The Modeling of Chemical Reactors Chapter 10

Chapter 10
The Perfectly
Mixed Flow
Reactor
10.1 Introduction
10.2 Mass and Energy Balances
10.2.1 Basic Equations
10.2.2 Steady-State Reactor Design
10.3 Design for Optimum Selectivity in Simultaneous Reactions
10.3.1 General Considerations
10.3.2 Polymerization in Perfectly Mixed Flow Reactors
10.4 Stability of Operation and Transient Behavior
10.4.1 Stability of Operation
10.4.2 Transient Behavior
Example 10.4.2.A Temperature Oscillations in a Mixed Reactor for
the Vapor-Phase Chlorination of Methyl Chloride
10.1 INTRODUCTION
This reactor type is the opposite extreme of the plug flow reactor dealt with in
Chapter 9. The essential feature is the assumption of complete uniformity of
concentration and temperature throughout the reactor, as contrasted with the
assumption of no intermixing of successive fluid elements entering a plug flow
vessel. Therefore, in the perfectly mixed flow reactor, the conversion takes place
at a unique concentration (and temperature) level which, of course, is also the
concentration of the effluent. To approach this ideal mixing pattern, it is
necessary that the feed be intimately mixed with the contents of the reactor in a
454 CHAPTER 10: THE PERFECTLY MIXED FLOW REACTOR
time interval that is very small compared to the mean residence time of the fluid
flowing through the vessel. Further discussions of deviations from these ideal
flow patterns are given in Chapter 12. In this chapter, it is assumed that perfect
mixing has been achieved.
The stirred flow reactor is frequently chosen when temperature control is
a critical aspect, as in the nitration of aromatic hydrocarbons or glycerine (Biazzi
process). The stirred flow reactor is also chosen when the conversion must take
place at a constant composition, as in the copolymerization of butadiene and
styrene, or when a reaction between two phases has to be carried out, or when a
catalyst must be kept in suspension as in the polymerization of ethylene with
Ziegler catalysts, the hydrogenation of α-methylstyrene to cumene, and the air
oxidation of cumene to acetone and phenol (Hercules Distillers process).
Finally, several alternate names have been used for what is called here
the perfectly mixed flow reactor. One of the earliest was “continuous stirred tank
reactor,” or CSTR, which some have modified to “continuous flow stirred tank
reactor,” or CFSTR. Other names are “backmix reactor,” “mixed flow reactor,”
and “ideal stirred tank reactor.”
10.2 MASS AND ENERGY BALANCES
10.2.1 Basic Equations

With complete mixing the volume is completely uniform in composition and
temperature, the continuity equations for the various components and the energy
equation may be integrated over the complete volume. From equations (7.1.1-1)
and (7.2.2-10) it follows that, in molar units,
dN j
= F j ,0 − F j ,e + VR j (10.2.1-1)
dt
For single reactions it is useful to write this equation in terms of the conversion
of the reactant A:
FA = FA0 (1 − x A )
so that
dx A
N A0 = − FA0 x A + VrA (10.2.1-2)
dt
Aris [1965] has discussed the reductions that are possible when the general set of
reactions
∑αj
ij Aj = 0
10.2 MASS AND ENERGY BALANCES 455
have to be considered. For arbitrary feed and/or initial compositions, which may
not have stoichiometrically interrelated compositions, the mass balance can be
written in terms of an extent for each independent reaction, plus variables related
to the incompatibility of the feed and initial compositions. For constant feed, this
single latter variable is related to the “washout” of the initial contents. In these
general situations it is probably just as easy to directly integrate (10.2.1-1).
The energy balance is written [see (7.2.4-5)]:
= ∑ F j ,0 (H j ,0 − H j ,e ) + V ∑ (− ∆H )i ri + Q (T )
dT
mt c p (10.2.1-3)
dt j i
where Q(T) represents external heat addition or removal from the reactor, for
example, AkU(TR – T). With mean specific heats the energy balance can be
written
= F0' ρ f c p (T0 − T ) + V ∑ (− ∆H i )ri + Q(T )
dT
Vρ f c p (10.2.1-4)
dt i
10.2.2 Steady-State Reactor Design

As a consequence of the complete mixing, a continuous flow stirred tank reactor
also operates isothermally. Therefore, in the steady state it is not necessary to
consider the mass and energy balances simultaneously. Optimum conditions may
be computed on the basis of the material balance alone, and afterwards the
energy balance is used, in principle (see Section 10.4), to determine the external
conditions required to maintain the desired temperature.
Thus, the design equation, from (10.2.1-2), is either
V
xA = r (10.2.2-1)
FA0 A
or, for constant densitiy,
V
C A0 − C A = rA = τ rA (10.2.2-2)
F'
where τ = V/F' = CA0V/FA0 is called the mean residence (or holding) time. Given
an expression for rA, the above equations can then be readily solved for xA as a
function of the system parameters. For a first-order reaction,
rA = kC A = kC A0 (1 − x A )
so that, with xA0 = 0,
kC A0V / FA0 1
xA = =1− (10.2.2-3)
1 + (kC A0V / FA0 ) 1 + (kC A0V / FA0 )
For constant density, the result is usually written as
CA 1 1
= = (10.2.2-4)
C A0 1 + (kV / F ) 1 + kτ
'
When two perfectly mixed reactors are connected in series, the mass
balance for the second reactor is
kC A0 (1 − x A 2 )
V V
x A2 − x A1 = rA ( x A2 ) = (10.2.2-5)
FA 0 FA 0
When xA1 is eliminated by means of (10.2.2-3), so that the final conversion is

written solely in terms of the conditions at the inlet (xA0 = 0), the following
equation is obtained:
1
x A2 = 1 − (10.2.2-6)
[1 + (kC A0V / FA0 )]2
Note that V is the volume of one reactor. For n reactors in series,
1
x An = 1 − (10.2.2-7)
[1 + (kC A0V / FA0 )]n
These formulas may be used for the study of the kinetics of a first-order reaction
by measuring xA, CA0, FA0, and V and then determining k. Alternatively, for a
given reaction, they can be used for determining the volume required to achieve a
certain production.
For second-order reactions, (10.2.2-1) becomes
FA0 x A = VkC A C B (10.2.2-8)
With the irreversible reaction A + B → products, when equimolar quantities of A

and B are fed to the reactor, the following equation is obtained:
1/ 2
FA 0  F 
2
FA 0 
xA = 1 + −  A0
 +
  (10.2.2-9)
2kC A0V  2kC A2 0V
2
 kC 2
A0 
V
 
The conversion at the exit of a second reactor of equal volume and placed in
series with the first is
1/ 2
  F 1/ 2
FA 0 
2 2
FA 0   FA 0  FA 0  
xA = 1 + − −   +  A0
 +  
2kC A0V   2kC A2 0V
2 
 kC A2 0V 2
 2kC A0V 
 kC A2 0V  
  
