OPERABILITY OF CHEMICAL REACTORS: MULTIPLICITY BEHAVIOR

OF A JACKETED STYRENE POLYMERIZATION REACTOR

Louis P. Russo and B. Wayne Bequette

Howard P. Isermann Department of Chemical Engineering

Rensselaer Polytechnic Institute
Troy, NY 12180-3590

bequeb@rpi.edu
Fax: (518)276-4030
Tel: (518)276-6683

Submitted to Chemical Engineering Science

July 1996

Keywords. Process Design, Operability, Steady-state Multiplicity, Polymerization, Bifurcation.

 ABSTRACT

Steady-state multiplicity analysis is used to study the operability of a jacketed exothermic styrene
polymerization CSTR. The global multiplicity behavior is characterized in terms of an initiator de-
composition Damkohler number and the dimensionless heat of reaction. Low and high temperature
infeasibility regions are shown to occur under certain design conditions. The approach developed is
based on using a combination of analytical and numerical techniques to guide the analysis, rather
than using a purely numerical approach. A reactor design used by previous researchers to show
poor closed-loop performance from a single input-single output control strategy is studied in this
paper. It is shown how this poor performance could have been predicted, and eliminated, at the
process design stage using our bifurcation-based approach.

2
1 Introduction
The integration of process design and control (or operability) has been recognized as an important
objective for many years. A number of relevant techniques have been proposed, including ex-
ibility analysis (based on nonlinear programming and steady-state models), resiliency (based on
linear, multivariable models), and steady-state and dynamic \back-o" analysis (where the actual
operating point is chosen by \backing o" from the optimum point which lies at the intersection
of constraints). In this paper we present an approach, based on bifurcation (singularity) theory,
to understand how design parameters in uence the characteristic input/output behavior of pro-
cess systems. We study the steady-state multiplicity behavior of a jacketed exothermic styrene
polymerization CSTR. Since the structure and properties of polymers are determined primarily by
the operation of the chemical reactor in which they are made, there is signicant motivation to
optimize the process design and operation to improve controllability. Previous researchers showed
poor single input-single output control performance for a given set of polymerization CSTR design
parameters. In this work we show how this poor performance could have been predicted, and
eliminated, at the process design stage using our bifurcation-based approach.

The bifurcation results presented in Russo and Bequette (1995, 1996a, 1996b) are particularly
important from a practical \controllability" point of view. This analysis demonstrates that in some
regions of the parameter space there does not exist any manipulated variable value which will allow
operation at a steady-state setpoint (using the cooling jacket owrate as the single manipulated
variable). Russo and Bequette (1995) showed that under certain conditions a two-state CSTR model
(neglecting cooling jacket temperature dynamics) could have a monotonic steady-state relationship
between the reactor temperature and cooling jacket temperature, while a three-state CSTR model
operated under the same conditions exhibited multiple steady-state behavior between the reactor
temperature and the cooling jacket owrate. Thus, we see that an analysis of the two-state CSTR
model could lead one to believe that the system is inherently \safer" and easier to operate than is the
case as predicted by a more realistic three-state CSTR model incorporating a cooling jacket energy
balance. We are motivated in our studies to consider these attributes of \process controllability"
and \process operability" in order to understand how modeling decisions (and ultimately, design
and operation decisions) eect the operating characteristics of the chemical reactor.

3
2 Industrially Relevant Application
Although a detailed analysis of the bifurcation behavior of a jacketed exothermic CSTR was pre-
sented in Russo and Bequette (1995, 1996a), the kinetic mechanism studied up to now is quite
simple in nature and hence is not generally sucient to capture the behavior of some industrially
relevant chemistries. Therefore, it is important to examine a chemical \system" in which these
bifurcation results can be of practical usage.
The production of synthetic polymers is an example of a chemical system that is important from an
industrial viewpoint. Synthetic polymer production exceeds one hundred million metric tons per
year worldwide (Ray, 1993). Hence, there is sucient incentive to obtain a deeper understanding of
the parameters which in uence the steady-state and dynamic behavior of polymerization chemical
reactors. There are many dierent types of polymers available and depending on the properties
that they exhibit, polymers range from low volume, high value added specialty materials at several
thousand dollars per kilogram to high volume material for approximately one dollar per kilogram
(Ray, 1993). The structure and properties of the polymer are determined primarily by the operation
of the reactor in which they are made. Therefore, it is important to have tight control of the
operating conditions inside the process. In order to do this in an eective manner, one should
have a good understanding of the underlying kinetics, thermodynamics, and transport properties
associated with the polymerization reactor. It is essential to have reliable and accurate sensors to
eectively monitor the conditions inside the reactor so that polymer with the desired properties is
produced.
Polymer science is a very broad eld of study, and as such there exists a wealth of literature on
the subject. The emphasis in this paper is on an understanding of the bifurcation behavior of
exothermic polymerization reactors. Ray (1993) serves as an excellent review of polymerization
reaction modeling and control, while Billmeyer (1984) presents a more general overview of polymer
science.

