Full Paper 169

Summary: Silica supported chromium oxide catalysts have agreement has been obtained for the polymerization condi-
been used for many years to manufacture polyethylene and tions employed.
they still account for more than 50% of world production
of high-density polyethylene. Along with its commercial
success, the catalytic mechanism and polymerization kinetics
of silica supported chromium oxide catalysts have been
the subject of intense research. However, there is a lack of
modeling effort for the quantitative prediction of polymer-
ization rate and polymer molecular weight properties. The
chromium oxide catalyzed ethylene polymerization is often
characterized by the presence of an induction period followed
by a steady increase in polymerization rate. The molecular
weight distribution is also quite broad. In this paper, a two-
site kinetic model is developed for the modeling of ethylene
polymerization over supported chromium oxide catalyst. To
model the induction period, it is proposed that divalent
chromium sites are deactivated by catalyst poison and the
reactivation of the deactivated chromium sites is slow and
rate controlling. To model the molecular weight distribution
broadening, each active chromium site is assumed to have
different monomer chain transfer ability. The experimental
data of semibatch liquid slurry polymerization of ethylene is Polymerization rates at different reaction temperatures:
compared with the model simulations and a quite satisfactory symbols – data, lines – model simulations.

Modeling of Ethylene Polymerization Kinetics over

Supported Chromium Oxide Catalysts
Kyu Yong Choi,* Shihua Tang, Won Jung Yoona
Department of Chemical Engineering, University of Maryland, College Park, MD 20742, USA
Fax: (301) 405-0523; E-mail: choi@eng.umd.edu

Received: August 27, 2003; Revised: November 5, 2003; Accepted: November 24, 2003; DOI: 10.1002/mats.200300017
Keywords: catalysts; ethylene polymerization; kinetic model; modeling; multi-site model

Introduction There are two major families of supported chromium

catalysts: organochromium-based catalysts and chromium
Supported chromium oxide catalyst, known as the Phillips
oxide-based catalysts.[1] The Cr/silica catalyst is prepared
catalyst, is an industrially important catalyst to manufacture
by supporting a chromium compound onto porous silica
high-density polyethylene (HDPE) in liquid slurry and gas
supports and then activating it by calcining. A typical
phase polymerization processes using loop reactors and
catalyst loading is less than 1 wt.-% Cr on high surface area
fluidized bed reactors. Although other types of catalysts
silica (
300 m2  g1). A supported chromium oxide
such as Ziegler-Natta catalysts and metallocene catalysts
catalyst is not active for ethylene polymerization until it is
are also used to make high-density and low-density olefin
calcined in oxygen at a temperature between 300 and
homopolymers and copolymers, a family of silica sup-
1 000 8C. The polymerization performance of a supported
ported chromium oxide catalysts still accounts for about
chromium oxide catalyst is strongly dependent on the
50% of the world’s HDPE production.
method of its preparation and the properties of a support
a
On leave from Kyungwon University, Department of Chemical material. It is mostly the catalyst that controls the polymer
and Bioengineering, Seongnam City, Kyunggi-do, 461-701 productivity and the key polymer properties, such as
Korea. molecular weight distribution and branching.