(10.2.2-10)
The results of (10.2.2-7) and (10.2.2-10) have been represented by

Schoenemann and Hofmann [see Schoenemann, 1952] in convenient diagrams.
Fig. 10.2.2-1 is the diagram for first-order reactions with constant density. The
conversion for more complex kinetic forms must often be obtained numerically,
by solving the algebraic equation (10.2.2-1) with the appropriate rate function on
the right-hand side.
Note that (10.2.2-1), (10.2.2-7), and (10.2.2-10) do not explicitly contain
the residence time, just as was the case for the continuity equations for the plug
flow reactor in Chapter 9. They could be reformulated [Levenspiel, 1962], but,
again as in Chapter 9, there is no advantage, and it is simpler to just use the
directly manipulated variables FA0, V, and CA0. It is only for constant-density
cases that the residence time V/F’ directly appears, as illustrated by (10.2.2-4).
Figure 10.2.2-1
Plot of x versus kV/F’ for first-order reactions. From Schoenemann [1952].
With the perfectly mixed flow reactor, the actual residence times of
individual fluid elements are a continuous spectrum: by the completely random
mixing, some fluid elements immediately reach the exit after their introduction,
whereas some remain in the reactor for a very long time. The above results did
not specifically consider this spread in residence time. The reason for this is that
the assumption of perfect mixing implies that each fluid element instantaneously
loses its identity. In principle, this means that the molecular environment is also
completely uniform for the reacting species. By implicitly defining the molecular
environment, the perfect mixing model only requires the conservation of mass to
predict the overall conversion. If the intensity of actual mixing does not generate
a uniform molecular environment before significant reaction occurs, then specific
account must be taken of the spectrum, or distribution, of fluid residence times.
These so-called “nonideal flow patterns” are considered in Chapter 12.
For a simple first-order irreversible reaction, with kV/F’ = 2.0 it follows
from (10.2.2-3) or (10.2.2-4) or Fig. 10.2.2-1 (the ordinate corresponding to the
intersection of kV/F’ = 2.0 and the n = 1 line) that the conversion will be xA =
0.667). In a plug flow or batch reactor, the conversion would be:
x A = 1 − exp[− kV / F '] = 0.865
If this conversion were desired in a perfectly mixed flow reactor a value for
kV/F’ = 6.5 would be required (the abscissa of the intersection of the ordinate
level of 0.865 and the n = 1 line in Fig 10.2.2-1). For the given k the reactor
volume would have to be 6.5 times the flow rate, rather than only twice, as with
plug flow. This example clearly illustrates that results obtained in a batch or plug
flow tubular reactor cannot be directly extrapolated to a continuous flow stirred
tank reactor — there may be large differences in conversion levels.
It also follows from the above discussion that it is difficult to obtain high
conversions in a continuous flow stirred tank reactor (at least for first-order
kinetics) without resorting to large volumes, in which perfect mixing may not be
easily achieved. Therefore, it is often preferable to connect two or more smaller
reactors in series, which will be shown to also reduce the total volume required to
achieve a given conversion. Indeed, from Fig. 10.2.2-1, it is seen that a
conversion of 0.865 can be obtained with kV/F’ = 1.75. This means that the
volume of each of the two tanks has to be 1.75 times the flow rate, for a total
volume ratio of 3.5 instead of 6.5 — a savings of almost a factor of 2.
When the total volume (= nV) is kept constant, the subdivision of the
reactor permits one to increase the overall conversion. Consider again the value
kV/F’ = 2.0 for a single-tank reactor, and determine the conversions when the
total volume is such that nVk/F’ = 2.0 while increasing n. The results can easily
be found from Fig. 10.2.2-1 by following the nVk/F' curve as it intersects the n =
1, 2, 3, ... curves, and reading the ordinate values:
n nVk/F' xA
1 2 0.67
2 2 0.75
3 2 0.78
5 2 0.81
∞ 2 0.87 (plug flow)
Alternatively, a given conversion may be reached with either a single large

reactor volume or with a series of smaller reactors. The ultimate choice is based
on economic factors, as illustrated in Fig. 10.2.2-2. The total reactor volume
required decreases with more subdivision (large n), but with the cost per reactor
proportional to V0.6, the total cost proportional to nV0.6 shows a definite minimum
— in this case at about n = 4. Plant operational difficulties may also increase
with n, and the optimum choice is usually a relatively small number of reactors in
series, especially since most of the savings in total volume occur for n < 5.
Exceptions are encountered in multistage contacting devices, but this is a more
complicated situation.
For reaction orders other than 1, the best choice is not two equal-size
tanks in series. Luss [1965] has provided a simple analytical procedure for
determining the optimum size ratio. For second-order reactions in two tanks in
series, this ratio is about 1:1 for low conversions and 1:2 for high conversion.
The overall advantage of the variable-sized multistage reactor is rather small
compared to that with equal sizes, so that usually equal-size tanks in series are
chosen.
The result that for a given conversion the perfectly mixed flow reactor
requires a larger volume than the plug flow reactor is only valid for reaction rate
expressions for which the rate monotonically decreases with decreasing reactant
concentration (e.g., simple orders greater than zero). For these reactions, it is
clearly advantageous to operate a reactor at the highest possible average
concentration level. In a perfectly mixed flow reactor, the conversion takes place
at the concentration level of the effluent, which is low, whereas the plug flow
reactor takes advantage of the higher concentrations in the inlet zone. The
subdivision of the total volume by series of stirred tanks is an intermediate
situation, which approaches the continuous concentration profile of the plug flow
reactor, and therefore yields a higher conversion compared to that in a single
tank.
Figure 10.2.2-2
Economic optimum choice of number of perfectly mixed reactors in series.
These conclusions can be readily quantitatively visualized as shown in

Fig. 10.2.2-3, which is based on the geometric nature of the plug flow or batch
reactor design equation versus that for the perfectly mixed flow reactor.
For a plug flow or batch reactor,

Aex
V dx A
= ∫
FA0 x A 0 rA ( x A )
For a perfectly mixed flow reactor,
V x − x A0
= Ae
FA 0 rA ( x Ae )
10.3 DESIGN FOR OPTIMUM SELECTIVITY IN SIMULTANEOUS REACTIONS 461
Figure 10.2.2-3
Comparison of plug flow and perfectly mixed flow reactor volumes.
The reactor size for plug flow is given by the area under the curve 1/rA versus xA
(area 1 in Fig. 10.2.2-3a). For perfectly mixed flow, on the other hand, the size is
given by the area of the rectangle with ordinate 1/rA(xAe) (i.e., evaluated at the
exit conversion), which is the sum of areas 1 + 2. Clearly, for this case where the
rate monotonically increases with concentration, the plug flow reactor will
always have the smaller area, and thus a smaller size. However, Fig. 10.2.2-3b is
a plot for another type of rate form, which could result from an autocatalytic
reaction, a dual-site catalytic mechanism, “negative order”, or any other form
where the rate has a maximum in the concentration range. Here, the optimum
arrangement is a perfectly mixed reactor followed by a plug flow reactor. The
combined volume could be significantly smaller than that of either type of single
reactor. Bischoff [1966] treated the case of Michaelis-Menten kinetics important
in enzyme and fermentation reactions and showed for a typical case that the total
volume is reduced by a factor of 2.77 with the optimal design.
In many cases the reactor volume is not the main factor in the choice of
the reactor type. Most reactions of industrial importance are actually complex
and the selectivity is far more important than the reactor size. Therefore, it is
important that a judicious choice of reactor type permits one to influence the
selectivity, which may depend on the concentration levels and, therefore, on the
degree of mixing in the reactor. This is discussed in the next section.
10.3 DESIGN FOR OPTIMUM SELECTIVITY IN SIMULTANEOUS

