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A Monte Carlo Method to Quantify the Effect of Reactor

Residence Time Distribution on Polyolefins Made with
Heterogeneous Catalysts: Part I—Catalyst/Polymer Particle
Size Distribution Effects
João B. P. Soares* and Jazmín Romero

of a catalyst tested in the laboratory and

Polyolefins are commercially produced in continuous reactors that have a the same catalyst when scaled up to indus-
broad residence time distribution (RTD). Most of these polymers are made trial production.
with heterogeneous catalysts that also have a particle size distribution (PSD). This fact has been recognized for a
while. Soares and Hamielec[4] and Debling
These are totally segregated systems, in which the catalyst/polymer par­
and co-workers[5] were the first to inves-
ticle can be seen as a microreactor operated in semibatch mode, where the tigate the effect of RTD on the PSD of
reagents (olefins, hydrogen, etc.) are fed continuously to the catalyst/polymer polyolefins made with heterogeneous
particle, but no polymer particle can leave. The reactor RTD has a large influ­ catalysts, but they used distinct math-
ence on the PSD of the polymer particles leaving the reactor, as well as in ematical approaches. Soares and Hami-
polymer microstructure and properties, polymerization yield, and composi­ elec[4] discretized the catalyst PSD into
populations of several size classes, and
tion of reactor blends. This article proposes a Monte Carlo model that can
followed these populations as they were
describe how particle RTD in a single or a series of reactors can affect the transported down a series of continuous
PSD of polymer particles made under a variety of operation conditions. It is reactors having any RTD. Their model
believed that this is the most flexible model ever proposed to model this pheno­ could handle catalysts with any PSDs, and
menon, and can be easily modified to track all properties of interest during reactors with ideal, nonideal, or experi-
mentally measured RTDs. Theirs was a
polyolefin production in continuous reactors with heterogeneous catalysts.
versatile approach, but somewhat cum-
bersome from a computational point of
view, particularly when many reactors in
1. Introduction series needed to be model. Debling and co-workers[5] adopted
a more elegant approach, using population balances to model
Most commercial polyolefins are made in continuous reactors multistage olefin polymerization processes. Their model also
using heterogeneous catalysts. Even though the polymeriza- allowed for consideration of particle size selection effects in the
tion medium (slurry diluent, slurry bulk, gas phase) and reactor process, and the authors used it to simulate gas-phase vertical
configuration (autoclave, loop, fluidized bed, riser/downer and horizontal stirred tank reactors, loop reactors, and fluid-
multizone) can vary substantially from among polymer pro- ized-bed reactors. In subsequent publications, Debling et al.[6]
duction technologies, all of these reactors are ideally operated and Zacca et al.[7] extended their previous model to study the
near steady-state conditions and the catalyst/polymer particles production of multilayered products such as impact polypro-
follow residence time distributions (RTDs) that approximate pylene and bimodal polyethylene. Khang and Lee[8] proposed a
those of a continuous stirred tank reactor (CSTR) or a series model to predict the PSD of polyolefins made in fluidized bed
of CSTRs.[1] Contrarily, most olefin polymerization catalysts reactors, considering nonideal mixing, and derived analytical
are tested in laboratory reactors that are operated in either expressions that took into account both mass transfer limita-
semibatch or batch mode and, consequently, are exposed to tions and catalyst deactivation. Hatzantonis et al.[9] developed
a completely different RTD.[2,3] Failing to consider the drastic a population balance model to describe the PSD of polyolefins
differences in RTD between laboratory and industrial reactors made in gas phase reactors, including the effects of attrition,
may lead to significant discrepancies between the performance elutriation, and agglomeration for catalysts populations with
either uniform sizes or size distribution. Hatzantonis and
Prof. J. B. P. Soares, Dr. J. Romero Kiparissides[10] also used their population balance model to study
Department of Chemical and Materials Engineering the effect of RTD on the PSD of polyethylene made in fluidized
University of Alberta bed reactors, as well as to quantify the effect of mean particle
T6G 2R3 Edmonton, AB, Canada
E-mail: jsoares@ualberta.ca diameter on fluidization dynamics. Prasetya et al.[11] proposed
a dynamic population balance to model the impact of reactor
DOI: 10.1002/mren.201700031 RTD impact polypropylene copolymers. Covezzi and Mei[12]