Macromol. Theory Simul. 2004, 13, 169–177 DOI: 10.1002/mats.200300017 ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
170
Supported chromium oxide catalysts exhibit some unique
catalytic behaviors. For example, a chromium oxide catalyst
may not be immediately active for ethylene polymerization
on its exposure to ethylene in the reactor; the polymeriza-
tion goes through a period in which no noticeable poly-
merization occurs. This period is called the induction period
or the nascent period, which may last from a few minutes to
over 1 h. When Cr6þ is reduced by ethylene to catalytically
active Cr2þ some byproducts such as aldehydes are
generated. These byproducts are near the active sites and
they are believed to poison the active Cr2þ sites. The rapid
poisoning of chromium sites and subsequent slow reactiv-
ation by ethylene is thought to be the possible causes for the
time-delayed site activation. The duration of the induction
time depends on several factors (e.g., method of catalyst
preparation, method of catalyst activation, and polymeriza-
tion conditions).
In contrast to a large number of publications on the
kinetics of chromium oxide catalyzed ethylene polymer-
ization, very little has been reported on the modeling of
ethylene polymerization with supported chromium oxide
catalysts. In the modeling work by Embry, a monomer-
assisted two-step initiation mechanism has been proposed
to model the induction period.[2] He proposes that the initial
catalyst activation occurs by the reaction between chro-
mium oxide catalyst and ethylene. Then, the site is further
activated by ethylene before polymer chain growth reaction
begins. The second step is likely the rate controlling
process. This kinetic behavior of chromium oxide catalyzed
ethylene polymerization is quite different from that obser-
ved in other olefin polymerization processes with Ziegler-
Natta type catalysts and metallocenes. With these
non-chromium catalyst systems, the catalytic site activation
is almost instantaneous and the polymerization rate quickly
rises to a maximum, followed by either a rapid, or a slow,
rate decrease due to site deactivation and/or diffusion
limited intraparticle monomer mass transfer.
After the induction period, the polymerization rate
with chromium oxide catalyst starts to increase steadily with
time until it levels off. We say that the polymerization rate
has reached a stationary rate. The steady increase in
polymerization rate with time suggests that the concentration
of active catalytic species (probably Cr2þ) is not constant but
increases with time. It is believed that the time-varying
polymerization rate also affects the molecular weight distri-
bution of polyethylene because the polymer chain length is
dependent on the chain propagation rate. In general, molec-
ular weight distribution of polyethylene made over suppor-
ted chromium oxide catalysts is generally much broader than
that made over other catalysts, such as Ziegler-Natta catalysts
and metallocene catalysts. Unlike titanium-based Ziegler-
Natta catalysts, chromium oxide catalysts show little
reactivity toward hydrogen for chain transfer reaction.
For the quantitative calculation of polymerization rate
and polymer molecular weight distribution, it is necessary
Macromol. Theory Simul. 2004, 13, 169–177 www.mts-journal.de
K. Y. Choi, S. Tang, W. J. Yoon
to understand the catalytic behaviors and develop a
mathematical kinetic model. Unfortunately, developing a
kinetic model for Cr/silica catalyst systems is not as
straightforward as it seems because a proper mechanism to
predict the induction period and time-varying polymeriza-
tion rate has not been well documented in open literature.
To develop a kinetic model, it would be instructive to
briefly review more details of the important characteristics
of the catalyst preparation, activation, and polymerization
with supported chromium oxide catalyst. After a chromium
compound is deposited onto a fully hydrated wide pore
silica support with surface silanol groups the supported
catalyst is calcined at high temperature in oxygen to activate
the catalyst.[3] Chromium oxide is anchored onto the silica
surface as a surface chromate or dichromate ester. Any
remaining surface hydroxyl groups might interfere with
polymerization if not removed.[1] When the catalyst is
exposed to ethylene, the hexavalent chromium (Cr6þ) is
reduced to a lower valent active species such as divalent
chromium. Also, some byproducts such as formaldehyde or
acetaldehyde are generated.[4,5] Then, the byproduct may
coordinate to the chromium until it is displaced by ethylene.
It is thought that the insertion of the first monomer molecule
into an active center (Cr2þ) (alkylation) might be a rate con-
trolling step, although the exact mechanism is still not
completely understood. The alkylation may not occur, or
may occur at a very slow rate, when the concentration of
reduced Cr2þ on the catalyst surface is very low. McDaniel
and Welch report that the polymerization activity of
supported chromium oxide catalysts is strongly dependent
upon the activation temperature, although the induction
time is little affected.[6] It is also reported that polymer
molecular weight tends to decrease as higher catalyst
calcination temperature is used. Their experimental data
shows that more dehydrated catalyst yields lower molecular
weight polymer and that the concentration of active sites on
the catalyst is probably not constant. The existence of
different types of chromium (VI) active centers with
different chain termination activities was also proposed.
Due to the complexity of chemical reactions that occur
during the calcination and activation stages, the chromium
oxide catalysts are very sensitive to minor variations in
catalyst purity, porosity, calcining history, and impurities.
Thus, it might be very difficult to develop a kinetic model