4
3 Review of Previous Bifurcation Results
The open-loop steady-state and dynamic behavior of polymerization reactors has been the focus
of much research during the last twenty-ve years. A primary reason behind this research is the
tremendous increase in demand for polymeric materials. The purpose of this section is to review
some of the more relevant literature on the bifurcation behavior of polymerization reactors.
Jaisinghani and Ray (1977) studied the bulk homopolymerizations of methyl methacrylate (MMA)
and polystyrene in a CSTR. They determined the in uence of reactor operating conditions on the
types of steady-state and dynamic behavior possible. Jaisinghani and Ray (1977) initially studied
a simpler model for the reaction kinetics (assuming constant initiator concentration). They found
evidence for the presence of steady-state multiplicity and periodic (Hopf bifurcation) behavior, but
were only able to nd unstable limit cycles in their analysis.
A \gel eect" which predicted that the termination rate could decrease up to ve orders of mag-
nitude under the right operating conditions was included in the models studied in Jaisinghani and
Ray (1977). The \gel eect" (also known as autoacceleration) is marked by a signicant increase
in reaction rate and molecular weight and results from a decrease in the rate at which the polymer
molecule diuses through the reaction solution (Billmeyer, 1984). The termination step is gener-
ally diusion controlled for liquid-phase polymerizations, hence a decrease in diusion (due to an
increase of viscosity with high conversion) results in a decrease in the termination rate (Billmeyer,
1984). This leads to an increase in overall polymerization rate and molecular weight.
Brooks (1981) considered the dynamic behavior of the bulk polymerization of styrene in a CSTR.
One important point of this work was that more sophisticated models which did not assume constant
heat capacity or constant density in the reactor were employed. It was shown that more realistic
models for these parameters were very important during the startup phase of the reactor; the
constant parameter assumptions were adequate only for steady-state analysis. Schmidt and Ray
(1981) analyzed the multiplicity behavior of MMA solution polymerization in an isothermal reactor
operating at the boiling point of the reactor mixture. They found that the multiplicity behavior in
this case was a result of the strong \gel eect" associated with the process. Multiple steady-state
behavior occurred as the solvent volume fraction was decreased.
Hamer et al. (1981) presented the rst account of stable limit cycles for the polymerization of
5
MMA. They studied the homopolymerizations of MMA and vinyl acetate, and their copolymer-
ization. The steady-state and dynamic behavior was classied in the parameter space by varying
system parameters and using the Routh-Hurwitz criteria to give conditions on the characteristic
equation coecients for a specied eigenvalue structure. Schmidt et al. (1984) demonstrated the
experimental existence of multiple steady-states under nonisothermal reactor conditions, and pre-
sented experimental verication of steady-state isolas for the homopolymerizations of MMA and
vinyl acetate. Previous modeling studies were used to guide experiments in nding multiplicity
behavior. Choi (1986) compared the bifurcation results for two models of the homopolymeriza-
tion of MMA. The rst model utilized the \standard" kinetic description (common to free radical
initiation), whereas the second model assumed that the initiator concentration was constant. A
slightly dierent dimensionless group parameterization was used which provided a more detailed
steady-state structure, as compared to previous work.
Teymour and Ray (1989) performed a bifurcation analysis of a model of an experimental poly-
merization reactor. The model parameters used were obtained from the literature (no adjustment
was made to these parameters for the present experimental system). They presented the rst ex-
perimental evidence of limit cycle behavior in the solution polymerization of vinyl acetate, and
classied the steady-state and dynamic behavior in the parameter space. This analysis was used to
guide experiments to nd regions of process parameters where limit cycles were predicted to occur.
Adebekun et al. (1989) analyzed the steady-state multiplicity behavior possible in the polymeriza-
tion of MMA in a CSTR. The primary focus of this work was to include polymer properties such
as the molecular weight distribution (MWD), number average chain length, and polydispersity of
the MWD in the bifurcation analysis. They rearmed work by Schmidt and Ray (1981) which
indicated that the multiplicity behavior in an isothermal polymerization reactor was the result of
the \gel eect". The presence of two steady-state isolas over a very small region of solvent volume
fractions was demonstrated.
Kim et al. (1991) studied the homopolymerization of styrene in a series of two CSTR's. One
important point made in this work was that an understanding of the reactor behavior is important
for the design of control systems for producing polymers with the desired physical properties.
The use of more than one reactor was justied by noting that often the rst reactor serves to
prepolymerize the monomer. Kim et al. (1991) found limit point bifurcations, Hopf bifurcations,
innite periodic orbits, period doubling bifurcations, isola behavior, and multiple Hopf bifurcation
6
points. Teymour and Ray (1992a) presented an extensive study of limit cycle behavior in an
experimental laboratory reactor. They found that a major problem with studying the dynamics of
small (lab-scale) reactors is the damping eect of reactor externals such as the reactor wall, impellor
blades and shaft, etc. Teymour and Ray (1992a) found that either increasing the residence time or
decreasing the coolant temperature lead to limit cycle behavior in the experimental polymerization
reactor. The model was able to predict the oscillation amplitudes and limit cycle periods well,
with only small adjustments in a heat transfer coecient. Teymour and Ray (1992b) focused their
analysis on a full-scale polymerization reactor. They modied the model used in previous studies
to more accurately describe conditions in an industrial polymerization reactor. The bifurcation
analysis package AUTO (Doedel, 1986) was used to obtain an understanding of the dierent types
of behavior possible in this reactor system. The full-scale model demonstrated even more complex
dynamics than the lab-scale model.
Pinto and Ray (1995a) constructed a mathematical model of the copolymerization of MMA and
vinyl acetate in a lab-scale reactor. The bifurcation behavior of the system was examined using
AUTO (Doedel, 1986) and the eect of perturbations in the heat transfer coecient and the
coolant temperature were studied. Experimental support for limit cycle behavior demonstrated
that decreasing the percentage of MMA monomer in the feed removed the stable limit cycle. Pinto
and Ray (1995b) studied the copolymerization of MMA and vinyl acetate in a lab-scale reactor.
They demonstrated that the system dynamics were very sensitive to small changes in the feed
conditions, particularly, the initiator feed concentration. In an extremely small area of parameter
space, two isolas were predicted. However, they determined that the appearance of the second isola
was related to the \gel eect" correlation and may not be an actual feature of the physical system.
They showed that a boiling constraint that arises due to operation at atmospheric conditions was
responsible for regions of up to ve steady-states. Multiple stable periodic orbits and isolas of
periodic solutions were also found.

7
4 Bifurcation Behavior of a Jacketed Exothermic Polymerization
Reactor
4.1 Motivation
One can surmise from the review in the previous section that there has been substantial research
activity in polymerization reactors. This relatively cursory review focused primarily on the studies
concerned with the bifurcation behavior. Overall, the general trend has been from analyzing simpler
kinetic models initially to more sophisticated chemistries such as copolymerization of two monomers.
A common theme in these studies is that a variety of industrially relevant polymerization reactions
are highly exothermic, and thus have interesting steady-state and dynamic behavior which may
make these systems dicult to operate and control. Kim et al. (1991) note that poor heat transfer
from the reactor to the cooling jacket in polymerization systems is one of the major causes for
strong process nonlinearity. A major problem is that industrial scale reactors have heat transfer
area per volume ratios which are much smaller than lab-scale units.
A fundamental question to consider is thus: How can one eectively \remove" the energy liberated
in highly exothermic reactions such as are encountered in polymerization systems? Perhaps the
easiest way to accomplish this is to add a \cold" stream directly to the reaction mixture; this
aords ecient and eective heat transfer since the entire volume is contacted with the heat transfer
medium. A major problem in doing this is that one is diluting the reactor contents, hence a larger
residence time is needed. The addition of a \foreign" chemical to the reaction mixture can change
the polymer properties. Another alternative is to operate the reactor at the boiling point of the
solvent, and to recondense and recirculate the solvent to the reaction mixture. This eectively limits
the reactor to a small range of operating temperatures (near isothermal behavior, as the boiling
point of the solvent - monomer - polymer mixture will change as more monomer is converted to
polymer). In order to achieve high conversion one may have to pressurize the reactor. However,
this may have an adverse eect on the reaction kinetics.

Perhaps the easiest and most common approach is to utilize a cooling jacket to remove the energy
liberated by the reaction mixture. A \cold" liquid (water, Dowtherm, glycol, etc.) is pumped
through the jacket to remove excess heat from the reactor. The cooling jacket owrate is the

8
primary manipulated variable used to control the reactor temperature (which in turn species the
conversion and thus the polymer properties). It is worthwhile to note that none of the studies
reviewed considered the eect of a cooling jacket on the steady-state and dynamic behavior of
polymerization CSTR's.
Congalidis et al. (1989) assumed that a \properly tuned" PI controller could be used to manipulate
the coolant ow rate in order to obtain any value of the reactor jacket temperature. However, it
was demonstrated in Russo and Bequette (1995) that for even simple 1st order kinetics (A ! B )
that including a thermal energy balance around the cooling jacket lead to interesting bifurcation
results which are not present in a lower order (two-state) model of the reactor. Perhaps the most
important result obtained was that even for the simple kinetic model used, the presence of infeasible
reactor operating regions is predicted. Therefore, it is a poor assumption to neglect the cooling
jacket energy balance in the control system design. It is well known that constraints on input
variables can result in severe diculties in obtaining robust control. However, these constraints are
not due to any process equipment limits (such as a maximum owrate for a pump) but are chosen
as physical limits on the cooling jacket owrate.

Pinto and Ray (1995b) stressed that the role of physical constraints on the model has been largely
overlooked in the past. These constraints, taken with the mathematical model, create a new model
which may or may not present completely dierent bifurcation structures that can improve the
design and operation of real processes (Pinto and Ray, 1995b). Since the cooling jacket owrate is
the primary manipulated variable for control of reactor temperature, it is crucial to use it as the
bifurcation parameter in order to understand how it in uences the behavior of the system.

4.2 Review of Hidalgo and Brosilow (1990)

One interesting study which incorporated an energy balance around the cooling jacket was per-
formed by Hidalgo and Brosilow (1990). Hidalgo and Brosilow implemented a low order nonlinear
model predictive control (NMPC) algorithm for the control of styrene polymerization in a CSTR.
A combination of NMPC and coordinated control provided safe and eective control about an
unstable operating point. Coordinated control consists of using two or more manipulated inputs
to maintain a single output at its desired setpoint (multiple input single output or MISO control).

9
In this case, the cooling jacket owrate was the primary manipulated variable while the monomer
owrate (the secondary manipulated variable) was only \changed" if the cooling jacket owrate
\hit" a constraint.
A number of dierent control case studies were conducted by Hidalgo and Brosilow (1990). The
response of a conventional SISO controller (manipulating cooling jacket owrate alone) was com-
pared to a MISO controller (coordinated control manipulating cooling jacket owrate and monomer
owrate). The performance of the MISO control strategy was substantially better than the SISO
control strategy. In fact, for a large enough setpoint change, the SISO control strategy is unstable.
However, Hidalgo and Brosilow never explain why the SISO controller performs so poorly, espe-
cially in light of the fact that a nonlinear model of the process is used which incorporates a great
deal of process information in the control strategy.
Hidalgo and Brosilow (1990) note that \safe control of an unstable process requires the availability
of a sucient control action to keep the process in a small region about the desired operating point
in spite of disturbances and control eort constraints." They claim that the styrene polymerization
CSTR \can not be safely controlled by manipulating only the cooling jacket owrate", yet no
physical explanation is presented. It has been surmised from the review section that few if any
bifurcation studies have been conducted on a jacketed polymerization CSTR. This fact coupled
with the intriguing results of Hidalgo and Brosilow (1990) make this polymerization system an
ideal choice for further study.