REACTIONS
10.3.1 General Considerations

The effect of the concentration levels on the selectivity of complex reactions can
most readily be seen by considering a few examples. For parallel reactions
where Q is the desired product, the rate equations for the formation of Q and S
are
rQ = k1C Aa '1
rS = k 2 C Aa '2
from which
rQ k1 a '1 − a '2
= CA (10.3.1-1)
rS k2
Figure 10.3.1-1
Conversions and selectivities for various degrees of mixing as a function of the mean
residence time τ = V/FA.
The relative rates of formation depend on the ratio of the rate coefficients k1/k2,
and on the difference in orders, a1' − a '2 . When both rates have the same order, it
is clear that the selectivity will not depend on the concentration level (although
the conversion will). For given k1/k2 and a1' ≠ a '2 , the selectivity can be altered by
the concentration environment, and this should then be chosen to maximize the
desired product Q. When a1' < a '2 , rQ/rS is small when CA is large. In batch and
plug flow reactors, part of the conversion is occurring at the high initial
concentrations. In the perfectly mixed flow reactor, the feed concentration is
immediately reduced to that of the outlet, which is low. Therefore, the selectivity
(to Q) will be higher in the perfectly mixed flow reactor. Similar reasoning
indicates that the opposite would be true for a1' > a '2 . The former case is
illustrated by the calculated results presented in Fig. 10.3.1-1, which compares
the conversions to Q, xQ = CQ/CA0, in batch or plug flow reactors with a cascade
of perfectly mixed reactors. It is seen, as expected, that a single stirred tank
would give the highest conversion to xQ and thus the highest selectivity for Q.
Next, consider consecutive reactions:
A
→
1
Q
→
2
S
where Q is the desired product. For both reactions first order, the resulting rate
equations have been integrated in Chapter 1 for the batch or plug flow reactors. A
few curves are shown by way of example in Fig. 10.3.1-2. Also from Chapter 1,
the maximum value of CQ is
 CQ 
  =
k1
( exp[− k1 / k lm ] − exp[− k 2 / k lm ] ) (10.3.1-2)
 C A0  max k 2 − k1
which occurs at the particular holding time
 V  1 ln (k / k )
τ max =  C A0  = ≡ 2 1
 FA0  max k lm k 2 − k1
For the perfectly mixed flow reactor, the mass balances (10.2.2-2), lead to
C A0
CA =
1 + (k1C A0V / FA0 )
k1C A2 0V / FA0
CQ =
[1 + (k1C A0V / FA0 )][(1 + (k 2 C A0V / FA0 )]
C S = C A0 − C A − C Q
Then, it can easily be shown that the maximum value of CQ is

−2
 CQ   k 
1/ 2

  =  2  + 1 (10.3.1-3)
 C A0  max  k1  
which occurs at
 V 
 C A0  = (k1 k 2 )−1 / 2
 F A0  max
Comparison of (10.3.1-2) and (10.3.1-3) shows that again there are differences
between the yields obtained in the reactor types discussed here. A specific
example is shown in Fig. 10.3.1-2, where it is seen that the batch or plug flow
reactor has greater selectivity for Q relative to the perfectly mixed flow reactor.
For sets of first-order reactions, Wei [1966] has shown that the convexity of
reaction paths is decreased from plug flow to mixed reactors because of the
intermingling of fluid elements with different extents of reaction, and so the
Figure 10.3.1-2
Consecutive reactions. Evolution of conversions with holding- or space time in batch or
plug flow and perfectly mixed reactors.
relative selectivities will decrease. Also, if the orders of the two reactions are
different, this can additionally affect the relative rates of the reactions in different
reactor types. The broader distribution of residence times of the fluid elements in
a perfectly mixed flow reactor will cause a broader maximum in the intermediate
species concentrations.
For more complicated reaction networks, it is not always completely
obvious how to apply the above concepts, as is seen from the example of van de
Vusse [1964]:
A
→
1
Q
→
2
S
A+ A
→
3
R
where Q is the desired product. The rates of the reactions are
rA = k1C A + k 3 C A2 (10.3.1-4)
rQ = k1C A − k 2 C Q (10.3.1-5)
and the yield CQ/CA0, or the selectivity CQ/(CA0 – CA), can be found from the ratio
of rates:
rQ k1 k 2 CQ
= − (10.3.1-6)
rA k1 + k 3 C A C A (k1 + k 3C A )
1 a 2 xQ
= −
1 + a1 (1 − x A ) (1 − x A )[1 + a1 (1 − x A )]
The results depend on the two parameter groups
k 3C A0 k2
a1 ≡ and a2 ≡ (10.3.1-7)
k1 k1
For k3CA0 >> k2, or a1 >> a2, it seems reasonable to expect that the parallel
reaction is more critical than the consecutive step in decreasing the yield of Q,
and based on the above paragraphs the optimum choice would be a perfectly
mixed reactor rather than a plug flow reactor. Also, for k3CA0 < k2, or a1 < a2, the
consecutive reaction should dominate, and the plug flow reactor should be
preferred. However, for a1 ≅ a2, it is not so clear which is the optimum reactor
type.
Van de Vusse [1964] performed computations to determine the proper
choices. Using the ratio of the mass balances for a perfectly mixed reactor,
(10.2.2-1) or (10.2.2-2), leads to:
rQ CQ xQ
= =
rA C A0 − C A xA
which, accounting for (10.3.1-6), has the solution
x A (1 − x A )
xQ = (10.3.1-8)
a1 (1 − x A ) + (1 − a 2 )(1 − x A ) + a 2
2
For plug flow the relationship is

dxQ rQ
=
dx A rA
from which, given (10.3.1-6)
[1 + a1 (1 − x )]a −1 dx
a2 x
 1 − xA  A 2
xQ =  
1 + a1 (1 − x A ) 
∫0 (1 − x )a 2
(10.3.1-9a)
=
(1 − x A ) ln 1  for a2 = 1 (10.3.1-9b)
1 + a1 (1 − x A )  1 − x A 
From these results, the maximum yield and selectivity is found from
dxQ d  xQ 
=0 or   = 0
dx A dx A  xA 
Results of such computations were summarized by van de Vusse in Fig. 10.3.1-3.

The conjectures concerning the optimum reactor type in the extreme regions of a1
and a2 are indeed verified, but also the more complicated middle region is
clarified.
Further consideration of the van de Vusse reaction sequence leads to the
conclusion that even better results might be obtained with a combination of
reactor types or with a reactor of intermediate mixing level. At low conversion,
when CA is high, and very little Q has been formed, it is most important to
suppress the parallel reaction, so that a perfectly mixed flow reactor is
advantageous. At higher conversion, when CA is relatively low, and an
appreciable amount of Q has been formed, the loss of yield by the consecutive
step dominates. To minimize this, plug flow is required. The optimum
configuration is a perfectly mixed reactor followed by a plug flow reactor. Using
a theoretical model of intermediate mixing levels, allowing for adjustment of the
levels along the reactor length, Paynter and Haskins (1970) were able to formally
Figure 10.3.1-3
Comparison of yield and selectivity in plug flow and perfectly mixed reactors. Points
correspond to pairs of values of a1 and a2 for which both types of reactor give the same
maximum yield. The upper line corresponds to equal selectivity for both types of reactor
(at zero conversion). From van de Vusse [1964].
optimize the intermediate mixing levels for complex reactions, including the one
under discussion. An alternate procedure was utilized by Gillespie and Carberry
[1966] and van de Vusse [1966] who considered a recycle reactor with a portion
of the product stream from a plug flow reactor being returned to the entrance. For
zero recycle one obviously has a plug flow reactor. For infinite recycle the
system in some sense behaves as a perfectly mixed reactor because of the large
feedback of material. Gillespie and Carberry [1966] showed that for certain
values of a1 and a2, an intermediate recycle rate indeed provided the best
performance.
Van de Vusse and Voetter [1961] also considered the parallel second-
order reactions
A+ B 
→
1
Q
A+ A
→
2
S
where Q is the desired product. Here, the best results would be obtained by
keeping CA low, throughout the reactor. The suggested way to do this was to
have a plug flow reactor with an entrance feed of B and some A, together with
side feed of A along the length of the reactor. The purpose was to always keep CA
low by continually converting it, but also provide sufficient A to convert the
amount of B fed to the reactor. A more practical system, of course, would be a