that can be universally applied to every chromium oxide
catalyst system.
There have been a large number of publications on the
chromium oxide catalyzed ethylene polymerization pro-
cesses. However, there is no general consensus about the
nature of the active site and polymerization mechanisms
with many controversial results reported in the litera-
ture.[3,7] Moreover, little has been published in the open
literature on the quantitative modeling of the polymeriza-
tion kinetics for the chromium oxide catalyst system. The
scarcity of kinetic modeling work for chromium oxide
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Modeling of Ethylene Polymerization Kinetics over Supported Chromium Oxide Catalysts
catalyst systems is quite surprising in view of the fact that
modeling of Ziegler-Natta or metallocene catalyzed ethylene
polymerization processes have been quite extensively stu-
died, and that chromium oxide catalyzed ethylene polymer-
ization is still industrially very important. A possible reason
for the lack of kinetic modeling lies probably in the com-
plexity of the redox and coordination chemistry of chromium
in combination with the heterogeneous silica surfaces.[8]
A good kinetic model is needed to develop a polymer-
ization process model that can be used to design improved
reactor controls. For example, consider a continuous slurry
ethylene polymerization process with a loop, or stirred tank
reactor where the overall reactor performance and polymer
properties are influenced by reactor residence time distri-
bution. Since silica supported chromium oxide catalyst
undergoes a finite induction time and time-varying poly-
merization rate period, there can be a great heterogeneity
in polymer particle size distribution and other properties
in the polymer produced in a continuous polymerization
reactor. For example, if the reactor is operated such that a
large amount of catalyst leaves the reactor with short
residence times, very little polymer will be produced
because the catalyst particles do not have enough time in the
reactor to go through the induction and activation periods.
Certainly, the catalyst is not fully utilized for polymer
production. Also, if polymer molecular weight varies with
reactor residence time, polymer particles produced in a
continuous flow polymerization reactor would exhibit
significant heterogeneity in molecular weight distribution.
Therefore, it would be very useful to have a kinetic model
that can predict the polymerization rate and polymer
molecular weight properties. Through such kinetic and
reactor modeling, we can gain improved understanding of
the polymerization process and develop improved process
operating conditions.
In this paper, we propose a kinetic model for a silica
supported chromium oxide catalyst for ethylene polymer-
ization where the induction period is present. Some other
types of chromium-based catalysts that do not exhibit the
induction period are excluded from our modeling con-
siderations. It is noted that we do not attempt in this work to
develop a model that incorporates every chemical and
physical aspect of Cr/silica catalyzed ethylene polymeriza-
tion. Instead, we limit our modeling to develop a model
capable of predicting the polymerization and molecular
weight averages so that the model can be used to better
understand the macroscopic behaviors of the ethylene
polymerization processes. The results of model simulations
are compared with experimental data obtained in an
industrial laboratory.
Model Development
The silica-supported chromium oxide catalyst considered
in our modeling is typically heat treated at high temperature
Macromol. Theory Simul. 2004, 13, 169–177 www.mts-journal.de
171
(e.g., 816 8C) for more than 10 h. The induction time be-
comes shorter with 1) increasing calcining temperature, 2)
increasing reaction temperature, and 3) increasing ethylene
concentration.[9] Aldehyde can be produced as a reaction
byproduct when Cr6þ is reduced to Cr2þ by ethylene. The
reduced Cr2þ site adsorbed by aldehyde might be unable to
initiate polymerization reaction. The type of catalyst poison
affects the duration of the induction period. The concentra-
tion of poison that has a visible effect on observed reaction
rates is on the order of 1 ppm.[10] Therefore, it would be very
difficult to measure the concentrations of poison species
during the reaction, making the poisoning reaction kinetics
and mechanism difficult to analyze.
Let us consider ethylene homopolymerization with a
typical silica supported chromium oxide catalyst. The
major goal of the modeling is to predict the polymerization
rate profiles and polymer molecular weight properties. We
postulate that Cr6þ is first reduced to the catalytically active
species Cr2þ by reacting with two ethylene monomers
(Scheme 1, Step 1). The reduction reaction generates a
poisonous compound such as aldehyde. Then, the reduced
chromium species is inactivated by the adsorption of
aldehyde (Scheme 1, Step 2).
The divalent chromium site (Cr*) adsorbed by the poison
(P) is unable to initiate ethylene polymerization. We assume
that the inactive chromium site is slowly reactivated by
ethylene-assisted alkylation. Since the ethylene concentra-
tion is several orders of magnitude larger than the catalytic
site concentration, we can approximate the alkylation
reaction as a pseudo-first order reaction as follows:
k30
Cr* þ M ! Cr2þ þ P*
rate ¼ k30 ½M½Cr*  k3 ½Cr* ð,½M  const:  ½Cr2þ
T Þ
where P* is the byproduct of alkylation or reactivation
reaction, which is not readsorbed onto the chromium site.
Qualitatively, the poisoning reaction might be very fast and
the above site reactivation reaction might be the rate
controlling step for the polymerization.
Scheme 1.
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
172 K. Y. Choi, S. Tang, W. J. Yoon