5 Styrene Polymerization CSTR Model

In this section the features of the styrene polymerization model of Hidalgo and Brosilow (1990) are
described. The free radical polymerization kinetic mechanism is modeled as:

10
 kd
I ?! 2R (initiator decomposition)

ki
M + R ?! P1 (chain initiation)

kp
Pn + M ?! Pn+1 (propagation)

ktd
Pn + Pm ?! T n + Tm (termination)

ktc
Pn + Pm ?! Tn+m (termination)

where I is the initiator, R is the radical produced by initiator decomposition, M is the monomer
species, P is the growing polymer chain, and T is the terminated polymer chain (cf. Billmeyer
(1984) for a discussion on free radical polymerization kinetics).
A number of assumptions were used by Hidalgo and Brosilow (1990) in obtaining the styrene
polymerization CSTR model. In particular, the quasi-steady-state approximation and the long
chain hypothesis were employed in the kinetic modeling. The quasi-steady-state approximation
can be made by realizing that the lifetimes of the radical species R, P are short compared to the
system time constants (Jaisinghani and Ray, 1977). Hence, the net reaction rate of the radicals is
near zero (rR  0, rP  0). The long chain hypothesis states that most of the monomer is added
to existing polymer chains as opposed to starting new polymer chains. In addition, the \gel eect"
(a decrease in termination rate associated with increased viscosity as the reaction proceeds) was
neglected, since the reactor was operated at a relatively high solvent volume fraction. Choi (1986)
notes that this is generally a good assumption for high solvent volume fractions. Termination for
the styrene polymerization is generally due to combination (i.e. kt = ktc ). Physical properties of
the reaction mixture such as density, heat capacity, heat transfer coecient, etc. were assumed
constant. The reader is referred to Appendix 1 and Hidalgo and Brosilow (1990) for additional
details concerning the modeling assumptions and derivation of the modeling equations.
The model for polystyrene polymerization as given by Hidalgo and Brosilow (1990) is:
dCi = (QiCif ? (Qi + Qm + Qs )Ci) ? k C (1)
dt V d i
dCm = (QmCmf ? (Qi + Qm + Qs)Cm) ? k C C (2)
dt V p m gp

11
 dT = (Qi + Qm + Qs)(Tf ? T ) + (?
Hr ) k C C ? UA (T ? T ) (3)
dt V Cp p m gp CpV c
dTc = Qc(Tcf ? Tc) + UA (T ? T ) (4)
dt Vc cCpcVc c
s 
Cgp = 2fkkdCi (5)
t
where Ci , Cm, T , Tc , Cgp , and Qc represent the concentration of initiator, concentration of monomer,
reactor temperature, cooling jacket temperature, concentration of growing polymer, and cooling
jacket owrate, respectively. The initiator is azobisisobutyronitrile (AIBN) dissolved in benzene,
while the monomer is styrene and the solvent is benzene. The process ow diagram for the styrene
polymerization CSTR with a cooling jacket is shown in Figure 1. Five dierent sets of numerical
values of the process parameters are given in Hidalgo and Brosilow (1990). The variables of the
styrene polymerization model are dened in Table 1, while a representative selection of the process
parameters is shown in Table 2. No analysis of the multiplicity or open-loop dynamic behavior of
this model has been performed.
The four-state polymerization CSTR model can be extended in order to calculate the number-
average molecular weight (NAMW) M n . Following Schmidt and Ray (1981), two polymer chain
moment equations are appended to the current model:
d0 = 1 k C 2 ? Qt  (6)
dt 2 tc gp V 0
d1 = 1 k C 2 ? Qt  (7)
dt 1 ?  tc gp V 1
where 0 is the total molar concentration of dead polymer and 1 is the total molar concentration
of monomer units present as polymer (Schmidt and Ray, 1981). It can be shown (Appendix 2) that
equation 7 becomes:
d1 = k C C ? Qt  (8)
dt p m gp V 1

The number-average molecular weight (NAMW) M n is dened as:

P1
M n = Pi=11 MNiNi (9)
i=1 i
where Mi is the molecular weight of the ith polymer and Ni is the number of molecules of type
i (Billmeyer, 1984). For most polymers the number-average molecular weight (NAMW) lies close
to the peak of the molecular weight distribution curve (Billmeyer, 1984). The number-average
12
molecular weight (NAMW) can be obtained from the moment equations by noting that M n is
simply:
Total mass of polymer = 1 MWmono V
M n = Total (10)
moles of polymer 0 V
where MWmono is the molecular weight of the repeating monomer unit, which in our case is styrene
(?CH2CH (C6H5 )?) with MWstyrene = 104:15g/mol.
Equations 1 { 5 can be written in the following dimensionless form:
dx1 = q x ? (q + q + q )x ?   (x )x (11)
d i 1f i m s 1 d d 3 1
dx2 = q x ? (q + q + q )x ?   (x )x x (12)
d m 2f i m s 2 p p 3 2 5
dx3 = (q + q + q )(x ? x ) +   (x )x x ? (x ? x ) (13)
d i m s 3f 3 p p 3 2 5 3 4
dx4 =  [q (x ? x ) +  (x ? x )] (14)
d 1 c 4f 4 s
2 3 4

x5 = 2f d d (x3 ) x
tt(x3) 1 (15)
where x1 , x2 , x3 , x4 , x5 , and qc are the dimensionless initiator concentration, monomer concentra-
tion, reactor temperature, cooling jacket temperature, growing polymer concentration, and cooling
jacket owrate, respectively. We demonstrated in Russo and Bequette (1996b) that this type of
cooling jacket energy balance holds for recirculating cooling jackets and that the use of multiple
cooling jacket compartments does not change the qualitative steady-state input-output behavior.
As noted by Aris (1993), if one is interested in examining the eect of varying reaction kinetics,
then it should not be used to scale the time variable. We are interested in varying the residence time
(by varying the reactor owrate) and the reaction kinetic parameters, hence time is scaled using a
nominal reactor residence time, QVt0 . The dimensionless variables and parameters are dened in the
Table 3, with values of the corresponding dimensionless parameters shown in Table 4 (for Table 2
conditions). The dimensionless moment equations are:
dx6 = 1   (x )x2 ? x (16)
d 2 t t 3 5 6
dx7 =   (x )x x ? x (17)
d p p 3 2 5 7
The number-average molecular weight (NAMW) M n is:
M n = MWmono xx7 (18)
6
The ratio of xx67 is the dimensionless number-average molecular weight (NAMW).