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used a population balance model to explain how the multi-
zone reactor could be used to achieve heterophasic and multi­
modal reactor blends with better homogeneity by alternating
two CSTRs, one operated as a fast fluidized bed (riser) and the
other as a moving packed bed reactor (downcomer). Zoellner
and Reichert[13] used a dynamic population balance approach
to describe PSD evolution in a lab-scale ethylene gas phase
polymerization under mass transfer limitations, and validated
their results by video microscopy. Their model did not include
RTD effects, since they assumed all particles stayed the same
time in the reactor, which is the right assumption for their lab
scale reactor, but they did not extend their model to continuous
polymerization cases. Yiannoulakis et al.[14] used steady-state
population balances to predict PSD of ethylene copolymers
produced in fluidized bed reactors under moderate particle
agglomeration conditions. They employed the polymeric flow
model[15] to describe heat and mass transfer limitations in the
polymer particles and, as a simplification, assumed that all
catalyst particles had the same size when they were fed to the
reactor. Yiagopoulos et al.[16] demonstrated that prepolymeri-
zation could be used to effectively minimize the drastic mass
and heat transfer limitations that may occur at the beginning
of the polymerization using the polymeric flow model, but did
not consider PSD or RTD effects in their model. Zacca and
Debling[17] used a population balance model based on their pre-
vious publication[5] to study particle overheating for an entire
population of particles. They applied their model to different
reactor types and multistage configurations, and analyzed the
effect of catalyst PSD, reactor RTD, and prepolymerization con-
ditions. Neto and Pinto[18] used a population balance approach
to describe the evolution of polypropylene PSD made in steady-
state slurry and bulk polymerization reactors. Their model also
predicted polypropylene microstructure, and used empirical
correlations to estimate product performance properties. Kim
and Choi[19] modeled particle segregation in fluidized bed reac-
tors using a multicompartment population balance approach,
employing size-dependent transfer constants to account for
the complex fluid dynamics of these reactors. Harshe et al.[20]
developed a generalized dynamic model based on a mixing cell
approach coupled with population balances to model the PSD
of polypropylene made in gas phase reactors. Dittrich and Mut-
sers[21] proposed a new model to study the effect of reactor RTD
on the PSD of polyolefin particles made on horizontal stirred
gas-phase reactors that did not rely on the commonly used
CSTR-in-series approach, but rather on experimental RTDs. In
a more sophisticated analysis, Fan et al.[22] combined popula-
tion balances with a computational fluid dynamics model to
compare the PSD of predicted and experimental polyethylene
particles made in a fluidized bed reactor. Finally, Luo et al.[23]
developed a steady-state population balance model to describe
the PSD of polypropylene made in tubular reactors, consid-
ering flow type, particle dynamics, particle growth, and attri-
tion; their model also included and empirical model to describe
single-particle heat and mass transfer effects.
All these previous modeling approaches—with the excep-
tion of the method proposed by Soares and Hamielec[4]—had
in common the use of population balances to describe how
the RTD (ideal, nonideal, or empirical) of a single or a series
of reactors influenced the PSD of the resulting polymer, the
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fractions of polymer made on different reactors in the series
(for the case of heterophasic or “bimodal” reactor blends) and,
in some cases, intraparticle mass and heat transfer resist-
ances. As powerful as they are, most of these models require
the solution of simultaneous differential-integral equations,
and cannot handle complex polymerization kinetics, catalyst
particle nonuniformities, reactor RTDs or catalysts PSDs of
unusual shapes, and inter- and intraparticle mass and heat
transfer effects very effectively. The model we are proposing
herein differs from the previously published methods because
it uses a Monte Carlo approach to simulate the polymer PSD
made in a series of reactors with RTDs of any shape, while
using catalysts with PSDs also of any shape. The approach
we adopted it to sample catalyst particles randomly from the
population entering the first reactor in the series, then follow
each particle as it flows down the reactor train, while deter-
mining its residence time in each reactor by randomly sam-
pling it from the RTD of each individual reactor. This method
allows not only for unprecedented flexibility regarding the
shapes of reactor RTD and catalyst PSD, but it also makes it
easy to consider catalyst particles with nonuniform active site
concentrations, different polymerization kinetics parameters,
slow activation and induction times, prepolymerization effects,
and volume-dependent reactor residence times, to men-
tion a few factors that can be investigated with this versatile
novel approach. Equally important, the computation time for
these simulations, one of the main concerns in Monte Carlo
methods, is not excessive even in a regular laptop computer,
as we will discuss in more details below. Other phenomena
such as polymer powder bulk density, particle composition of
polymer reactor blends (such as bimodal polyethylenes and
heterophasic impact polypropylene), influence of inter- and
intraparticle mass, and heat transfer resistances, electrostatics,
agglomeration, and particle melting may contribute to the PSD
of polyolefins made in commercial processes, and will be the
subject of future publications from our group.
2. Model Development
The rationale for the proposed Monte Carlo method is illus-
trated in Figure 1. The model assumes that polyolefins are
made on catalyst/polymer particles that act as completely seg-
regated semibatch reactors. Reagents (monomer, comonomer,
hydrogen, etc.) are fed at a constant rate to the polymer particle,
but the produced polymer stays in the particle “microreactor”
until it leaves the reactor train. The polymerization reactors (the
“macroreactors”, not the particle “microreactors”) may be of any
applicable type, such as stirred autoclaves, fluidized bed reac-
tors, plug flow reactors, each of them associated with a given
reactor RTD, which is assumed to be known a priori. This is not
an unrealistic assumption as most of industrial reactors have
known (or, at least approximately known) underlying RTDs. The
model also assumes that catalyst particles are spherical and that
the underlying catalyst particle size distribution (PSD) is known.
The objective of our Monte Carlo method is to compute the
polymer PSD at the exit of each reactor in the train, as well
as the fractions of polymer made on each reactor, taking into
account the reactor RTD and the catalyst PSD, under a variety
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Figure 1.  Schematic of the proposed Monte Carlo method.