series of stirred tank reactors with intermediate feeds of A.
If a specified product distribution has to be achieved, rather than just the
maximization of a yield, the problem is naturally more complicated. Usually,
numerical simulations with the reactor design equations are necessary, often
combined with formal optimization procedures. A study of choice of reactor
type, together with separation and recycle systems, was presented by Russell and
Buzzelli [1969] for the important class of reactions
A+ B 
→
1
P1
P1 + B 
→
2
P2
M
Pn −1 + B 
→
n
Pn
which are encountered in industrial processes such as the production of mono-,

di-, and triethylene glycol from ethylene oxide and water; mono-, di-, and
triethanolamine from ethylene oxide and ammonia; mono-, di-, and triglycol
ethers from ethylene oxide and alcohols; mono-, di-, and trichlorobenzenes from
benzene and chlorine; and methylchloride, di- and trichloromethane from
methane and chlorine. In these cases, usually the lower members of the product
spectrum, P1 or P2 , are primarily desired and the proper reactor design is crucial
to success of the operation. Except for a few general cases such as this, most
cases must be handled on an individual basis by the above methods.
10.3.2 Polymerization in Perfectly Mixed Flow Reactors

One of the most important areas in which the concepts discussed in the previous
section can be applied is the selection and design of polymerization reactors. The
properties of polymers depend on their molecular weight distribution (MWD),
and the design should account for this. The subject is a vast one, therefore only
the basic concepts will be briefly discussed here. Several excellent reviews,
covering various aspects of the area from a chemical reaction engineering
viewpoint, in particular mathematical modelling, exist: Shinnar and Katz [1972],
Keane [1972], Gerrens [1976], Laurence and Chiovetta [1983], Ray [1972], Min
and Ray [1974], Tirrell et al. [1987], and Kiparissides [1996].
Performing polymerization reactions in perfectly mixed flow reactors
leads to quite different results from those obtained in batch or plug flow reactors,
as discussed in 1951 already by Denbigh [1951]. The key point concerns the
relative lifetimes of the active propagating polymer species. If this is long
relative to the mean holding time of the fluid in the reactor, the rules in Section
10.3.1 apply, and so the product distribution (the MWD) is narrow in a batch
reactor (BR)/plug flow reactor (PFR) and broader in a perfectly mixed flow
reactor (PMFR), just as in the earlier examples. The reason was the broader
distribution of residence times in the PMFR. However, if the active propagating
polymer lifetimes are much shorter than the mean holding time, the residence
time of almost all the fluid elements is approaching infinity compared to the local
reaction velocity. In this case, the constant availability of monomer tends to
produce a more uniform product, and so the PMFR produces a narrower MWD
than the BR/PFR. Figures 10.3.2-1a and 10.3.2-1b show results computed by
Denbigh [1951] for the free radical polymerization considered in Section 1.6.2 of
Chapter 1, illustrating the striking differences that may be obtained. Also, for the
Figure 10.3.2-1a
Chain length distribution by weight when the lifetime of the propagating macroradical is
long compared to the mean holding time in the reactor. After Denbigh [1951], from
Levenspiel [1962].
Figure 10.3.2-1b
Chain length distribution by weight when the lifetime of the propagating macroradical is
short compared to the mean holding time in the reactor. After Denbigh [1951], from
Levenspiel [1962].
TABLE 10.3.2-1
MOLECULAR WEIGHT DISTRIBUTIONS RESULTING FROM POLYREACTIONS
PREDICTED BY VARIOUS REACTOR MODELSa
Reactor BR or
Reaction PFR HCSTR SCSTR
Monomer (1.1)- Broader (1.2)- Schulz- (1.3)-Broader
coupling with than Schulz-Flory Flory distribution than 1.1.
termination
Monomer (2.1)- Narrower (2.2)- Schulz- (2.3)- Between
coupling without than Schulz-Flory Flory distribution (2.1) and (2.2)
termination (Poisson)
Polymer coupling (3.1)- Schulz- (3.2)- Much (3.3)- Between
Flory distribution broader than (3.1) and (3.2)
Schulz-Flory
a
From Gerrens [1976]. BR = batch reactor; PFR = plug flow reactor; HCSTR =
homogeneous continuous stirred tank reactor = perfectly mixed flow reactor of this
chapter; SCSTR = segregated continuous stirred tank reactor.
copolymerization of two monomers, the uniform concentrations of a PMFR tend

to produce a product of more uniform composition than a BR/PFR.
Monomer coupling with termination is encountered in free radical
polymerization (Chapter 1), without termination in living polymerization,
discussed in Chapter 8, and polymer coupling in polycondensation, encountered
e.g., in the production of nylon.
SCSTR in Table 10.3.2-1 refers to a reactor model with “segregated
flow”, considered in more detail in Chapter 12. In this special state of mixing the
fluid elements are randomly distributed in the reactor, like in HCSTR, but also
retain their individual identities. This situation is considered to be characteristic
for very viscous fluids [see Nauman, 1974]. In (1.1) and (1.2) the life time of the
growing radical is much smaller than the average residence time in the reactor. In
(2.1) and (2.2) it is long and equals the residence time. For the free radical
polymerization considered in Section 1.6.2 of Chapter 1, Fig. 10.3.2-2 indicates
how the MWD evolves with conversion in a HCSTR and gets narrower with
increasing conversion.
The polymerization model used by Gerrens is very simple. A more
complete description of the polymerization process would include steps like
thermal initiation; chain transfer to monomer, solvent and polymer; diffusion
control of propagation (glass effect) and of termination (Trommsdorff effect). As
second steps in a series of consecutive reactions the chain transfer, or branching,
steps, are very sensitive to mixing effects. They are very important for the
polymer properties.
10.4 STABILITY OF OPERATION AND TRANSIENT BEHAVIOR 471
Figure 10.3.2-2
Weight distribution of polymer in HCSTR; parameter: conversion, x; number average
degree of polymerization PN at zero conversion = 1000. From Gerrens [1976].
Figure 10.3.2-3
Vinyl acetate polymerization. Evolution of polydispersity with fractional conversion in
three reactor types for typical parameter values. From Nagasubramanian and Graessley
[1970].
Nagasubramanian and Graessley [1970] compared MWD obtained in

vinyl acetate polymerization — a rapid reaction — carried out in a batch reactor
and in HCSTR and SCSTR. Branching was included in the model. Figure 10.3.2-
3 shows that the polydispersity is higher or the MWD wider in a CSTR than in a
BR/PFR, regardless of the degree of segregation of the liquid elements—the
opposite of what is shown in Fig. 10.3.2-1b. For typical parameter values the
residence time distribution of the fluid elements becomes the predominant factor
in this case.
10.4 STABILITY OF OPERATION AND TRANSIENT BEHAVIOR
10.4.1 Stability of Operation