13
6 Steady-state Multiplicity Analysis
6.1 Introduction
It was demonstrated in Russo and Bequette (1995, 1996a, 1996b) that incorporating cooling jacket
dynamics in the CSTR modeling equations has an important eect on the open-loop steady-state
and dynamic behavior. An important point is that because the polymer chain moment equations
given in the previous section are decoupled from the CSTR material and energy balance equations,
they do not change the steady-state multiplicity or dynamic behavior of the underlying four-state
polymerization model. However, the polymer chain moment equations may exhibit interesting
bifurcation behavior in their own right. An analysis of the steady-state multiplicity behavior of the
four-state polymerization CSTR model is presented in the following sections. The eect of a number
of dierent parameter variations (such as the dimensionless heat of reaction, dimensionless heat
transfer coecient, dimensionless cooling jacket feed temperature, and the dimensionless cooling
jacket owrate) on the multiplicity behavior is considered. These results are similar in nature to
those obtained previously with the lower order CSTR model.
The structure of the modeling equations for the four-state polymerization CSTR model makes an
analytical treatment of the multiplicity behavior substantially harder than the corresponding three-
state A ! B CSTR model. Razon and Schmitz (1987) note the analytical diculties associated
with studying the behavior of more complicated reaction networks. The steady-state modeling
equations could be collapsed to one nonlinear algebraic equation in the three-state CSTR case
studied in Russo and Bequette (1995). This allows one to use results from elementary catastrophe
theory in order to analyze the multiplicity behavior. In general, the modeling equations can not
be \collapsed" to one single nonlinear equation, hence more sophisticated techniques are necessary.
Balakotaiah et al. (1985) use a Liapunov-Schmidt reduction procedure to characterize the behavior
of more complicated reaction networks that can not be reduced to a single nonlinear algebraic
equation.
Fortunately, the steady-state modeling equations for the four-state polymerization system can be
\collapsed" into a single nonlinear algebraic equation. In particular, note that at steady-state
equation 11 can be solved for x1 as a function of x3 . Then, one can substitute x1 into equation 15
to obtain x5 as a function of x3. Next, substitute x5 into equation 12 which gives x2 as a function

14
of x3 . Finally, equation 14 can be solved for x4 as a function of x3. Now, substituting this into
equation 13 (at steady-state) gives:
h(x3; qc; p) = qm x2f q + q +pqp(+x3)( x(3x) )(x ) + (x4f ? x3)  q+c qc +
i m s p p 3 3 2
(qi + qm + qs )(x3f ? x3 ) = 0 (19)
where (x3 ) is s
(x3) =   (x )(2qf+d q d (x+3)qqi +
x1f = x5 (20)
t t 3 i m s d d (x3))
where x3 (dimensionless reactor temperature) is the controlled output, qc (dimensionless cooling
jacket owrate) is the manipulated input, and p is a vector of parameters.
It is interesting to note that this equation is very similar in nature to the equivalent equation for
the three-state CSTR model.
h(x2; qc; p) = qx1f q +
(x2 ) + q (x ? x ) + (x ? x ) qc = 0
(x2) 2f 2 3f 2  + q (21)
2 c
The essential dierences in these two equations are in the numerator and denominator of the
 term. In the three-state CSTR case there is a single nonlinearity ((x2)) while in the four-
state polymerization CSTR case the nonlinearities (p (x3)(x3)) multiply each other. This makes
a complete analytical treatment for the bifurcation analysis much more dicult. Therefore, a
combination analytical/numerical bifurcation analysis is performed.

6.2 Determination of Global Multiplicity Diagrams

The necessary conditions for output multiplicity, input multiplicity, and the formation of isolas,
respectively, are obtained from the implicit function theorem.
@h = 0
h = @x (22)
3
@h = 0
h = @q (23)
c
@h = @h = 0
h = @x (24)
3 @qc
Now, we want to determine if it is possible for the polymerization CSTR model to have input
multiplicity or isolas. Consider the value of @q@hc . The result is:
@h 2 (x4f ? x3)
@qc =  2 (2 + qc)2 6= 0 (25)

15
Therefore, when qc is the manipulated variable then input multiplicities, isolas, transcritical bi-
furcations, and pitchfork bifurcations cannot occur between x3 and qc . Upon examination of the
derivatives of h(x3; qc ; p) with respect to the parameters, it can be determined that qi , qm , and qs
are the only parameters that when varied can lead to input multiplicities or isola behavior; these
are therefore important disturbance variables. The derivatives of h(x3; qc ; p) with respect to the
other parameters remain the same sign.
Elementary catastrophe theory allows one to characterize the number of multiple steady-state
solutions to equations 11 { 15. The appearance or disappearance of output multiplicities occurs
when higher order derivatives of h with respect to x3 are zero.
@h = @ 2h = : : : = @ k h = 0
h = @x
3 @x23 @xk3
@ k+1h 6= 0 (26)
@xk3+1
The highest order singularity (value of k) satisfying equation 26 determines the number of steady-
state solutions. A multiplicity of k + 1 solutions exists around the codimension k singular point
satisfying equation 26 (Stewart, 1981). As noted previously, the more complicated structure of
the polymerization CSTR modeling equations make an analytical treatment dicult. The highest
order singularity found numerically corresponds to k = 2, hence up to three dierent steady-state
dimensionless reactor temperatures may exist for a given dimensionless coolant owrate.

The determination of regions of feasible and infeasible reactor operation are important for feedback
control purposes, since one can see directly if the current operating conditions are \feasible" in
a steady-state sense. Therefore, the global parameter space is divided into regions with dierent
types of multiplicity behavior. However, there are a large number of parameters associated with
the polymerization system so it is not clear how to best present the bifurcation results.
This current study portrays the singularity loci on the d -  2-D cross section of the parameter
space. This follows the development in Russo and Bequette (1995, 1996a, 1996b) in that kinetic
and thermodynamic properties of the system are used to classify the behavior. d is the Damkohler
number associated with the dissociation of the initiator into the radical species. If one examines
equation 19 we see that as d ! 0 no reaction occurs, since there are no radicals present to initiate
the the reaction.  (dimensionless heat of reaction) is a direct measure of the exothermicity of the
reaction.
16
The singularity described by equation 26 is strictly not a \point" but a locus of points in the
global parameter space. It is possible to construct singularity loci for a number of low dimensional
cross sections of the parameter space. However, since we are interested in how changes in process
parameters in uence the location and existence of these singularities on the steady-state input-
output (x3 - qc ) curves, the singularity locus is constructed over the bounds on the dimensionless
coolant owrate (qc ).
@h = @ 2h = 0
h = @x (27)
3 @x23
qc 2 [0; 1)
We denote d ,  , and x3 that satisfy the hysteresis condition (equation 27) as d?hyst , hyst , and
x3?hyst . The singularity locus described by equation 27 bounds the region of output multiplicity
behavior in the parameter space. A codimension 1 fold bifurcates from the bounds on the cooling
jacket owrate. This lower order singularity separates the global multiplicity behavior in the d -
 parameter space.
@h = 0
h = @x
3
qc = 0 (28)

@h = 0
h = @x
3
qc ! 1 (29)

Equations 28 and 29 satisfy the \0-disjoint" and \1-disjoint" loci, respectively. In general, equa-
tions 28 and 29 can be satised for \low" and \high" temperature limit points, as qc approaches
zero or innity, respectively. Hence, there are a total of four curves in the d -  space that bifurcate
from the singularity locus given in equation 27.

6.3 Global Multiplicity Behavior

Let us consider a simple parametric study in order to understand how changes in d and  in uence
the steady-state input-output curves. Figure 2 shows the eect of varying d for a \smaller" value of
; as d is decreased the characteristics of the steady-state input-output (x3 - qc ) curve changes from
monotonic to multiple steady-states to a region of low temperature infeasibility. This infeasibility is

17
also seen if one neglects the cooling jacket energy balance in the modeling equations, which results
in a three-state model. Figure 3 corresponds to the same conditions as the d = 0:006 line on Figure
2. Notice that over a range of dimensionless cooling jacket temperatures the reactor temperature
is predicted to be less than the cooling jacket temperature, which results in the cooling jacket
owrate being negative (cf. Figure 2). A negative cooling jacket owrate is physically impossible.
The reactor temperature can not be less than the cooling jacket temperature, since the reactor and
cooling jacket have equal feed temperatures and the reaction is exothermic.