of polymerization conditions. To achieve this goal, the model The polymerization rate, Rp, is given by Equation (1)
generates a population with N catalyst particles, wherein the
∞
diameter of each particle is randomly sampled from the catalyst d[M ]
PSD. The model then follows the trajectory of each catalyst par- Rp = − = kp [M ]∑ [Pr ] = kp [M ][Y0 ]
dt (1)
r =0
ticle as it flows down the CSTR train according to the RTD of 
each reactor in the series.
At the beginning of the polymerization train, the model where [M] is the monomer concentration at the active sites, [Pr]
randomly selects a catalyst particle p with a diameter dp using is the molar concentration of living chains with length r, [Y0] is
the PSD provided for the catalyst. The duration (or time span) the total molar concentration of living chains in the reactor, and
that particle p spends in Reactor 1, tp1, is randomly sam- kp is the propagation rate constant.
pled from the RTD of reactor 1 (RTD1). The particle p will In semibatch reactors commonly used to collect polymeriza-
grow into a polymer particle with diameter dp1, following a tion kinetics data, the polymerization rate can be obtained by
predetermined polymerization kinetics mechanism. After dividing the monomer feed flow rate to the reactor, F, by the
exiting Reactor 1, particle p (which is now a polymer particle) reactor volume, VR
is transferred to Reactor 2; similarly, the residence time in
Reactor 2, tp2, is randomly sampled from the residence time F
Rp = (2)
distribution for Reactor 2 (RTD2), which may, or may not be, VR
the same as for Reactor 1, making the particle p grow to a 
diameter dp2. In similar way, particle p continues travelling For all practical purposes, [Y0] is equal to molar concentra-
down the reactor train, while the program keeps track of how tion of active sites in the reactor, since the fraction of polymer-
much polymer is made on each reactor, and how large the free active sites is negligible due to the high activity of coordi-
particle becomes. nation catalysts. [Y0] can be calculated using the chemical equa-
This algorithm is repeated for every catalyst particle in the tions in Table 1, as shown below.
population of N particles selected for the simulations. When The molar balance for the catalyst precursor added at the
the simulation is finished, a population of N polymer particles beginning of the polymerization in a semibatch reactor is
of different sizes was generated, which can be used for the
several calculations described later in this article. We used the d[C ]
numerical inverse method to randomly sample numbers from = −ka [ Al ][C ] (3)
dt 
a specified probability distribution.[24]
A crucial step in determining how much the polymer parti- Table 1.  Olefin homopolymerization mechanism for the determination
cles will grow as they flow down the reactor train is to define of chain growth.
the polymerization kinetics model for this system. Most olefin
polymerization kinetic curves can be modeled with relatively Description Chemical equation Rate constant
simple expressions involving only site activation, propagation, Activation C + Al →P0 ka
and catalyst deactivation (Table 1). Since chain transfer reac-
Propagation Pr + M →Pr + 1 kp
tions are assumed to have no effect on the polymerization rate,
they do not need to be included in the present treatment. More First-order Deactivation Pr → Cd +Dr kd
complex polymerization kinetic schemes can be easily intro- C, catalyst; Al, cocatalyst, P0, active site, Pr, living chain of length r, M, monomer.
duced in the proposed Monte Carlo approach without altering Cd, deactivated site, Dr, dead chain of length r, ka, activation rate constant, kp, prop-
the main conclusions drawn herein. agation rate constant, kd, deactivation rate constant.

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where [C] and [Al] are the concentrations of catalyst and cocata-
lyst, respectively.
Since the cocatalyst is generally present in large excess, the
product ka[Al] = Ka may be assumed to be nearly constant,
which permits the straightforward solution of Equation (3) with
the initial condition [C](0) = [C0]
[C ] = [C0 ]exp(−K a t ) 
A molar balance for Y0 can then be developed
d[Y0 ]
= K a [C ] − kd [Y0 ] = K a [C0 ]exp(−K a t ) − kd [Y0 ]
dt  of the train is given by the integration of Equation (7) or
Equation (5) is a first-order linear differential equation that
can be solved with the initial condition [Y0](0) = 0 to obtain
order Markovian models. Likewise, multiple site type catalysts,
such as heterogeneous Ziegler–Natta and Phillips catalysts may
be modeled with similar polymerization kinetics equations.[1]
For the purposes of the following simulations, it suffices
to realize that the expression for Rp of copolymerization,
Equation (8), is essentially the same as for homopolymeriza-
tion, Equation (7), except for the fact that pseudo kinetic con-
(4) stants for copolymerization replace the homopolymerization
kinetic constants.[1]
It follows that for a catalyst that follows the general poly­
merization scheme listed in Table 1, the polymer yield Qi,p
for a particular polymer particle p produced in the ith reactor
(5)
Equation (8)
kp [M ][C o ] ti  − K a  1− d  t 
 k 

Q i,p =
k ∫ ti − 1


1 − e  K a   e − kd t d t

(10)
 k 
− K a  1− d  t 1− d
1− e  Ka  Ka 
[Y0 ] = [C0 ] e − kd t (6)
k where ti−1 is the time particle p exits Reactor i−1 and enters
1− d
Ka  Reactor i, and ti is the time particle p exits Reactor i in the
series. Equation (10) can be solved analytically (Equation (5.8)
Finally, substituting Equation (6) into Equation (2), we obtain an in Soares and McKenna[1]).
expression for olefin polymerization rate with a single-site catalyst[1] In this way, the polymer yield for particle p during the
whole polymerization process is obtained by simply adding the
 k 
−K a 1− d  t poly­mer yield in each of the n reactors
F 1 − e  Ka 
Rp = = kp [M ] [C0 ] e −kdt (7)
k Q ( p) = ∑ Q i ,p
n
VR 1− d (11)
Ka i =1 

The parameters Ka (or ka), kp and kd are estimated by fitting Finally, assuming that the particles are spherical, the diam-
experimental monomer uptake curves with Equation (7). eter Dp of each particle at the exit of the train is obtained as
Equation (7) can be easily modified for binary copolymeri- follows
zations. Assuming that the propagation rate depends only on
monomer type and not on the type of last monomer added to 6Q ( p) m
the polymer chain (Bernoullian model or 0th order Markov Dp = 3 (12)
πρ
model), it can be rewritten as 
where m is the average molar mass of the repeating unit and
ρ is the density of the polymer particle. Equation (12) assumes
  k  
1 − exp  −K a  1 − d  t  that the particle density is constant, which is probably a
  Ka  
R p = (kp,1 [M1 ] + kp,2 [M2 ]) [C0 ] exp ( −kd t ) reasonable assumption for most of the polymerization time,
k except for the few seconds that take place after initial particle
1− d
Ka break up and growth. Since the average residence time in usual
  kd   olefin polymerization reactors with heterogeneous catalysts
1 − exp  −K a  1 −  t 
  Ka   is in the order of tenths of minutes to hours, changes in par-
= kˆp [M ] [C0 ] exp ( −kd t ) (8) ticle density is not an important factor in these simulations. If
k
1− d required, however, it could be easily accounted for by defining
Ka
a ρ = f(t) function.