The problem addressed in this section is the state arrived at by the reactor on a
perturbation of the operating conditions. Do small perturbations necessarily lead
to slight differences in operating conditions or can they lead to drastic changes?
Will the reactor necessarily return to its original steady state when the
perturbation is removed? The answers depend on whether the original steady
state is “stable” or not.
Considerable, but not complete, information on the stability of a steady
state can be derived from the combined steady-state continuity and energy
equations. Therefore, (10.2.2-1) is considered simultaneously with the steady-
state form of (10.2.1-3):
rA
xA = τ (10.4.1-1)
C A0
τ rA
T − T0 = − QH (T ) (10.4.1.-2)
λ C A0
with
C A0V V
τ= = '
FA0 F0
ρ f cp
λ=
C A 0 ( − ∆H )
Q
QH (T ) = −
ρ f c p F0'
Equation (10.4.1-2) can be written
= [T − T0 + QH (T )]
rA ( x A , T ) 1
λC A 0 τ
When QH(T) is explicited in the following way,
QH (T ) =
UAk
(T − Tr )
ρ p c p F0'
with Tr the temperature of the heat exchanging fluid, (10.4.1-2) becomes
rA ( x A , T )  1 UAk  T UAk 
= + T − 0 + Tr  (10.4.1-3)
λC A 0 τ ρ c V  τ ρ cV 
 f p   f p 
Equation (10.4.1-3) is a nonlinear algebraic equation, to be solved for T, given

values for all the parameters. The equation has been arranged in such a way that
the left-hand side represents the rate of heat generated per total heat capacity of
the reactor, QG(T), and the right-hand side represents the rate of heat removal by
flow and heat exchange, QH(T). The heat balance just states, then, that at a
steady-state operating point, QG(T) = QH(T).
The two relationships are plotted in Fig. 10.4.1-1 versus the reactor
temperature for an exothermic irreversible reaction. The S shape of QG results
from the Arrhenius dependence of the rate coefficient, whereas from (10.4.1-3) it
follows that QH leads to an (essentially) straight line. When τ is kept constant, a
variation in T0 does not affect QG; but in the first quadrant, the QH lines are
shifted to the right as T0 is increased. For a value T01 , only one intersection of QG
and QH is observed, namely, point 1. For a range of T0 values between T0 2 and
T0 4 , three intersections are observed; therefore three steady states are possible
for one and the same operating condition.
Figure 10.4.1-1
Shift of heat removal line QH with increasing feed temperature T0 and resulting shift of
intersection with heat generation curve, QG.
This multiplicity of steady states is caused by the highly nonlinear nature of the
heat generation expression and by the internal thermal feedback associated with
complete mixing. Note that the phenomenon is not limited to completely mixed
reactors but can also occur with plug flow reactors with external recycle, as
discussed by van Heerden [1953] and, a long time before, by Liljenroth [1918]
(see Chapter 11).
Of the three possible steady states 3, 5, and 7, the middle one is unstable,
while 3 and 7 are naturally stable. Van Heerden explained this in terms of the
shapes of QG and QH at these points. A small increase in temperature from T5
leads to a more important increase of QG than of QH, since the slope of QG at 5 is
much larger than that of QH. Consequently, the reactor temperature increases to a
value T7, corresponding with the higher intersection and a higher conversion. A
slight decrease in reactor temperature would again have a larger effect on QG than
on QH, and the reactor would continue to cool until T3 is reached, corresponding
to a low conversion. Point 5, therefore, corresponds to an unstable steady state
and would not be maintained without automatic control. By the same reasoning,
based on the local slopes of QG and QH, it can be shown that the conditions
corresponding to points 3 and 7 are naturally stable.
If T0 is slowly increased from T01 to T0 3 , the reactor will behave as
indicated by the so-called lower branch of the S curve. But as T0 slightly exceeds
T0 4 , the reactor conditions jump to values corresponding to point 8, on the upper
branch of the QG curve. The reactor is said to ignite. Any further increase in T0
leads to a gradual increase in T along the upper branch. Upon reducing T0 from
T0 5 to T0 2 , for example, the temperature slowly decreases, but any further
decrease in T0 leads to an intersection 2 on the lower branch. The reactor is said
to be quenched. Further decreasing T0 now leads to a gradual decrease in T. The
hysteresis of reactor conditions upon increasing and decreasing one of the
operating parameters, in this case T0, is typical for the occurrence of multiple
steady states. It is illustrated in Fig. 10.4.1-2.
An experimental illustration of the above theoretical derivations was
provided by Vejtassa and Schmitz [1970] by means of the exothermic reaction
between sodium thiosulfate and hydrogen peroxide in an adiabatic flow reactor
with complete mixing.
For an adiabatic reactor (10.4.1-1) and (10.4.1-2) can be combined to
give
x A = λ (T − T0 )
This relationship between conversion and temperature can be used to express the
Figure 10.4.1-2
Hysteresis of steady reactor temperature T upon variation of feed temperature T0.
rate of reaction solely in terms of the temperature, so that (10.4.1-3) becomes
1 1
rA (T ) = (T − T0 )
λC A 0 τ
The heat generation curve shown in Fig. 10.4.1-3 was derived from
adiabatic batch reactor data. For given inlet concentration this curve depends
only on the reactor temperature. Each point on the curve corresponds to a given
conversion and holding time, therefore reactor temperature. The increasing part
results from the increase of the reaction rate with temperature, while the
decreasing part reflects the depletion of reactants. The curve drops to zero as the
complete adiabatic temperature rise is achieved; that is, the reaction rate drops to
zero as the limiting reactant, hydrogen peroxide, is completely consumed. Heat is
only removed through the exit stream. The heat removal is a function of T – T0,
with T0 a constant. For each value of T, and therefore of τ, a different straight line
is obtained. The steady state requires QH = QG, and Fig. 10.4.1-3 illustrates how
three steady states are possible with this reaction between holding times of 6.8
and 17.8 s. Figure 10.4.1-4 shows the hysteresis observed in the steady state
when the holding time is progressively increased and decreased.
Multiplicity of steady states was also observed by Schmidt et al. [1984]
who studied the solution polymerization of methylmethacrylate in a continuous
stirred tank with complete mixing. With endothermic reactions the straight lines
QH(T) have negative slopes, and only one intersection is possible.
Figure 10.4.1-3
Heat generation and removal functions versus reactor temperature for a feed mixture of
0.8-M Na2S2O3 and 1.2-M H2O2 at 0°C. From Vejtassa and Schmitz [1970].
Figure 10.4.1-4
Steady-state hysteresis results. From Vejtassa and Schmitz [1970].
Reversible exothermic reactions have an ultimate decrease in rate with

temperature, and so the heat generation curve turns down (as in Fig. 10.4.1-3);
therefore, the qualitative features remain the same. The heat generation curve for
complex reactions can have more than one “hump”, and thus more than three
steady states are possible for given operating condition. The humps also tend to
be smaller, leading to more readily obtained transitions between steady states
[Westerterp, 1969]. Also, other types of multiple steady states and instabilities
can occur. For example, with certain forms of rate expressions highly nonlinear
in concentration, just the mass balance (10.4.1-1) may have more than one
solution, as discussed in Perlmutter [1972].
These considerations can be cast in analytical form, following the
reasoning of van Heerden [1953] given above. The slopes of the heat removal
and generation rates in (10.4.1-3) are found as follows:
dQH d 1  1  dQH 
=  [T − T0 + QH (T )] = 1 +  (10.4.1-4)
dT dT τ  τ dT 
dQG d  1 
=  rA ( x A , T ) (10.4.1-5)
dT dT  λC A0 
Now,
drA ∂rA dx A ∂rA
= +
dT ∂x A dT ∂T
∂rA τ drA ∂rA

= ⋅ +
∂x A C A0 dT ∂T
where the last line utilized the mass balance (10.4.1-1). The total change of the
heat generation rate with temperature is
1 ∂rA
dQG λC A0 dT
= (10.4.1-6)
dT τ ∂rA
1−
C A0 ∂x A
Then, the reactor can be stable if the heat removal slope is greater than the heat
generation slope at the steady-state operating point, that is, when
dQH dQG
>
dT dT
leading to
 τ ∂rA  dQH  τ ∂rA