Figure 4 shows the eect of increasing d for a \larger" value of  ; as d is increased the steady-state
input-output curve behavior changes from multiple steady-states to a region of high temperature
infeasibility. The high temperature limit point (LP) moves toward innite cooling jacket owrate.
Once again, this infeasibility can be seen in a lower dimensional model that neglects the cooling
jacket energy balance. Figure 5 corresponds to the same conditions as the d = 0:008 line on
Figure 4. Notice that over a range of dimensionless cooling jacket temperatures the cooling jacket
temperature is predicted to be less than the cooling jacket feed temperature. This is impossible,
since the reaction is exothermic and the feed temperatures of the reactor and cooling jacket are
equal.
The codimension 2 (cusp) singularity locus (which species the set of hysteresis points) and codi-
mension 1 (fold) \0-disjoint" and \1-disjoint" loci (which specify the set of limit points) divide the
d -  parameter space into ve dierent regions as shown in Figure 6. These regions correspond to
ve dierent steady-state input-output curves, shown in Figure 7. The d and  values in regions
I - V of Figure 7 are given in Table 5. Region I in the d -  parameter space corresponds to a

monotonic relationship between x3 and qc , while in region II output multiplicity exists between
x3 and qc (inverse S shaped input-output curve). Regions III and IV exhibit low temperature
and high temperature infeasibilities, respectively, corresponding to \0-disjoint" and \1-disjoint"
bifurcations. The presence of \0-disjoint" behavior is associated with overcooling of the reactor
by the cooling jacket, whereas \1-disjoint behavior occurs when there is not sucient cooling by
the cooling jacket (the heat transfer characteristics of the reactor are poor, as seen in large scale
industrial reactors). Region V is an overlap of regions III and IV, where low and high tempera-
ture infeasibilities exist when the \0-disjoint" and \1-disjoint" loci intersect. The \dimensional"
steady-state input-output curve indicated by the + mark in Figure 6 is shown in Figure 8; notice
the reactor operation falls in a \high" temperature operating region of region I. Figure 9 is a plot
18
of the steady-state number-average molecular weight (NAMW) M n as a function of the coolant
owrate. Notice that the \high" temperature operating region has resulted in the production of
polymer with \low" number-average molecular weight (NAMW).
The d -  diagram for the nominal dimensionless operating parameters (given in Table 4) is shown
in Figure 10; notice the reactor operation falls in region IV. The steady-state input-output (x3 - qc )
curve is shown in Figure 11; this reactor design exhibits a \high" temperature infeasibility region.
This input-output curve is shown in \dimensional" form in Figure 12, where the reactor temperature
is shown as a function of the cooling jacket owrate. Figure 13 is a plot of the steady-state number-
average molecular weight (NAMW) M n as a function of the coolant owrate for the low and high
temperature branches. Notice that the \high" temperature infeasibility region shown in Figure 12
has resulted in a corresponding infeasibility region of number-average molecular weights. Values
of the NAMW from 8400 to 12000 do not exist under these operating conditions. The number-
average molecular weight for the upper branch of Figure 13 is shown as a function of the steady-state
temperature in Figure 14. The NAMW changes by almost an order of magnitude over a 40 degree
Celsius range. The number-average molecular weight for the lower branch of Figure 13 is shown as a
function of the steady-state temperature in Figure 15. The NAMW changes by approximately 15%
over a 100 degree Celsius range, with a minimum around 115 oC . The number-average molecular
weight is plotted versus the corresponding steady-state coolant owrate in Figure 16. Figure 16
shows that there could be potential problems controlling the number-average molecular weight by
manipulating coolant owrate solely, due to the input multiplicity behavior in the \low" molecular
weight region.

Hidalgo and Brosilow (1990) claimed that this reactor could not be operated safely using only
the coolant owrate as the manipulated variable for feedback control, but did not present an
explanation. It is clear that the problem is that near the operating range of interest (corresponding
to x3  0:75 or T  80 oC ) the gain between the dimensionless reactor temperature and the cooling
jacket owrate is approaching zero as one moves further into the infeasibility region (cf. Figure 12.
Hidalgo and Brosilow (1990) also placed a maximum constraint on the cooling jacket owrate of
Qc = 60 liters
min ; this corresponds to a maximum dimensionless cooling jacket owrate of qc = 3:8095.
Notice from Figures 11 and 12 that this constraint virtually eliminates any ability to operate in
the reactor range of interest with only the cooling jacket owrate.

19
7 In uence of Polymerization CSTR Parameters on the Multi-
plicity Behavior
7.1 Introduction
It is clear from the results presented in the previous section that the physical constraints imposed
on the cooling jacket owrate lead to interesting multiplicity behavior. We saw that incorporating
more complicated kinetics did not change the nature and types of multiplicity diagrams that occur.
The multiplicity behavior shown in Figures 2 and 3 is now easily explained. As d is decreased in
Figure 2, we move from region I through region II into region III. As d is increased in Figure 3,
we move from region II into region IV.
The focus of this section is to explore the in uence of process design or operation changes on
the bifurcation behavior of the four-state polymerization CSTR model. The number of process
parameters used to describe the dimensionless polymerization model makes a complete parametric
study impractical; however, by using the multiplicity results of the previous section we are able to
demonstrate the more relevant parametric eects.

7.2 Eect of Reactor Scaleup

Let us consider the eect of reactor sizing on the hysteresis locus behavior. In Russo and Bequette
(1995) we showed that when the cooling jacket feed temperature was equal to the reactor feed tem-
perature, the Damkohler number along the hysteresis locus (hyst ) is a constant. The dimensionless
heat of reaction along the hysteresis locus (hyst ) changes by a factor of q+q  (recall that  is the
dimensionless heat transfer coecient and q is the dimensionless owrate).

hyst (qc ! 1) = q +q  hyst (qc = 0) (30)

Hence, in this case we can clearly see how the multiplicity behavior changes as a function of the
dimensionless heat transfer coecient ( ). If the residence time is held constant upon reactor
scaleup, then   D1r , where Dr is the diameter of the reactor. Therefore, a \larger" reactor will
have a lower value of  , resulting in a shorter hysteresis locus. This larger reactor has less ecient
cooling characteristics, which can shift the reactor operation into an undesirable region.

20
We compare the d -  diagrams for two dierent reactor systems in order to demonstrate that the
polymerization CSTR system exhibits the same type of dependence on dimensionless heat transfer
coecient (when the cooling jacket feed temperature is equal to the reactor feed temperature).
Figure 6 corresponds to a 3000 liter reactor volume ( = 0:74074) whereas Figure 17 has a reactor
volume of 1500 liters ( = 0:93328). As one can see, the larger reactor has a shorter hysteresis
locus. It is clear that if we scale down the reactor size \enough" the reactor operation will move
from region I through region IV into region II, resulting in multiple steady-state behavior. The
multiplicity behavior in this case is a result of the \low" temperature operating region becoming
feasible as the heat transfer characteristics improve when we \scaledown" the reactor size.
An important point is that the hysteresis locus length is once again related to the value of the
dimensionless heat transfer coecient ( ) and the process owrates. Table 6 shows the values of
hyst (qc = 0) and hyst(qc ! 1) for a number of process owrates and dimensionless heat transfer
coecients (the unspecied parameters are the default values given in Table 4). If we examine
hyst(qc !1) we see that
hyst(qc=0)
hyst(qc ! 1) = qi + qm + qs +  (31)
hyst (qc = 0) qi + qm + qs
which is the same relationship that was seen in the simpler three-state CSTR model presented in
Russo and Bequette (1995).

7.3 Positive Exponential Approximation

A common assumption in steady-state multiplicity studies is the \so-called" positive exponential
approximation. This approximation has been used by a number of researchers (Farr and Aris,
1986). The beauty in using the positive exponential approximation is that it often enables one to
obtain an analytical expression for characterizing the multiplicity behavior. However, it was shown
in Russo and Bequette (1995) that this approximation tends to overestimate the multiplicity area
in the global parameter space.
Generally, the positive exponential approximation consists of allowing the dimensionless activation
energy terms to become \large" (in the limit sense) with respect to the reactor temperature. This
simplies the dimensionless Arrhenius temperature dependence of the reaction rates, given by
p(x3), t(x3), and d (x3) (shown in Table 3). However, recall that d = EEdp , t = EEpt , and

21
 p = RTEpf 0 , hence it does not make physical sense to allow these dimensionless activation terms to
become large. Consider instead a situation where the individual activation energies become large
with respect to the reactor temperature. In this case, we see that d ! 1, t ! 1, and p ! 1. The
resulting d -  diagram is shown in Figure 18. The multiplicity behavior is grossly overestimated
and shifted in the parameter space, as compared to Figure 6. The reactor operation is predicted
to lie in region III whereas the operation exists in region I. We see that this form of the positive
exponential approximation obscures the true nature of the multiplicity behavior.