where [M1] and [M2] are the concentrations of monomers type 1
Table 2.  Polymerization rate constants and concentrations.
and 2, respectively (for instance, ethylene and 1-hexene), [M] is the
total monomer concentration, [M1] and [M2], and kˆp is the pseudo
Parameter Value
propagation rate constant for copolymerization, defined as
Ka 0.1–1 × 10−3 s−1

kˆp = f 1kp,1 + (1 − f 1 )kp,2 (9) kd 1 × 10−4–3 × 10−4 s−1


kp 2 × 105–1.0 × 105 L mol−1 s−1
and f1 is the molar fraction of monomer type 1 in the reaction [C*] 1 × 10−4 mol L−1
medium. A similar approach can be used to treat copolymers that
[M] 1 mol L−1
follow the terminal model (first-order Markov model) or higher

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Figure 2.  Model catalyst particle size distribution (PSD): Normal distribution with an average of 20 µm and a standard deviation of 3 µm.

3. Results and Discussion
3.1. Effect of the Number of CSTRs in Series on Polymer PSD
Table 2 lists the range of values for polymerization kinetic con-
stants, catalyst and monomer concentrations that will be used
in all simulations described below. These values correspond
to typical estimates for olefin polymerization constants with
Ziegler–Natta and metallocene catalysts.
Figure 2 depicts the PSD of a model catalyst described by
a normal distribution with an average diameter of 20 µm and
a standard deviation of 3 µm. This choice is arbitrary; the
catalyst PSD may be replaced with experimental values for
the PSD of an actual heterogeneous catalyst for olefin poly­
merization without affecting the conclusions of the following
simulations.
The first simulation assumes that the catalyst activates
instantaneously (Ka = ∞) and does not deactivate (kd = 0).
Figure 3 shows that, under these conditions, the cumulative
PSD of the polymer made in one ideal CSTR deviates signifi-
cantly from that obtained when the catalyst PSD is replicated
perfectly, as would be the case if the polymerization took place
in a tubular plug flow reactor, or in an autoclave reactor oper-
ated in batch or semibatch mode. The polymer PSD approaches

Figure 3.  Comparison of the cumulative polymer PSD made under perfect replication conditions (plug flow, batch, or semibatch reactors), in one ideal
CSTR with τ = 1 h, and a) 10 ideal CSTRs each with τ = 6 min per reactor, and b) 20 ideal CSTRs each with τ = 3 min per reactor. (Simulation parameters:
kp = 1.5 × 105 L mol−1 s−1, Ka = ∞, kd = 0, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, and ρpol = 900 g L−1.)

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Figure 4.  Comparison of the PSD of polymer made in 10 ideal CSTRs in series with τ = 6 min per reactor (numbered lines) and the PSD of polymer made
in one CSTR (dashed line) with τ = 60 min. (Simulation parameters: kp = 1.5 × 105 L mol−1 s−1, Ka = ∞, kd = 0, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1,
m = 42 g mol−1, ρpol = 900 g L−1.)

perfect replication when more CSTRs are added to the series:
Figure 3a illustrates the case for 10 CSTRs in series, and
Figure 3b for 20 CSTRs. These results are expected, since the
RTD of an infinite series of CSTRs is equal to the RTD of a
plug flow reactor, and they confirm that the proposed Monte
Carlo algorithm is working correctly.
Figure 4 illustrates similar trends to those in Figure 3, but
using the differential PSDs of polymers made in a single
ideal CSTR or in 10 ideal CSTRs in series, with the same
overall average residence time. The polymer particles exiting
the last reactor in the series (labeled 10/10) have a consid-
erably narrower PSD than those leaving the single CSTR
because the CSTR-in-series configuration has a much nar-
rower RTD.
3.2. Effect of Polymerization Kinetic Constants on Polymer PSD
It is illustrative to compare the effect slower catalyst activa-
tion rates have on the polymer PSD. Figure 5 shows how
decreasing Ka (see insert for polymerization kinetics plot) nar-
rows the PSDs of polymers made in a single CSTR, shifting
them to lower average particle diameters, since catalyst sites
that activate more slowly will not grow as large as catalyst sites
that activate instantaneously.
The deactivation rate constant has a similar effect on the
polymer PSD. Figure 6 shows that, as kd increases, the poly­mer
PSD becomes narrower and shifts toward lower averages
because some of the active sites deactivate before the catalysts
particles leave the reactor; consequently, the polymer particles
cannot grow as large as for catalysts that deactivate more slowly.
Differently from the slower activation in Figure 5 that caused
the polymer PSD to shift toward lower particle sizes, faster cata-
lyst deactivation has little to no effect in the fraction of particles
with small diameters, but rather decreases the fraction of parti-
cles with larger diameters in the population.
From these plots, it follows that since most olefin poly­
merization catalysts deactivate during the polymerization due
to impurities present in the reactor and/or via thermal deacti-
vation mechanisms, the polymer PSD that results will be nar-
rower than the predicted using a simpler model that does not
include catalyst activation and deactivation kinetics.
A more unique case occurs when the olefin polymerization
catalyst is characterized by an induction period. Phillips-type chro-
mium oxide catalysts generally behave in this fashion. In this case,
the induction period prevents the catalyst to start making polymer

Figure 5.  Effect of Ka on the PSD of polymers made in a single CSTRs with τ = 60 min. (Simulation parameters: kp = 1.5 × 105 L mol−1 s−1, kd = 0, [M] =
1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1.)

