EXAMPLES OF MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS 57

FIGURE 3.8
Dynamic flash drum.

C. PRACTICAL MODEL. 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.
Total continuity :
4-=PoFo-P,F,-PLFL
v, ~3
dt
Component continuity :

d
PO Fo P” f’,
(3.58)
PLFL
dt My ’
=~XOj-M:‘Yj-px’

Energy :
, dK',p,h)
= PoFoho - P”F,H - pLF,h
dt
The NC vapor-liquid equilibrium equations [Eqs. (3.53)], the three enthalpy
relationships [Eqs. (3.55)], the two density equations [Eqs. (3.48) and (3.49)], the
two molecular-weight equations [Eq. (3.50)], and the feedback controller equa-
tions [Eqs. (3.56)] are all needed. The total number of equations is 2NC + 9,
which equals the total number of variables: P,, V,, p”, F,, My, y,, y,, . . .,
YN~-~,P~,F~,MBLV,X~,X~,...,~N~-~,T,~,~~~H.
Keep in mind that all the feed properties, or forcing functions, are given:
Fo, PO, ho, Xoj, and JG"'V.,,,,t
i.

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
s MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS

Reactants charged initially

I Temperature transmitter

, f Steam
, V-l
water
outlet
I
sensor

T.U , v-2
3
Cooling
water
inlet

4
-I-
Condensate
A
w, Products withdrawn finally

FIGURE 3.9
Batch reactor.

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 reac-
tions (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 tem-
perature controller as a setpoint signal. The setpoint varies with time.
First-order consecutive reactions take place in the reactor as time proceeds.
 EXAMPLES OF MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS 59

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 temperature-
dependences of the specific reaction rates kl and k2 are the same (if their activa-
tion 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 k, 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 kl is less temperature-dependent that k,, 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 T,,,. We will use the
optimum temperature profile as the setpoint 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
-I Batch pro!ilcs.
60 MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS

total continuity equation for the reaction mass, after the reactants have been
charged and the batch cycle begun, is
4p VI
-=0-o (3.60)
dt
There is no inflow and no outflow. Since p is constant, dV/dt = 0. Therefore the
volume of liquid in the reactor is constant.
Component continuity for A:

v%= -Vk,C, (3.61)

Component continuity for B :

V f$$ = Vk,C, - Vk, C,

Kinetic equations :
k, = ClIe-ElIR= k, = a2 ,-EzIRT (3.63)
Using a lumped model for the reactor metal wall and the simple enthalpy equa-
tion h = C, T, the energy equations for the reaction liquid and the metal wall
are :
Energy equation for process :

pVC, $f = -A,Vk,C, - A2 Vk, C, - h,A,(T - TM) (3.64)

Energy equation for metal wall :

pM V, C, $ = h, A,(TJ - TM) - hi A,(T, - T)

where 1, and 2, are the exothermic heats of reaction for the two reactions.
Notice that when the reactor is heated with steam, TJ is bigger than TM and
TM is bigger than T. When cooling with water, the temperature differentials have
the opposite sign. Keep in mind also that the outside film coefficient h, is usually
significantly different for condensing steam and flowing cooling water.
This switching from heating to cooling is a pretty tricky operation, particu-
larly if one is trying to heat up to T,,, as fast as possible but cannot permit any
overshoot. A commonly used system is shown in Fig. 3.9. The temperature con-
troller 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
 EXAMPLES OF MATHEMATICAL MODELS OE CHEMICAL ENGINEERING SYSTEMS 61

follow the setpoint. Valve v-3 must be opened and valve V-4 must be shut when-
ever 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 setpoint minus the reactor temperature) and
the volumetric flow rates of steam F, and cooling water F, .

F, = h(E) Fw =.fm (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.

A. HEATING PHASE. 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.
Total continuity:

(3.67)

where pJ = density of steam vapor in the jacket

V, = volume of the jacket
pS = density of incoming steam
WC = 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:

v W,p,)
J -=FF,p,H,-h,A,(T,-T,)- W,h, (3.68)
dt

where UJ = internal energy of the steam in the jacket

H, = enthalpy of incoming steam
h, = enthalpy of liquid condensate
The internal energy changes (sensible-heat effects) can usually be neglected com-
pared with the latent-heat effects. Thus a simple algebraic steadystate energy
equation can be used
w = ho ‘%tTJ - Th4)
e (3.69)
Hs - k
62 MATHEMATICAL MODELS OF CHEMICAL ENGINEERING SYSTEMS

The equations of state for steam (or the steam tables) can be used to calcu-
late temperature TJ and pressure P, from density . For example, if the perfect-
pJ

gas law and a simple vapor-pressure equation can be used,

(3.70)

where M = molecular weight of steam = 18

A, and B, = vapor-pressure constants for water
Equation (3.70) can be solved (iteratively) for TJ if pJ is known [from Eq. (3.67)].
Once TJ is known, P, can be calculated from the vapor-pressure equation. It is
usually necessary to know PJ 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 heat-
transfer relationship (Q = UA 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.

PJ vJ cJ z = Fw CJ PATJO - TJ) + ho 4Ui.t - q) (3.7 1)

where TJ = temperature of cooling water in jacket

pJ= density of water
C, = heat capacity of water
TJ, = inlet cooling-water temperature
Checking the degrees of freedom of the system during the heating stage, we
have seven variables (C, , CB , T, TM, TJ , p J, and W,) and seven equations [Eqs.
(3.61), (3.62), (3.64), (3.65), (3.67), (3.69), and (3.70)]. During the cooling stage we
use Eq. (3.71) instead of Eqs. (3.67), (3.69), and (3.70), but we have only TJ instead
OfT,,p,,and WC.

3.10 REACTOR WITH MASS TRANSFER

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