7.4 Eect of Process Flowrates on the Multiplicity Behavior

In addition to studying the eect of reactor size it is also important to consider how process
operation aects the multiplicity behavior. In particular, it is interesting to understand how the
process owrate in uences the bifurcation behavior. In Russo and Bequette (1995) we saw that
when the cooling jacket feed temperature is equal to the reactor feed temperature, then the value
of the Damkohler number along the hysteresis locus (hyst ) was linearly proportional to the process
owrate (q ). Therefore, if the reactor operation is in a region of multiple steady-states, one could
simply decrease the process owrate such that hyst < , which will move the reactor operation
region into region I, where the steady-state input/output curve is monotonic.
In the case when the cooling jacket and reactor feed temperatures are not equal, then one has to
decrease the process owrate such that max
qc (hyst) <  in order to assure a monotonic steady-state
input-output curve. However, for the three-state CSTR it is easy to show @@hyst > 0, as long as the
hyst

reactor feed temperature was greater than the cooling jacket feed temperature, hence the maximum
hyst occurs as qc ! 1. When the reactor feed temperature is less than the cooling jacket feed
temperature, @@hyst < 0, so the maximum hyst occurs as qc ! 0. We are interested in seeing if
hyst

these same relationships hold for the four-state polymerization CSTR model.
Notice that these conditions on the Damkohler number are sucient conditions; there exists region
I behavior (monotonic steady-state input-output curves) in the parameter space when d?hyst > d

(cf. Figures 6, 10, 17, etc.). However, if d?hyst < d then we are guaranteed monotonic steady-
state input-output curve behavior (no output multiplicities).

For the purposes of this case study, we choose the cooling jacket feed temperature equal to the

22
reactor feed temperature. We want to understand how the various process owrates (initiator,
monomer, and solvent) in uence the multiplicity behavior. The Damkohler number along the
hysteresis locus (d?hyst ) is not simply a linear function of the owrate as it was in the three-
state CSTR model. For example, notice the behavior of d?hyst in Figure 19. We see that as one
varies the initiator owrate (qi ) that d?hyst initially decreases and then it levels out and starts
increasing (for a xed value of the solvent owrate qs ). This behavior is unique to the four-state
polymerization CSTR model, in that there are multiple values of the initiator owrate for the same
hysteresis Damkohler number. There exist certain operating regimes in which multiple steady-states
can be avoided by either increasing the initiator owrate \enough" (thus decreasing the residence
time of the reactor for a lower conversion), or by decreasing the initiator owrate \enough" (thus
eectively \quenching" the reaction due to an absence of radicals).
In addition, notice on Figure 19 that decreasing the monomer owrate (qm ) tends to decrease
d?hyst . Therefore, one can remove multiple steady-state behavior by decreasing the monomer
owrate. This gure allows one to nd process operating conditions to guarantee a monotonic
steady-state input-output curve over a range of operating conditions. For example, consider a
Damkohler number of d = 0:015. For monomer owrates of qm = 0:3 and below (with a xed
solvent owrate of qs = 0:48571) we see that there exists a wide range of initiator owrates which
guarantee operation with a monotonic steady-state input-output curve.

It is well-known that the amount of initiator present in the system generally controls the polymer
properties (Hidalgo and Brosilow, 1990), hence the initiator owrate may only be varied over a
narrow range to obtain the desired polymer properties. We see in Figure 20 that d?hyst initially
decreases then starts increasing as one increases the initiator owrate (qi ) for a xed value of
qm . We can set the desired initiator owrate and nd from Figure 20 the solvent owrate which
guarantees monotonic steady-state input-output behavior. For example, for a value of d = 0:0175
and qi = 0:1, values of the solvent owrate qs = 0:4 and lower satisfy the monotonicity conditions.
Figures 21 and 22 represent cases where the initiator owrate is xed and the monomer (qm ) and
solvent (qs ) owrates were varied. We see in these cases that the hysteresis Damkohler number
is a monotonic increasing function of both the solvent and the monomer owrates. Consider a
polymerization CSTR with d = 0:0175 and a monomer owrate of qm = 0:4. We see in Figure 21
that we are guaranteed monotonic steady-state input-output behavior only if the solvent owrate is

23
lower than qs  0:5. However, if the monomer owrate is decreased from qm = 0:4 to qm = 0:2 then
monotonic steady-state input-output behavior is possible with larger values of the solvent owrate
(qs  0:7 and lower).

7.5 Eect of Process Design and Operation Changes

We want to explore the eect of process design or operation changes on the bifurcation behavior
of the polymerization CSTR model. The system parameters given in Hidalgo and Brosilow (1990)
result in the dimensionless parameters shown in Table 4. The d -  diagram for this parameter set
was shown in Figure 10. The reactor operation fell in region IV (\high" temperature infeasibility
region); the corresponding input-output (x3 - qc ) curve was shown in Figure 11.
Let us rst consider a change in the reactor size. If we decrease the reactor volume from 3000 liters
( = 0:74074) to 1500 liters ( = 0:93328), the reactor operation shifts from region IV (Figure 10)
into region II (associated with steady-state multiplicity), as shown in Figure 23. Although this
design obviously suers from multiple steady-state behavior (shown in Figure 24), we now are able
to operate over the entire range of desired reactor temperatures. However, the presence of output
multiplicities in the open-loop steady-state output curve means that we will need to use feedback
control to guarantee stable operation.

Now, consider a change in the cooling jacket feed temperature for a 3000 liter reactor. If we decrease
the cooling jacket feed temperature from x4f = ?1:14320 to x4f = ?1:5, the reactor operation shifts
from region IV to region II, as shown in Figure 25. Once again, we have multiple steady-states,
shown in Figure 26, which necessitates the use of feedback control to stabilize the system. However,
we have removed the \high" temperature infeasibility region.

Finally, we re-examine Figure 6. We see that by increasing the cooling jacket feed temperature
(from x4f = ?1:14320 to x4f = 0:0) that the reactor operation has shifted from region IV to region
I (monotonic steady-state input-output curve). However, we lose the ability to operate the reactor

in a \low" temperature operating region (cf. Figure 8).

24
8 Conclusions
We have shown in this work that the bifurcation analysis shown in Russo and Bequette (1995, 1996a,
1996b) could be applied to a jacketed styrene polymerization CSTR. The role of physical constraints
on the steady-state input-output behavior of a styrene polymerization model was studied. In
particular, an analysis of the steady-state multiplicity behavior was conducted, and the eect of
dimensionless values of the heat of reaction, overall heat transfer coecient, cooling jacket feed
temperature, and physical limits on the cooling jacket owrate were considered. It was shown
in Russo and Bequette (1996b) that this type of cooling jacket energy balance holds true for
recirculating cooling jackets and that the use of multiple cooling jacket compartments does not
change the qualitative steady-state input-output behavior.
The global multiplicity behavior was characterized in terms of a Damkohler number for initiator
decomposition and the dimensionless heat of reaction. The presence of low and high temperature
infeasibility regions associated with disjoint bifurcation behavior was demonstrated. Polymer chain
moment equations were appended to the four-state polymerization model. These equations were
used to calculate the number-average molecular weight (NAMW). The addition of these equations
does not change the underlying steady-state multiplicity or dynamic behavior of the polymerization
CSTR. However, these polymer chain moment equations may exhibit interesting behavior of their
own. For example, when the polymerization CSTR has a high temperature infeasibility region,
there exists a range of infeasible number-average molecular weights. A polymerization CSTR with
solely a high temperature operating region (e.g. the cooling jacket feed temperature may be too
high) results in the production of polymer with a low number-average molecular weight (NAMW).
Polymers with a low NAMW may exhibit input multiplicity with respect to cooling jacket owrate
and thus may be dicult to control.
The eect of process design and operation parameters on the bifurcation behavior was considered.
In particular, when the cooling jacket feed temperature is equal to the reactor feed temperature,
the hysteresis locus length (which species the dierent types of input-output behavior) was a
function of the process owrates and the dimensionless heat transfer coecient. The positive
exponential approximation was shown to obscure the true nature of the multiplicity behavior. The
hysteresis Damkohler number (d?hyst ) was not a linear function of the process owrates, unlike

25
the A ! B reaction network case. However, the in uence of the various process owrates on the
Damkohler number hysteresis locus was determined in order to guarantee monotonic steady-state
input-output behavior. We saw that under certain conditions a 3000 liter CSTR exhibited a region
of high temperature infeasibility which was not present when the reactor was scaled down to 1500
liters. Decreasing the cooling jacket feed temperature was also found to move the steady-state
input-output behavior into a globally feasible operating region.