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Figure 6.  Effect of kd on the PSD of polymer made in a single ideal CSTRs with τ = 60 min. (Simulation parameters: kp = 1.5 × 105 L mol−1 s−1, Ka = ∞,
[M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1.)

before a certain elapsed time. In the limiting case, if this time is
larger than the residence time of a particular catalyst particle in the
reactor, that catalyst particle will leave the reactor without making
any polymer at all. Figure 7a shows how increasing the catalyst
induction time affects the PSD of polymer particles made in a
single CSTR. It is interesting to notice how higher induction times
increase the fraction of very small particles that could not grow
sufficiently large before exiting the reactor, resulting in bimodal
polymer PSDs, even though the catalyst PSD was unimodal and
followed the normal distribution shown in Figure 2. PSD bimo-
dality, however, starts to decrease and eventually disappears as
more CSTRs are added to the series (Figure 7b) because the resi-
dence time of individual particles converge toward the average
residence time when more CSTRs are added to the reactor train.

Figure 7.  Effect of induction time in the polymer PSD: a) Single ideal CSTR with τ = 120 min and different induction times, b) 1, 2, 4, and 8 CSTRs with
10 min of induction time. (Simulation parameters: kp = 1.2 × 105 L mol s−1, Ka = ∞, kd = 0, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 mol L−1,
ρpol = 900 g L−1.)

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Figure 8.  Effect of Ka in the PSD of polymer particles made with a catalyst with an induction time of 5 min and varying Ka values in a CSTR with
τ = 120 min. (Simulation parameters: kp = 1.5 × 105 L mol−1 s−1, kd = 0, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1.)

We assumed instantaneous catalyst activation in the results
presented in Figure 7. If in addition to an induction time, the
catalyst has a slower activation rate, the profiles change again,
increasing the fraction of particles that experience no or very
little polymerization before exiting the reactor, as illustrated in
Figure 8.
3.3. Dealing with PSDs and RTDs with Unusual Shapes
Since the proposed Monte Carlo method adopts a procedure
of random sampling of a particular catalyst PSD, catalysts with
arbitrary PSDs can be as easily modeled as those with more
uniform PSDs. For instance, we will use the bimodal catalyst
PSD with a large-diameter shoulder shown in Figure 9 in our
next simulations.
When this catalyst is allowed to polymerize either in a single
CSTR or in 20 CSRTs in series, assuming instantaneous activa-
tion and no deactivation, the model predicts the polymer PSDs
shown in Figure 10. For the single CSTR case, the polymer PSD
differs substantially from the catalyst PSD because the expo-
nential reactor RTD evens out the bimodality and tailing of the
original catalyst PSD, producing a polymer that has broad but
unimodal PSD. It is interesting to compare this result with the
obtained in the series of 20 CSTRs. In this case, the catalyst PSD
bimodality is nearly replicated in the polymer PSD. This obser-
vation has important implications for scale-up studies from lab-
oratory-scale reactors. Laboratory polymerization reactors used
to test new polymerization catalysts (or optimize existing ones)
are typically operated in semibatch mode, whereas the catalyst
and liquid comonomers are fed in batch mode, while the gas-
eous monomers (ethylene or propylene) are fed continuously. In
this situation, the PSD of the produced polymer particles would
resemble the PSD of the catalyst. If this catalyst is then trans-
ferred to a continuous reactor, either in pilot plant or industrial
scales, the PSD of the formed polymer would be drastically
different from that obtained in the laboratory tests. These dif-
ferences could have important consequences in slurry reactors
(due to differences in suspension viscosity, for instance) and in
gas phase reactors (due to distinct fluidization properties), and
also affect the postreactor processing of the reactor fluff. In fact,
this is always a consideration for any catalyst PSD, as shown in
the figures above, but this somewhat extreme case of a bimodal
catalyst PSD helps emphasize this phenomenon.

Figure 9.  Bimodal catalyst PSD with a large-diameter shoulder, having an average diameter μ =23 µm and a standard deviation σ = 7 µm.

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Figure 10.  Particle size distribution of polymer particles made in a single CSTR (τ = 1 h) or in 20 CSTRs in series (τ = 3 min per reactor). (Simulation
parameters: kp = 1.5 × 105 L mol−1 s−1, Ka = ∞, kd = 0, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1.)

Figure 11.  Particle size distribution of polymer particles made in a single CSTR (τ = 1 h) or in 20 CSTRs in series (τ = 3 min per reactor). (Simulation
parameters: kp = 1.5 × 105 L mol−1 s−1, Ka = 1 × 10−3 s−1, kd = 1 × 10−4 s−1, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1.)

Figure 12.  Comparison of RTDs for ideal CSTRs and Levenspiel’s Model M. (Simulation parameters: τ = 30 min, e = 0.5, f = 1.5.)

Figure 11 illustrates how the PSD of polymer made with the
same bimodal catalyst would be affected if the catalyst activa-
tion was not instantaneous and the catalyst activity decreased
during the polymerization.
Since the proposed Monte Carlo model uses random
sampling of the RTD to determine how long a given cat-
alyst/polymer particle will remain in the reactor, it can
handle equally well reactor RTDs with any shape. The next
simulation compares the effect of changing from an ideal
CSTR RTD to a nonideal RTD expressed by the classic Lev-
enspiel Model M shown in Figure 12. Levenspiel’s model
M represents stagnant zones in a nonideal CSTR of total
volume V as a combination of two ideal CSTR zones of
volume eV and (1−e)V, connected in series, with a forward
flow rate fν and a backwards flow rate (f−1)ν, where ν is the
volumetric flow rate exiting the nonideal CSTR. The higher

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Figure 13.  Effect of nonideal reactor RTD on the PSD of polymers made in a series of four CSTRs. (Simulation parameters: τ = 30 min per reactor, kp =
1.5 × 105 L mol−1 s−1, Ka = 1 × 10−3 s−1, kd = 1 × 10−4 s−1, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1.)

