is an example of an actual temperature that could be achieved in a real reactor. The reaction mass must be heated up to We will use the optimum temperature profile as the signal. With this background, let us now derive a mathematical model for this process. We will assume that the density of the reaction liquid is constant. The

FIGURE 3.10

Batch

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total continuity equation for the reaction mass, after the reactants have been charged and the batch cycle begun, is
dt

(3.60) = 0. Therefore the

There is no inflow and no outflow. Since p is constant, volume of liquid in the reactor is constant. Component continuity for A:

(3.61) Component continuity for B :

V = Vk,

Kinetic equations : (3.63) Using a lumped model for the reactor metal wall and the simple enthalpy equation = T, the energy equations for the reaction liquid and the metal wall are : Energy equation for process :
= Vk,

(3.64)

Energy equation for metal wall :

= T)

where

and are the exothermic heats of reaction for the two reactions. Notice that when the reactor is heated with steam, is bigger than and is bigger than T. When cooling with water, the temperature differentials have the opposite sign. Keep in mind also that the outside film coefficient is usually significantly different for condensing steam and flowing cooling water. This switching from heating to cooling is a pretty tricky operation, particularly if one is trying to heat up to as fast as possible but cannot permit any overshoot. A commonly used system is shown in Fig. 3.9. The temperature controller keeps the steam valve (V-l) open and the cooling water valve (V-2) shut during the heat-up. This is accomplished by using split-ranged valves, discussed later in Part III. Also during the heat-up, the cooling-water outlet valve (V-3) is kept closed and the condensate valve (V-4) is kept open. When cooling is required, the temperature controller shuts the steam valve and opens the cooling-water valve just enough to make the reactor temperature

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follow the setpoint. Valve must be opened and valve V-4 must be shut whenever cooling water is added. We will study in detail the simulation and control of this system later in this book. Here let us simply say that there is a known relationship between the error signal E (or the temperature minus the reactor temperature) and the volumetric flow rates of steam and cooling water . =
(3.66)

To describe what is going on in the jacket we may need two different sets of equations, depending on the stage: heating or cooling. We may even need to consider a third stage: filling the jacket with cooling water. If the cooling-water flow rate is high and/or the jacket volume is small, the time to fill the jacket may be neglected. During heating, a total continuity equation and an energy equation for the steam vapor may be needed, plus an equation of state for the steam.
A. HEATING PHASE.

Total continuity:
(3.67)

where

= density of steam vapor in the jacket = volume of the jacket = density of incoming steam = rate of condensation of steam (mass per time)

The liquid condensate is assumed to be immediately drawn off through a steam trap. Energy equation for steam vapor:
J

dt

(3.68)

where

= internal energy of the steam in the jacket = enthalpy of incoming steam = enthalpy of liquid condensate

The internal energy changes (sensible-heat effects) can usually be neglected compared with the latent-heat effects. Thus a simple algebraic steadystate energy equation can be used
(3.69)

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The equations of state for steam (or the steam tables) can be used to calculate temperature and pressure from density . For example, if the gas law and a simple vapor-pressure equation can be used, (3.70) where A, and = molecular weight of steam = 18 = vapor-pressure constants for water

Equation (3.70) can be solved (iteratively) for if is known [from Eq. Once is known, can be calculated from the vapor-pressure equation. It is usually necessary to know in order to calculate the flow rate of steam through the inlet valve since the rate depends on the pressure drop over the valve (unless the flow through the valve is critical). If the mass of the metal surrounding the jacket is significant, an energy equation is required for it. We will assume it negligible. In most jacketed reactors or steam-heated reboilers the volume occupied by the steam is quite small compared to the volumetric flow rate of the steam vapor. Therefore the dynamic response of the jacket is usually very fast, and simple algebraic mass and energy balances can often be used. Steam flow rate is set equal to condensate flow rate, which is calculated by iteratively solving the transfer relationship (Q = AT) and the valve flow equation for the pressure in the jacket and the condensate flow rate. B. COOLING PHASE. During the period when cooling water is flowing through the jacket, only one energy equation for the jacket is required if we assume the jacket is perfectly mixed.
= +

(3.7 1)

where

= temperature of cooling water in jacket = density of water = heat capacity of water = inlet cooling-water temperature

Checking the degrees of freedom of the system during the heating stage, we have seven variables (C, , , T, , and and seven equations [Eqs. and During the cooling stage we use Eq. (3.71) instead of Eqs. and but we have only instead

3.10 REACTOR WITH MASS TRANSFER As indicated in our earlier discussions about kinetics in Chap. 2, chemical reactors sometimes have mass-transfer limitations as well as chemical reaction-rate limitations. Mass transfer can become limiting when components must be moved