Acknowledgment
This work was partially supported by a grant from the Petroleum Research Foundation, admin-
istered by the American Chemical Society. A portion of this work was performed while Wayne
Bequette was on sabbatical at Northwestern University.

26
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29
 Table 1: Variables in the styrene polymerization model.
f - Initiator eciency
Ci - Initiator concentration
Cm - Monomer concentration
Cgp - Growing polymer concentration
T - Reactor temperature
Tc - Cooling jacket temperature
0 - Concentration of dead polymer
1 - Concentration of monomer units present as polymer

Hr - Heat of reaction
 - Density of the reaction mixture
c - Density of the cooling jacket mixture
Cp - Heat capacity of the reaction mixture
Cpc - Heat capacity of the cooling jacket mixture
U - Overall heat transfer coecient
A - Heat transfer area
kd - Rate constant for initiator decomposition
kp - Rate constant for propagation
kt - Rate constant for termination
t - time
Qi - Initiator owrate
Qm - Monomer owrate
Qs - Solvent owrate
Qt - Total owrate through reactor
Qc - Cooling jacket owrate
V - Reactor volume
Vc - Cooling jacket volume
Cif - Initiator feed concentration
Cmf - Monomer feed concentration
Tf - Reactor feed temperature
Tcf - Cooling jacket feed temperature

30
Table 2: Representative values of the styrene polymerization parameters (taken from Hidalgo and
Brosilow, 1990).

f = 0.6 Qi = 0.03 l s?1

kd0 = 5.95 * 1013 s?1 Qs = 0.1275 l s?1

Ed = 123,855.658 J mol?1 Qm = 0.105 l s?1

kt0 = 1.25 * 109 s?1 Qc = 0.131 l s?1

Et = 7008.702 J mol?1 V = 3000 l

kp0 = 1.06 * 107 l mol?1 s?1 Vc = 3312.4 l

Ep = 29572.898 J mol?1 Cif = 0.5888 mol l?1

?
Hr = 69,919.56 J mol?1 Cmf = 8.6981 mol l?1

UA = 293.076 J s?1 K?1 Tf = 330 K

Cp = 1507.248 J l?1 K?1 Tcf = 295 K

cCpc = 4045.7048 J l?1 K?1

31
Table 3: Dimensionless variables and parameters for the four-state polymerization CSTR model
(Qt0 = Qio + Qm0 + Qs0 ).

x1 = CCmfi 0 x2 = CCmfm0

x3 = T ?TfT0f 0 p x4 = TcT?fT0f 0 p

x6 = Cmf0 0 x7 = Cmf1 0

qi = QQti0 qm = QQtm0

qs = QQts0 qc = QQtc0

x1f = CCmfif 0 x2f = CCmf

mf
0

x3f = TfT?fT0f 0 p x4f = TcfT?f 0Tf 0 p

d = EEdp t = EEpt

p = RTEpf 0  = (?
Hr )Cmf 0

Cp Tf 0 p

1 = VVc 2 = C p
c Cpc

 = CUA
p Qt0 d = QVt0 kd0 exp(? d p )

t = V CQmf
t0 kt0exp(? t p)
0
p = V CQmf
t0 kp0exp(? p )
0

 = QVt0 t d xx3 )
d(x3) = exp( 1+ 3
p

t xx3 )
t(x3) = exp( 1+ p(x3) = exp( 1+x3x 3 )
3
p p

x5 = CCmfgp0 32
Table 4: Dimensionless four-state polymerization model parameters values.

qi = 0.11429 qm = 0.4

qs = 0.48571 x1f = 0.06769

x2f = 1.0 x3f = 0.0

x4f = -1.14320 d = 4.18808

t = 0.23699 p = 10.77879

 = 13.17936 1 = 0.90569

2 = 0.37256  = 0.74074

d = 0.01688 t = 9.6583e12

p = 2.19560e7

Table 5: d and  values used in Figure 7 (x4f = 0:0).

region d 
I 0.018 8
II 0.01 8
III 0.003 8
IV 0.004 14
V 0.001 14

33
Table 6: Representative values of hyst (qc = 0) and hyst (qc ! 1) for a number of dierent process
parameters.
Parameter hyst (qc = 0) hyst (qc ! 1) hyst (qc!1)
hyst(qc =0)
 = 0.74074 4.86712 8.47244 1.74074
 = 0.93328 4.86712 9.40955 1.93328
qi = 0.15 4.88992 8.38717 1.71520
qm = 0.3 5.65829 10.31529 1.82304
qs = 0.4 4.33069 7.83932 1.81018

34
Appendix 1
Derivation of the Polymerization Kinetic Expressions
Reaction rates of the free-radical polymerization kinetics (Hidalgo and Brosilow, 1990):

rI = ?kd Ci (32)
rR = 2fkd Ci ? ki Cm Cr (33)
rP 2
= ki Cm Cr ? ktCgp (34)
rM = ?ki CmCr ? kp Cm Cgp (35)

The long chain hypothesis is made to the monomer reaction rate, i.e. ki Cm Cr  kpCm Cgp, because
most of the polymer consumed is added to existing polymer chains and not in forming new polymer
chains. In this case, rM becomes:
rM = ?kpCmCgp (36)
The quasi-steady-state approximation is made to the radical species R, P , since the radical species
lifetimes are short compared to the system time constants (Jaisinghani and Ray, 1977). It is also
assumed that no radicals exit the reactor.
In this case, the radical reaction rates are set to zero (quasi-steady-state approximation), i.e. rR  0,
rP  0. Solving these equations allows us to obtain the expression for the growing polymer chain
concentration Cgp .

2fkd Ci = ki Cm Cr (37)
kiCmCr = ktCgp2 (38)

By equating these two equations we obtain:

ktCgp2 = 2fkdCi (39)

Solving for the growing polymer concentration, Cgp:

s
Cgp = 2fkd Ci  (40)
kt

35
Appendix 2
Derivation of the Polymer Chain Moment Equations
From Schmidt and Ray (1981), the two polymer moment equations are written as:
d0 = 1 k C 2 ? Qt  (41)
dt 2 tc gp V 0
d1 = 1 k C 2 ? Qt  (42)
dt 1 ?  tc gp V 1
Here, 0 is the total molar concentration of dead polymer and 1 is the total molar concentration
of monomer units present as polymer (Schmidt and Ray, 1981) and  is:

 = k C kp+Ckm C (43)
p m tc gp
Substituting  into the equation for ddt1 we obtain:
d1 = k C 2 + k C C ? Qt  (44)
dt tc gp p m gp V 1

However, from the quasi-steady-state approximation: ki Cm Cr = ktc Cgp 2 . From the long chain

hypothesis we note that: ki Cm Cr  kpCm Cgp. Therefore, under these assumptions

ktcCgp2  kpCmCgp (45)

So, the second polymer moment equation becomes:

d1 = k C C ? Qt  (46)
dt p m gp V 1

36
 feed solvent
monomer Tf Q s flowrate
flowrate Qm temp
Q i initiator
flowrate
monomer
feed conc
Cmf initiator
C if feed conc
feed temp Tf Tf feed temp
coolant
Tcf feed temp
Qc coolant
flowrate
C i (initiator conc)
C m (monomer conc) Qt total flowrate
T (reactor temp) C i initiator conc
coolant C m monomer conc
temp Tc Tc (coolant temp)
T reactor temp
Figure 1: Process ow diagram for the jacketed styrene polymerization CSTR.

1.7

1.5
φd = 0.018
1.3 φd = 0.015
1.1 φd = 0.012
φd = 0.009
φd = 0.006
x3

0.9

0.7
0.5

0.3

0.1
0.0 0.1 0.2 0.3
qc

Figure 2: Steady-state dimensionless reactor temperature versus cooling jacket owrate,  = 6,

x4f = 0:0.