Figure 14.  Nonideal bimodal RTD with slight bimodality (τ = 30 min).

Figure 15.  Comparison of PSDs generated with ideal CSTRs and the RTD depicted in Figure 13. Effect of arbitrary reactor RTD on the PSD of polymers
made in a series of four CSTRs. (Simulation parameters: τ = 30 min per reactor, kp = 1.5 × 105 L mol−1 s−1, Ka = 1 × 10−3 s−1, kd = 1 × 10−4 s−1, [M] =
1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1.)

the f value, the higher the recirculation effect in the stag-
nant zone, and the higher the e value, the higher the size of
the stagnant zone.
Figure 13 shows that, because of the narrower reactor RTD
of Model M, the polymer PSD also becomes narrower than
the PSD obtained in ideal CSTRs. This difference is more pro-
nounced for the first reactor in the series, since the RTD of a
series of CSTR becomes narrower as more reactors are added to
the system.
A more extreme situation in introduced in Figure 14. In
this case study, the reactor RTD is bimodal, indicating by pass
and stagnant zones. The resulting polymer PSD is shown in
Figure 15, demonstrating that our generic Monte Carlo algo-
rithm can model RTDs of arbitrary shapes very easily.

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Figure 16.  Effect of propagation rate constant during prepolymerization on the PSD of polymer particles made in a single ideal CSTR with τ = 1 h.
(Simulation parameters: kp = 1.5 × 105 L mol−1 s−1, Ka = 1 × 10−3 s−1, kd = 1 × 10−4 s−1, [M] = 1.0 mol L−1, [M]prepoly = 0.1 mol L−1 , [C*] = 1 × 10−4 mol L−1,
m = 42 g mol−1, ρpol = 900 g L−1). Insert Rp profiles refer only to the prepolymerization stage.

3.4. Prepolymerization Effects
The proposed Monte Carlo model can also predict the effect of
prepolymerization on the PSD of the prepolymer particles, of
course without including heat and mass transfer phenomena
(in its current version) during the gentler particle fragmenta-
tion that takes place in prepolymerization reactors.
Figure 16 shows the effect of changing the value of the prop-
agation constant during the prepolymerization stage (kp,prepoly),
which could be achieved, for instance, by changing the tem-
perature of the prepolymerization reactor. Introducing a prepo-
lymerization stage substantially reduces the fraction of polymer
particles with smaller diameters, but changing the value of
kp,prepoly has only a small effect on the PSD of the polymer made
in the main CSTR reactor. Prepolymerizations with higher
kp,prepoly values make more prepolymer (Table 3) and narrow the
PSD of the whole polymer slightly, but this is a relatively small
effect.
Figure 17 illustrates a similar effect for when the monomer
concentration during prepolymerization changes but the value of
kp,prepoly remains the same. Very similar trends are observed: pol-
ymer PSDs without and with prepolymerization differ substan-
Table 3. Polymer partition between prepolymerization and main poly­
merization CSTRs for simulations shown in Figure 16.
Propagation constant % of mass prepolymer
kp,prepoly = kp 3.30%
kp,prepoly = ½ kp 1.96%
kp,prepoly = 1/8 kp 0.65%
tially, but among the prepolymerized samples, only slight differ-
ences appear among the polymers, with increased prepolymer
fractions (Table 4) producing slightly narrower polymer PSDs.
Figure 18 investigates the prepolymerization effect from
another angle. In this case, we kept the monomer concen-
tration in the prepolymerization reactor constant, but varied
its average residence time. It is interesting to see that dif-
ferent prepolymerization times have a larger effect on the
polymer PSD than when we change kp,prepoly or monomer
concentration during the prepolymerization stage. In par-
ticular, longer prepolymerization times lead to narrow pol-
ymer PSDs (Figure 19), which is a direct reflection of the
narrower RTDs of two CSTRs in series having closer average

Figure 17.  Effect of monomer concentration during prepolymerization on the PSD of polymer particles made in a single ideal CSTR with τ = 1 h.
(Simulation parameters: kp,prepoly = ¼ kp, kp = 1.5 × 105 L mol−1 s−1, Ka = 1 × 10−3 s−1, kd = 1 × 10−4 s−1, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m =
42 g mol−1, ρpol = 900 g L−1). Insert Rp profiles refer only to prepolymerization stage.

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Table 4. Polymer partition between prepolymerization and main poly­ more than one type of active site, nonuniformity of conditions
merization CSTRs for simulations shown in Figure 17. during catalyst preparation could, in principle, generate particles
with a distinct balance of active site types. These interparticle
Monomer concentration % of mass prepolymer nonuniformities would cause particles with different diameters
[M]prepoly = [M]/5 1.97% to have distinct apparent polymerization kinetic constants.
[M]prepoly = [M]/10 1.15% In the following simulations, we will assume that Ka, kd, and
[M]prepoly = [M]/100 0.17%
kp depend on the initial volume of the catalyst particles. For the
sake of argument, we will also assume that this dependency
is linear with volume, and that the particles with the smallest
residence times. Table 5 lists the fractions of prepolymer for diameters have the highest Ka, kd, and kp values, that is, the
these three simulations. smallest particles activate, propagate, and deactivate with the
highest frequencies.
The following expression was used to obtain a weighting
3.5. Catalyst Particles with Unequal Polymerization Kinetics factor, w(Vp), that depends linearly on particle volume

In this section, we use our Monte Carlo model to explore the

w (Vp ) = w min +
(Vp,max − Vp ) (w max − w min )
effect of catalyst particles with different polymerization kinetics Vp,max − Vp,min (13)
on polymer PSD. Such a situation could happen if the catalyst 
supporting procedure was not done uniformly, in which case
one could expect catalyst particles with different diameters to where, wmin and wmax are the minimum and maximum
have different catalyst loadings, cocatalyst/catalyst ratios, or weighting factors, respectively, Vp is the particle volume, and
donor/catalyst ratios. Since most supported olefin polymeriza- Vp,min and Vp,max are the minimum and maximum volumes for
tion catalysts, such as Ziegler–Natta and Phillips catalysts, have the catalyst particles fed to the first reactor in the series.