1 − 1 + > (10.4.1-7)
 C A0 ∂x A  dT  λC A0 ∂T
For the case of a first-order irreversible reaction in a reactor with simple heat
exchange, from (10.4.1-3) with (10.4.1-1), this criterion becomes
 UAk  1 E kτ
(1 + kτ )1 + > (10.4.1-8)
 ρ c F '  λ RT 2 1 + kτ
 f p 0 
Equation (10.4.1-7) is a necessary but not sufficient condition for

stability. In other words, if the criterion is satisfied, the reactor may be stable; if
it is violated, the reactor will be unstable. (Aris [1965] prefers to use the reverse
inequality as a sufficient condition for instability.) The reason is that in deriving
(10.4.1-6), it was implicitly assumed that only the special perturbations in
conversion and temperature related by the steady-state heat generation curve
were allowed. To be a general criterion giving both necessary and sufficient
conditions, arbitrary perturbations in both conversion and temperature must be
considered. Van Heerden’s reasoning actually implied a sense of time (“tends to
move ...”). Therefore, the proper criteria can only be clarified and deduced by
considering the complete transient mass and energy balances.
10.4.2 Transient Behavior

The transient mass and energy balances are given by (10.2.1-2) and (10.2.1-4):
dx A r
τ = −xA + τ A (10.4.2-1)
dt C A0
dT τ rA
τ = T0 − T + − QH (T ) (10.4.2-2)
dt λ C A0
Analytical solution of this system of differential equations is not possible.

Therefore, Aris and Amundson [1958] linearized it by a Taylor expansion, about
the steady-state operating points. Consider the small perturbations
x = x A − x A, s
y = T − Ts
where the subscript s refers to a steady-state solution. Then, subtracting equations

(10.4.1-1) and (10.4.1-2) from equations (10.4.2-1) and (10.4.2-2) gives
dx τ
τ = −x + (rA − rA, s ) (10.4.2-3)
dt C A0
dy τ
τ = −y + (r − r ) − [QH (T ) − QH (Ts )] (10.4.2-4)
dt λC A 0 A A, s
Expanding rA and QH(T) in Taylor series and neglecting second-order terms leads
to
 ∂r   ∂r 
rA = rA,s +  A  x +  A  y
 ∂x A  s  ∂T  s
 dQ 
QH (T ) = QH (Ts ) +  H  y
 dT  s
Substituting into (10.4.2-3) and (10.4.2-4) yields
dx  τ  ∂rA    τ  ∂rA  
τ = − 1 −    x +    y (10.4.2-5)
dt  C A0  ∂x A  s   C A0  ∂T  s 
dy  τ  ∂rA    τ  ∂rA   dQH  

τ =    x − 1 −   +  y (10.4.2-6)
dt  λC A0  ∂x A  s   λC A0  ∂T  s  dT  s 
These equations, (10.4.2-5) and (10.4.2-6), are linear differential equations

whose solutions are combinations of exponentials of the form exp[mt/τ], where
the values of m are solutions of the characteristic equation
m 2 + a1m + a0 = 0 (10.4.2-7)
where
 τ  ∂rA     dQH    τ  ∂rA  
a1 = 1 −    + 1 +   −   
 C A0  ∂x A  s    dT  s   λC A0  ∂T  s 
 τ  ∂rA     dQH    τ  ∂rA  

a0 = 1 −    1 +   −   
 C A0  ∂x A  s    dT  s   λC A0  ∂T  s 
The solutions will only go to zero as t → ∞ when the real parts of the roots are
negative [e.g., see Himmelblau and Bischoff, 1968]. The solution of (10.4.2-7) is
1
m= (−a1 ± a12 − 4a0 )
2
This stability condition is always met when
a1 > 0 (10.4.2-8)
and
a0 > 0 (10.4.2-9)
If a0 < 0, at least one of the roots will be positive, and the solution will diverge
for t → ∞. If a1 = 0 and a0 > 0, the roots will be purely imaginary numbers, with
oscillatory solutions for x and y. Thus, the necessary and sufficient conditions for
stability (i.e., xA and T return to the steady state after removal of the perturbation
or x and y → 0 as t → ∞) are equations (10.4.2-8) and (10.4.2-9). In terms of the
physical variables those equations can be written as follows:
 τ  ∂rA     dQH    τ  ∂rA  

1 −    + 1 +   >    (10.4.2-10)
 C A0  ∂x A  s    dT  s   λC A0  ∂T  s 
and
 τ  ∂rA     dQH    τ  ∂rA  
1 −    1 +   >    (10.4.2-11)
 C A0  ∂x A  s    dT  s   λC A0  ∂T  s 
Comparing (10.4.2-11) with (10.4.1-7) reveals that they are identical, and the
above discussion shows that the “slope” criterion, a0 > 0, is indeed a necessary
condition for stability. Also, the condition a0 > 0 is not sufficient, for if a1 = 0,
the oscillations are not stable, in that xA and T do not return to their steady-state
values. Thus, the second criterion, (10.4.2-10), is related to oscillatory
behavior—a discussion is given by Gilles and Hofmann [1961].
For the case of a first-order irreversible reaction with simple heat
exchange, the second (“dynamic”) criterion (10.4.2-10) becomes
 UAk  1 E kτ
(1 + kτ ) + 1 + > (10.4.2-12)
 ρ c F '  λ RT 2 1 + kτ
 f p 0 
For an adiabatic reactor, in which QH ≡ 0, the “slope” criterion (10.4.2-11)

implies the other equation (10.4.2-10). In that case the slope criterion is both
necessary and sufficient.
EXAMPLE 10.4.2.A
TEMPERATURE OSCILLATIONS IN A MIXED REACTOR FOR THE
VAPOR-PHASE CHLORINATION OF METHYL CHLORIDE
The reaction
CH 3Cl Cl
→ 2
CH 2Cl 2 Cl
→ 2
CHCl 3 Cl
→ 2
CCl 4
was studied by Bush [1969]. First, the steady-state heat generation and removal
rates were determined as shown in Fig. 10.4.2.A-1.
The necessary “slope” criterion is satisfied over the entire range of
conditions:
dQH dQG
>
dT dT
so that there may be a unique steady-state reactor temperature for a given bath
temperature Tr.
It was found, however, that the reactor showed oscillatory behavior in
certain ranges [see Bush, 1972]. Therefore, the second “dynamic” criterion,
(10.4.2-10) was also checked with relationships similar to (10.4.2-12), but also
accounting for some of the additional complexities in the real (gas phase)
experimental system. The results are shown in Fig. 10.4.2.A-2, where the left-
hand side (LHS) and right-hand side (RHS) of the criterion are plotted. A central
region exists where the criterion is violated.
Figure 10.4.2.A-1
Steady-state temperature: ●, heat evolution; ×, heat removal for Tr = 400°C; ▲, heat
removal for Tr = 390°C; , steady-state temperatures Ts. From Bush [1969].
Figure 10.4.2.A-2
Stable and unstable reaction temperatures: ●, LHS; ×, RHS. From Bush [1969].
If a control device acts upon the reactor temperature e.g., by modifying