37
 1.6
1.4

1.2

1.0
x3

0.8
0.6
0.4 x3 > x4
x3 < x4
0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
x4

Figure 3: Steady-state dimensionless reactor temperature versus cooling jacket temperature, d =

0:006,  = 6, x4f = 0:0.

3.5

3.0 φd = 0.008
φd = 0.0065
2.5 φd = 0.00625
2.0 φd = 0.006
x3

1.5

1.0

0.5

0.0
0 5 10 15 20
qc

Figure 4: Steady-state dimensionless reactor temperature versus cooling jacket owrate,  = 10,
x4f = 0:0.

38
 2.0

1.5
x3

1.0

x4 > x4f
0.5 x4 < x4f

0.0
0.0 0.2 0.4 0.6 0.8
x4

Figure 5: Steady-state dimensionless reactor temperature versus cooling jacket temperature, d =

0:008,  = 10, x4f = 0:0.

20.0x10-3
I
16.0

Hysteresis locus
12.0 "0-disjoint" loci
II "∞-disjoint" loci
φd

8.0

4.0 IV
III
0.0
4 6 8 10 12 14 16 18 20
β

Figure 6: Global multiplicity behavior for the styrene polymerization CSTR model, x4f = 0:0,
 = 0:74074.

39
 2.6 2.6

2.2 I 2.2 II
1.8 1.8
x3

x3
1.4 1.4

1.0 1.0

0.6 0.6

0.2 0.2
0 1 2 3 4 5 6 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
qc qc
2.8

2.4 III
2.0

1.6
x3

1.2

0.8

0.4

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
qc
5
4 IV
4
V
3
3
x3

x3

2
2

1
1

0 0
0 5 10 15 20 25 30 0 5 10 15 20 25
qc qc

Figure 7: Bifurcation diagrams for the styrene polymerization CSTR.

40
 210

190
T (oC)

170

150

130
0 20 40 60 80
Qc (liters/min)

Figure 8: Steady-state reactor temperature versus cooling jacket owrate, d = 0:01688,  =

13:17936, x4f = 0:0.

8400

8200
NAMW (g/mol)

8000

7800

7600

7400

7200
0 20 40 60 80
Qc (liters/min)

Figure 9: Number-average molecular weight (NAMW) versus cooling jacket owrate, d = 0:01688,
 = 13:17936, x4f = 0:0.

41
 0.25

Hysteresis locus
0.20 "0-disjoint" loci
I "∞-disjoint" loci
0.15
φd

0.10
II
0.05 IV
0.00
4 6 8 10 12 14 16 18 20
β

Figure 10: Global multiplicity behavior for the styrene polymerization CSTR model, x4f =
?1:14320.

3.0

2.5

2.0

1.5
x3

1.0

0.5

0.0

-0.5
0 2 4 6 8 10 12 14
qc

Figure 11: Steady-state dimensionless reactor temperature versus cooling jacket owrate, d =
0:01688,  = 13:17936, x4f = ?1:14320.

42
 160

140

120
T (oC)

100

80

60

40
0 50 100 150 200
Qc (liters/min)

Figure 12: Steady-state reactor temperature versus cooling jacket owrate, d = 0:01688,  =
13:17936, x4f = ?1:14320.

3
80x10
70
NAMW (g/mol)

60
50
40
30
20
10
0
0 50 100 150 200
Qc (liters/min)

Figure 13: Number-average molecular weight (NAMW) versus cooling jacket owrate, d =
0:01688,  = 13:17936, x4f = ?1:14320.

43
 3
80x10

70
NAMW (g/mol)
60

50

40

30

20

10
40 50 60 o 70 80
T ( C)

Figure 14: Number-average molecular weight (NAMW) versus steady-state reactor temperature:
low temperature operating region, d = 0:01688,  = 13:17936, x4f = ?1:14320.

8400

8200
NAMW (g/mol)

8000

7800

7600

7400

7200

7000
100 120 140 160 180 200
o
T ( C)

Figure 15: Number-average molecular weight (NAMW) versus steady-state reactor temperature:
high temperature operating region, d = 0:01688,  = 13:17936, x4f = ?1:14320.

44
 8400

NAMW (g/mol) 8200

8000

7800

7600

7400

7200

7000
0 50 100 150 200
Qc (liters/min)

Figure 16: Number-average molecular weight (NAMW) versus cooling jacket owrate: high tem-
perature operating region, d = 0:01688,  = 13:17936, x4f = ?1:14320.

-3
20.0x10
I Hysteresis locus
"0-disjoint" loci
16.0 "∞-disjoint" loci

12.0
II
φd

8.0

4.0 IV
III
0.0
4 6 8 10 12 14 16 18 20
β

Figure 17: Global multiplicity behavior for the styrene polymerization CSTR model, x4f = 0:0,
 = 0:93328.

45
 40.0x10-3
35.0 I Hysteresis locus
"0-disjoint" loci
30.0 "∞-disjoint" loci

25.0
II
φd

20.0
15.0
10.0
IV
5.0 III
0.0
10 15 20 25 30
β

Figure 18: Global multiplicity behavior for the styrene polymerization CSTR model using the
positive exponential approximation, t ! 1, d ! 1, p ! 1, x4f = 0:0.

50x10-3
qm = 0.2
qm = 0.3
40 qm = 0.4
qm = 0.5
qm = 0.6
φd-hyst

30

20

10

0.2 0.4 0.6 0.8 1.0

qi

Figure 19: Damkohler number hysteresis locus as a function of the initiator owrate for various
values of the monomer owrate, x4f = 0:0, qs = 0:48571.

46
 70x10-3
qs = 0.2
60 qs = 0.4
qs = 0.6
50 qs = 0.8
qs = 1.0
φd-hyst

40

30

20

10

0.2 0.4 0.6 0.8 1.0

qi

Figure 20: Damkohler number hysteresis locus as a function of the initiator owrate for various
values of the solvent owrate, x4f = 0:0, qm = 0:4.

70x10-3
qs = 0.2
60 qs = 0.4
qs = 0.6
50 qs = 0.8
qs = 1.0
φd-hyst

40

30

20

10

0.0 0.2 0.4 0.6 0.8

qm

Figure 21: Damkohler number hysteresis locus as a function of the monomer owrate for various
values of the solvent owrate, x4f = 0:0, qi = 0:11429.

47
 60x10-3

50 qm = 0.2
qm = 0.3
qm = 0.4
40
qm = 0.5
qm = 0.6
φd-hyst

30

20

10

0
0.2 0.4 0.6 0.8 1.0
qs

Figure 22: Damkohler number hysteresis locus as a function of the solvent owrate for various
values of the monomer owrate, x4f = 0:0, qi = 0:11429.

0.35
Hysteresis locus
0.30 "0-disjoint" loci
"∞-disjoint" loci
0.25
I
0.20
φd

0.15

0.10 II
IV
0.05

0.00
4 6 8 10 12 14 16 18 20
β

Figure 23: Global multiplicity behavior for the styrene polymerization CSTR model, V = 1500
liters,  = 0:93328, x4f = ?1:14320.

48
 4

2
x3

0.0 0.5 1.0 1.5 2.0 2.5 3.0

qc

Figure 24: Steady-state dimensionless reactor temperature versus cooling jacket owrate, V = 1500
liters, d = 0:01688,  = 13:17936,  = 0:93328, x4f = ?1:14320.

0.6
Hysteresis locus
0.5 "0-disjoint" loci
"∞-disjoint" loci
0.4
I
φd

0.3

0.2
II
0.1 IV

0.0
4 6 8 10 12 14 16 18 20
β

Figure 25: Global multiplicity behavior for the styrene polymerization CSTR model, x4f = ?1:5.

49
 3.4

2.6

1.8
x3

1.0

0.2

-0.6
0 1 2 3 4 5
qc

Figure 26: Steady-state dimensionless reactor temperature versus cooling jacket owrate, d =
0:01688,  = 13:17936, x4f = ?1:5.

50