Figure 18.  Effect of prepolymerization time during prepolymerization on the PSD of polymer particles made in a single ideal CSTR with τ = 1 h.
(Simulation parameters: kp,prepoly = ¼ kp, kp = 1.5 × 105 L mol−1 s−1, Ka = 1 × 10−3 s−1, kd = 1 × 10−4 s−1, [M] = 1.0 mol L−1, [M]prepoly = 0.1 mol L−1 [C*] =
1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1).

Figure 19.  RTDs for simulations shown in Figure 17.

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Table 5. Polymer partition between prepolymerization and main poly­
merization CSTRs for simulations shown in Figure 18.
Prepolymerization time % of mass prepolymer
τprepoly = 2.5 min 0.27%
τprepoly = 5.0 min 0.55%
τprepoly = 10 min 1.15%
The weighting factor is used to adjust the polymerization
kinetic constants for particles of different volumes with the
generic equation
k (Vp ) = w (Vp ) k
 (14)
where k stands for Ka, kd, or kp.
This is clearly an arbitrary factor, used to illustrate how
the proposed Monte Carlo approach can handle changes of
polymerization kinetic constants from particle to particle, and is
not meant to represent any real catalyst system. In the following
simulations, we corrected all three kinetic constants by the same
factor for the sake of simplicity, since we are not trying to simu-
late an actual catalyst system. A different set of weights, following
dependencies very likely other than linear, could be developed for
a particular catalyst if experimental data was collected using cata-
lyst particles with different average diameters.
Figure 20 shows that when the values of the polymerization
constants of the smaller particles are higher than those for the
larger particles, the PSD of the polymer exiting the reactors will
be narrower, which is a reasonable result, since smaller particles
will grow faster, and larger particles will grow more slowly as they
flow down the polymerization reactors. In the simulations dis-
cussed in this section, the model parameters were chosen so that
the total mass of polymer made in the nonuniform catalyst and in
the comparative uniform catalyst case was the same, to allow for
an equitable comparison between these two cases.
We reach a similar conclusion if we assume that the con-
centration of active sites depends on the volume of the cata-
lyst particle, but that they have the same apparent kinetic
Figure 20.  Effect of unequal polymerization kinetics on polymer PSD. Solid curves correspond to the PSD of polymer made in four ideal CSTRs in
series (with τ = 15 min per reactor) under equal polymerization kinetics, while the PSD made in the same reactor train with unequal poly­merization
kinetics is indicated with dashed lines. (wmin = 0.26 wmax = 1.26 kp = 1.5 × 105 L mol−1 s−1, Ka = 1 × 10−3 s−1, kd = 1 × 10−4 s−1, [M] = 1.0 mol L−1, [C*] =
1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1).
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constants for all particles. We may assume, for instance, the
smaller particles have a higher concentration of active sites
that larger particles, which may indeed happen in the case of
supported metallocene catalysts, since smaller particles are
less prone to diffusion limitations during the catalyst sup-
porting stage. In this case, we may propose the following
equation to account for this dependency
C *  (Vp ) = w (Vp ) C *  (15)

Accordingly, Figure 21 shows that catalysts with nonuniform
active site distribution will produce polymers with narrow PSD,
since the smaller particles will grow at faster rates than the
larger ones.
Even though it was not our intention to model the effect of
intraparticle mass transfer limitations in these case studies—
although it would be relatively easy to combine the proposed
Monte Carlo approach with models such as the polymeric flow
or multigrain models—similar results would be observed:
smaller particles, less prone to mass transfer limitations, would
grow at faster rates than larger particles. The main difference, of
course, is that as the polymer particles grow, the relative impor-
tance of intraparticle mass transfer resistances decrease, while
in our case the polymerization kinetics remains unchanged as
the particles grow larger due to polymer formation.
3.6. Biased Sampling and Fluidized Bed Reactors
The proposed Monte Carlo approach also can handle a more
complex case, often ignored in previous modeling approaches:
the effect of particle size on the residence time of particles in
the polymerization reactor. The best example of this situation
refers to fluidized bed reactors, whereas larger and heavier par-
ticles are more likely to exit the polymerization from the bottom
of the reactor increases.
We implemented a biased sampling method to handle this
phenomenon, a weighting factor proportional to the volume of
the particle and to the volume of the mean of the population is
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Figure 21.  Effect of unequal catalyst concentrations on polymer PSD. Solid curves correspond to the PSD of polymer made in four ideal CSTRs in series
(with τ = 15 min per reactor) under the same catalyst concentration, while the PSD made in the same reactor train with different catalyst concentra-
tions is indicated with dashed lines. (wmin = 0.43 wmax = 1.2 kp = 1.5 × 105 L mol−1 s−1, Ka = 1 × 10−1 s−1, kd = 1 × 10−4 s−1, [M] = 1.0 mol L−1, [C*] = 1 ×
10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1).