the flow rate of the heat exchanging fluid, QH in (10.4.2-2) has to be adapted into
QH + [ β + µ (T − Ts )]
and the corresponding term in the linearized equation (10.4.2-6) is changed into
 dQH   dQ 
  → H  +µ
 dT  s  dT  s
This adapted derivative has to be substituted into the two criteria, (10.4.2-10) and
(10.4.2-11). This will increase the value of the LHS and make it easier to satisfy
the criteria. An inherently unstable reactor can be made stable by proper control.
Real life control problems require more detail, however.
All of the above conclusions were based on the linearized equations for
small perturbations about the steady state. A theorem of differential equations
states that if the linearized calculations show stability, then the nonlinear
equations will also be stable for sufficiently small perturbations. For larger
excursions, the linearizations are no longer valid, and the only recourse is to
(numerically) solve the complete equations. Uppal, Ray, and Poore [1974]
performed extensive calculations and laid the basis for a detailed mathematical
classification of the many various behavior patterns possible; refer to the original
work for the extremely complex results. The evolution of multiple steady states
when the mean holding time is varied leads to even more bizarre possible
behavior [see Uppal et al., 1976]. Further aspects can be found in Aris [1965],
PROBLEMS 483
Perlmutter [1972], and Denn [1975], and in reviews of Schmitz [1975], Razón
and Schmitz [1987], and Morbidelli et al. [1987]. Balakotaiah and Luss [1982,
1983, 1984] presented penetrating analyses of multiplicity encountered with
parallel and consecutive reactions using singularity theory. The fundamentals of
multiplicity of steady states and oscillatory behavior have been studied
extensively by Prigogine and his co-workers, also in living organisms
[Babloyantz, 1986].
PROBLEMS
10.1 Kermode and Stevens [1965] studied the reaction of ammonia and
formaldehyde to make hexamine:
4NH 3 + 6HCHO → (CH 2 ) 6 N 4 + 6H 2 O

(A) (B)
The continuous flow reactor was a 490-cm3 baffled stainless steel tank
stirred at 1800 rpm, with several precautions to ensure almost perfect
mixing. The overall reaction had a rate
rA = kC A C B2 mol A/l s
with k = 1.42 × 103 exp(-3090/T). The reactants were fed in streams of

1.50 cm3/s, with the ammonia concentration 4.06 mol/l and the
formaldehyde concentration 6.32 mol/l. The temperature in the reactor
was 36°C. Calculate CA and CB, the concentrations in the reactor and in
the effluent.
10.2 A perfectly mixed flow reactor is to be used to carry out the reaction
A → R. The rate is given by
rA = kC A kmol/m3 s
with
 8000  -1
k = 4 × 10 6 exp−  s
 T (K ) 
Other physicochemical data are
∆H = -167,480 kJ ρcp = 4,187 kJ/m3°C

MA = 100 kg/kmol CA0 = 1 kmol/m3
At a temperature of 100°C and a desired production rate of 0.4 kg/s,

determine (a) the reactor volume required at a conversion of 70 percent;
(b) the heat exchange requirement.
10.3 The first-order reversible reaction
is carried out in a constant-volume perfectly mixed flow reactor. The

feed contains only A, at a concentration of CA0, and all initial
concentrations are zero.
(a) Show that the concentration of A is given by
t /τ
CA 1 + k 2τ k2 k1e − (1+ k1τ + k2τ )
= − e −t / τ −
C A0 1 + k1τ + k 2τ k1 + k 2 (k1 + k 2 )(1 + k1τ + k 2τ )
where τ = V/F’ = mean residence time.

(b) Find CA/CA0 at steady state, and also show that for very rapid
reactions, (k1,k2) → ∞, the equilibrium concentration is
CA 1 k1
= K≡
C A0 1 + K k2
(c) For very rapid reactions, (k1,k2) → ∞, show that, in general,
CA 1 1
= − e −t / τ
C A0 1 + K 1 + K
and explain how this can be physically interpreted as the final

steady-state equilibrium minus the equilibrium “washout”.
10.4 For a first-order reaction, the conversion to be expected in a series of n

stirred tanks can be formed from Fig. 10.2.2-1. Alternatively, at given
conversion level, and for a given rate coefficient and mean residence
time, kτ, the total volume required to carry out the reaction can be
determined.
(a) With this basis, plot Vtotal/Vplug flow versus the fraction of unreacted
reactant, 1 – xA, for various values of n = 1, 2, 5, 10, 40. Study the
effect of utilizing several stirred tank reactors in series compared to
a plug flow reactor.
PROBLEMS 485
(b) Add further lines of constant values of the dimensionless group

kτtotal to the plot — these are convenient for reactor design
calculations.
10.5 (a) For the reversible consecutive reactions
taking place in a steady-state, constant-volume perfectly mixed

reactor, show that the concentration of R, when the feed contains
only A at concentration CA0, is
k1τ  k 2τ 
1 + 
CR 1 + k1τ  K b 
=
C A0  k1τ 1  k τ 
 + 11 + 2  + k 2τ
 1 + k1τ K a  Kb 
where
Ka = k1/k2 = equilibrium constant for the first reaction
Kb = k3/k4
(b) For both reactions irreversible, show that the results of part (a)
reduce to the equation given in Section 10.3.
(c) If the first reaction is very rapid, it is always close to its equilibrium
as R is reacting further to S. Explain how this can be represented by
k1 → ∞ but Ka = finite, and find the expression for CR/CA0 by
appropriately reducing the result of part (a). This is similar to a
rate-determining step situation, and is more simply derived by
taking the first reaction to always be in instantaneous equilibrium,
CA ≈ CR/Ka. Show that a new derivation of the mass balances with
this basis leads to the same result as above. Note that this is a useful
technique in more complex situations of this type, when the general
expression may not be possible to derive.
10.6 Consider the startup of a perfectly mixed flow reactor containing a

suspended solid catalyst. For a first-order reaction, rA = kCA, and
assuming constant volume, show that the outlet concentration of reactant
A is
 
 C ( 0) 
C A (t ) 1  1
= + A − 
C A0  (1 − ε )V   C A0  (1 − ε )V 
1 + F ' k
  1 + F ' k
 
  (1 − ε )V   F ' 
× exp− 1 + k  t 
  F'   εV  
where
CA(0) = initial concentration

CAi = feed concentration
ε = void fraction, not occupied by solids
ε V = fluid volume
Note that the steady-state (t → ∞) result depends only on the group (1 –

ε) Vk/F', the solid catalyst inverse space velocity-rate coefficient group,
but the transient effects also require knowledge of (F’/εV)-1, or the fluid
mean residence time.
10.7 In a process to make compound R, the following reactions occur:
A+ B
→
1
2R
A+ A
→
2
2S
(a) Based on the text, explain why the optimum chemical composition
would be high B and low A concentrations.
(b) An idealized reactor configuration to achieve this is reactor with
side stream feeds of A, as shown below:
where f(V) (in m3 side feed/h m3 reactor volume) is the distribution

of side feed additions along the reactor length (volume) to be
determined. Assuming the reactor to operate with plug flow, derive
the following mass balances:
PROBLEMS 487
Total:
dF '
= f (V )
dV
A:
d
( F ' C A ) = C AW f (V ) − k1C A C B − k 2 C A2
dV
B:
d
( F ' C B ) = − k 1C A C B
dV
(c) As an appropriate optimal design, the condition will be used that
the side feed be adjusted to maintain CA = constant (i.e., CA = CA0 =
CAL). Also, a high conversion of A is desired, and to simplify the
calculations, it will be assumed that the side feed concentration is
high, CAW >> CA = CA0 = CAL. For these special conditions, show
that the three mass balances become
F ' ≅ constant = F0'
0 = C AW f (V ) − k1C ALC B − k2C AL

2
dC B
F' = − k1C AL C B
dV
(d) Using the simplified balances, determine the total reactor volume
required as a function of F0' , CAl, CB0, and CBL.
(e) Show that to maintain the above condition of constant CA, the side
feed distribution as a function of reactor length, has to satisfy
f (V ) =
C AL
C AW
(
k 2C AL + k1CB0 e − k1C ALV / F0
'
)
(f) As a final condition, equal stoichiometric feeds of A and B are to be
used:
VL
F0'C B 0 = F0'C A0 + C AW ∫ f (V )dV