used to increase or decrease the polymerization of a given par- mean particle volume, tp is polymerization time, wmin and wmax
ticle: the smallest particles will increase their polymerization are parameters determining decrease or increase in residence
time tp by wmaxtp, while the largest particles will decrease them time, respectively. Figure 22 is a graphical representation of this
by wmintp, where wmax ≥ 1 and wmin ≤ 1. The closer the diameter weighting factor.
of the particle is to the mean diameter of the whole population, In the following simulations, we apply the biased sampling
the less affected is its polymerization time. method for all the reactors in the train, that is, Vp,min, Vp,max,
The biased sampling weighting factor is computed as follows and Vp,mean were recalculated for each reactor. In addition, we
assumed that wmin = 1 − w and wmax = 1 + w for a given value w.
 w max − 1  Figure 23 shows that narrower PSD should be expected if
w (Vp ) = 1 + (Vp,mean − Vp )   , if Vp < Vp,mean
Vp,mean − Vp,min  (16) smaller particle are likely to stay longer, while larger particle
 are likely to stay shorter times in the polymerization reactor.
Once again, this result is intuitively expected, but the proposed
 1 − w min  Monte Carlo method allows us to precisely calculate the effect
w (Vp ) = 1 − (Vp − Vp,mean )   , if Vp > Vp,mean (17)
Vp,max − Vp,mean  of this variable in the polymer PSD for any arbitrary biased
 sampling correction.

tp = w (Vp ) tp (18)
 3.7. Computational Time Considerations

where, Vp is the particle volume, Vp,min is the minimum particle One of the main criticisms Monte Carlo simulations face is
volume, Vp,max is the maximum particle volume, Vp,mean is the the relatively high computational time they require to obtain

Figure 22.  Plot of the biased sampling weight factor adopted for the following simulations.

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Figure 23.  Comparison of the PSD predicted with the biased sampling method and an ideal CSTR RTD. The simulation considered four reactors in
series with a mean residence time of 15 min (1 h, combined). The solid curve corresponds to the PSD obtained for four ideal CSTRs, while the dashed
black and solid gray curves corresponds to the biased sampling method for w = 0.5 and w = 0.2, respectively. (kp = 1.6 × 105 L (mol s)−1, Ka = 1 ×
10−2 s−1, kd = 1 × 10−4 s−1, [M] = 1.0 mol L−1, [C*] = 1 × 10−4 mol L−1, m = 42 g mol−1, ρpol = 900 g L−1).

statistically valid results. The running time of our algorithm
increases linearly with the number of particles (N) and
number of reactors (n). However, the number of reactors could
be considered as a negligible factor, since it is much smaller
than the number of polymer particles required to represent a
polymerization system. For industrial applications, where typi-
cally there are 1 to 3 reactors in series (or a few more if one
decides to model a horizontal gas-phase reactor as a series of 4
to 6 CSTRs), the number of reactors is of little concern from a
computational point of view.
Table 6 compares the runtimes for different N and n values,
assuming a normal polymer PSD and exponential (ideal CSTR)
reactor RTDs. All simulations were performed in a laptop PC
with Intel Core i3-4030U CPU at 1.90 GHz and 8.00 GB of
RAM, which is a rather ordinary computer. The computation
time, even for the extreme case of 5 million particles in 60 reac-
tors in series (which only has theoretical relevance, since no
such industrial process exist) is still under 30 min, proving that
this approach is not computational onerous, even in limiting
cases.
All sample sizes probed in this investigation, from 1 to 5
million, generate smooth PSDs that are statistically valid. It
may be possible to use even smaller sample sizes, but the sta-
tistical noise level will increase with decreasing sample size.
Moving average or similar smoothing algorithms may be used
to reduce the noise levels in these cases, further decreasing
the required computation time, but we have not studied this
type of correction in the present investigation.
In addition, it should be mentioned that the proposed
approach is ideal for implementation in parallel computers,
Table 6. Run times of our Monte Carlo method considering different number of catalyst/
polymer particles and reactors.
Number of particles 1 Reactor 6 Reactors 12 Reactors
1 000 000 8s 45 s 1 min
2 000 000 17 s 1 min 2 min
5 000 000 36 s 3 min 6 min
where the trajectory of many particles could be tracked simul-
taneously, thus reducing the computation time by orders of
magnitude.
4. Conclusion
We have demonstrated that the proposed Monte Carlo model
is extremely versatile, being able to describe reactor systems
with any arbitrary RTD for catalyst particles also having any
PSD shape. Since our modeling approach randomly samples
the catalyst PSD and RTD to determine which particles stay
which time in each of the reactors in series, these distribu-
tions can take any shape. For the same reason, each catalyst/
polymer particle can be considered individually, and be sub-
ject to distinct polymerization kinetics, selective residence
time characteristics, and prepolymerization regimens. Con-
sidering that the computation time required for these calcu-
lations is quite short for most cases of industrial relevance,
where only a few reactors in series need be considered, the
proposed approach seems to be ideal to treat practical cases
for industrial applications.
In this article, we focused our attention on RTD effects on
polymer PSD, but these applications only scratch the surface of
the many uses made possible by this methodology. In the next
articles in this series, we will apply our Monte Carlo approach
to study how reactor RTD may influence polymer powder
bulk density, particle composition of polymer reactor blends
(such as bimodal polyethylenes and heterophasic impact poly-
propylene), and the influence of inter- and
intraparticle mass and heat transfer resist-
ances on polyolefin production.
60 Reactors
6 min
13 min Conflict of Interest
27 min The authors declare no conflict of interest.

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Keywords
particle size distribution, polyethylene, polyolefins, polypropylene,
reactor residence time distribution
Received: June 7, 2017
Revised: August 17, 2017
Published online: October 9, 2017
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