0
Show for this case that the relationship between the outlet levels of
A and B is
C BL
C AL =
k C
1 − 2 ln BL
k1 C B 0
(g) A useful measure is the weight yield of the desired R:
total R formed
Y≡
total A fed
For k2/k1 = 1, compare the yield as a function of conversion with

that found in a single perfectly mixed reactor and with a single plug
flow reactor without side feeds.
Note:
This problem was first solved by van de Vusse and Voetter [1961], who also
considered more general cases and a true mathematically optimal profile, f(V).
These latter results were rather close to the approximately optimal basis of CA =
constant. Finally, such an ideal scheme might be implemented in practice by
using a series of stirred tank reactors with intermediate feed additions of A.
10.8 A perfectly mixed reactor is to be used for the hydrogenation of olefins

and will be operated isothermally. The reactor is 10 m3 in size, and the
feed rate is 0.2 m3/s, with a concentration of CA0 = 13 kmol/m3. For the
conditions in the reactor, the rate expression is
CA kmol
rA =
(1 + C A ) m3 ⋅ s
2
It is suspected that this nonlinear rate form, which has a maximum value,
may cause certain regions of unstable operation with multiple steady
states.
(a) From the reactor mass balance (10.2.2-2), determine if this is the
case by plotting rA and (1/τ)(CA0 – CA) on the same graph.
(b) To what concentration(s) should the feed be changed to avoid this
problem?
Note:
This problem was investigated by Matsuura and Kato [Chem. Eng. Sci., 22, 17
(1967)], and general stability criteria are provided by Luss [Chem. Eng. Sci., 26,
1713 (1970)].
10.9 Using the expressions for the necessary and sufficient conditions for
stability of a stirred tank chemical reactor as derived in Section 10.4,
REFERENCES 489
(a) Show that for a single endothermic reaction the steady state is
always stable.
(b) Show that for an adiabatic reactor the slope condition
 τ  ∂rA     dQH    τ  ∂rA  

1 −    1 +   >   
 C A0  ∂x A  s    dT  s   λC A0  ∂T  s 
is sufficient, as well as necessary.

(c) If the reactor is controlled on concentration,
QH ( x, y ) = QH ( y ) + vx
show that it is not always possible to get control of an unstable

steady state. Note here that QH = QH(x, y), and be careful of the
criteria that you use.
10.10 Show that recycling the effluent of a perfectly mixed reactor has no
effect on the conversion.
10.11 Consider two perfectly mixed reactors in series. For a given total
volume, determine optimal distribution of the subvolumes for (a) first-
order reaction, (b) second-order reaction.
REFERENCES
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(1984).
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109, p. 610, Washington, D.C. (1972).
Chang, M., and Schmitz, R.A., Chem. Eng. Sci., 30, 21 (1975).
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227 (1951).
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Cliffs, N.J. (1975).
Gerrens, H., in Proc. 4th Int. Symp. Chem. Reac. Eng., 585-614, Dechema (1976).
Gilles, E. D., and Hofmann, H., Chem. Eng. Sci., 15, 328 (1961).
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Himmelblau, D.M., and Bischoff, K.B., Process Analysis and Simulation, Wiley, New
York (1968).
Keane, T.R., in Proc. 2nd Int. Symp. React. Eng., Elsevier, Amsterdam (1972).
Kermode, R.I., and Stevens, W.F., Can. J. Chem. Eng., 43, 68 (1965).
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Kramers, H., and Westerterp, K.R., Elements of Chemical Reactor Design and
Operation, Academic Press, New York (1963).
Laurence R.L., and Chiovetta, M.G., in Proc. of Berlin Workshop on Polymer Reactor
Engineering, K.H. Reichert, Carl Hanser Verlag, Munich (1983).
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Liljenroth, F.G., Chem. Metal. Eng., 19, 287 (1918).
Luss, D., Chem. Eng. Sci., 20, 17 (1965).
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(1974).
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ed. by J.J. Carberry and A. Varma, M. Dekker, New York (1987).
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(1972).
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Chapter 10

10.2 MASS AND ENERGY BALANCES

10.2.1 Basic Equations

10.2.2 Steady-State Reactor Design

For constant density, the result is usually written as

When xA1 is eliminated by means of (10.2.2-3), so that the final conversion is

FA0 x A = VkC A C B (10.2.2-8)

With the irreversible reaction A + B → products, when equimolar quantities of A

The results of (10.2.2-7) and (10.2.2-10) have been represented by

x A = 1 − exp[− kV / F '] = 0.865

Alternatively, a given conversion may be reached with either a single large

These conclusions can be readily quantitatively visualized as shown in

For a plug flow or batch reactor,

For a perfectly mixed flow reactor,

10.3 DESIGN FOR OPTIMUM SELECTIVITY IN SIMULTANEOUS

10.3.1 General Considerations

which occurs at the particular holding time

Then, it can easily be shown that the maximum value of CQ is

where Q is the desired product. The rates of the reactions are

The results depend on the two parameter groups

which, accounting for (10.3.1-6), has the solution

For plug flow the relationship is

Results of such computations were summarized by van de Vusse in Fig. 10.3.1-3.

amount of B fed to the reactor. A more practical system, of course, would be a

which are encountered in industrial processes such as the production of mono-,

10.3.2 Polymerization in Perfectly Mixed Flow Reactors

copolymerization of two monomers, the uniform concentrations of a PMFR tend

Nagasubramanian and Graessley [1970] compared MWD obtained in

10.4 STABILITY OF OPERATION AND TRANSIENT BEHAVIOR

10.4.1 Stability of Operation

Equation (10.4.1-2) can be written

When QH(T) is explicited in the following way,

with Tr the temperature of the heat exchanging fluid, (10.4.1-2) becomes

Equation (10.4.1-3) is a nonlinear algebraic equation, to be solved for T, given

rate of reaction solely in terms of the temperature, so that (10.4.1-3) becomes

Reversible exothermic reactions have an ultimate decrease in rate with

∂rA τ drA ∂rA

 τ ∂rA  dQH  τ ∂rA

Equation (10.4.1-7) is a necessary but not sufficient condition for

10.4.2 Transient Behavior

Analytical solution of this system of differential equations is not possible.

where the subscript s refers to a steady-state solution. Then, subtracting equations

Substituting into (10.4.2-3) and (10.4.2-4) yields

dy  τ  ∂rA    τ  ∂rA   dQH  

These equations, (10.4.2-5) and (10.4.2-6), are linear differential equations

 τ  ∂rA     dQH    τ  ∂rA  

This stability condition is always met when

 τ  ∂rA     dQH    τ  ∂rA  

For an adiabatic reactor, in which QH ≡ 0, the “slope” criterion (10.4.2-11)

If a control device acts upon the reactor temperature e.g., by modifying

4NH 3 + 6HCHO → (CH 2 ) 6 N 4 + 6H 2 O

with k = 1.42 × 103 exp(-3090/T). The reactants were fed in streams of

Other physicochemical data are

∆H = -167,480 kJ ρcp = 4,187 kJ/m3°C

At a temperature of 100°C and a desired production rate of 0.4 kg/s,

10.3 The first-order reversible reaction

is carried out in a constant-volume perfectly mixed flow reactor. The

where τ = V/F’ = mean residence time.

(c) For very rapid reactions, (k1,k2) → ∞, show that, in general,

and explain how this can be physically interpreted as the final

10.4 For a first-order reaction, the conversion to be expected in a series of n

(b) Add further lines of constant values of the dimensionless group

10.5 (a) For the reversible consecutive reactions

taking place in a steady-state, constant-volume perfectly mixed