Another important aspect of chromium oxide catalyzed when the deactivated site recovers its activity, desorbed
ethylene polymerization is the broadening of polymer poison species diffuses out quickly from the solid surface.
molecular weight distribution (e.g., M w =M n >> 2.0). Like In other words, we assume that the desorbed poison is
in heterogeneous Ziegler-Natta catalyst systems, the not adsorbed again. Both vacant Cr2þ sites and active
molecular weight distribution (MWD) broadening might propagation site (Cr2þ-polymer) are subject to poisoning.
be due to the presence of multiple active sites (site Then, the kinetic modeling equations take the following
heterogeneity). In heterogeneously catalyzed polymeriza- form:
tions, intraparticle monomer diffusion resistance can also
d½Cr6þ 
contribute to the MWD broadening, but the diffusion effect ¼ k1 ½Cr6þ ½M2 ð8Þ
is usually much smaller than the effect of site heterogeneity. dt
!
Although long chain branching (LCB) might also con- d½P Xm X1
tribute to the MWD broadening, we assume that the LCB ¼ 2k1 ½Cr6þ ½M2  k2 ½P Nðr; jÞ ð9Þ
dt j¼1 r¼0
concentration is not large enough to significantly broaden
the MWD and hence, LCB formation reactions are not dNð0; jÞ
¼ k1 ½Cr6þ ½M2 fð jÞ  ka ð jÞ½MNð0; jÞ
included in our simplified kinetic model. dt
In the kinetic model we propose in this work, the focus is  k2 ½PNð0; jÞ þ k3 N 0 ð0; jÞ ð10Þ
placed on the prediction of induction period and broad
molecular weight distribution. Hence, we employ a multi- dNð1; jÞ
¼ ka ð jÞ½MNð0; jÞ  kp ð jÞ½MNð1; jÞ
site polymerization model where a stepwise activation dt !
mechanism for chromium sites is incorporated. The X1
þ kfm ð jÞ½M Nðr; jÞ  Nð1; jÞ
proposed kinetic scheme is given as follows:
r¼1
Reduction of Cr6þ to Cr2þ and poison species:
 k2 ½PNð1; jÞ þ k3 N 0 ð1; jÞ ð11Þ
k1
Cr6þ þ 2M ! Nð0; jÞ þ 2P ð1Þ
dNðr; jÞ
¼ kp ð jÞ½MðNðr1; jÞNðr; jÞÞ kfm ð jÞ½MNðr; jÞ
Poisoning of active site: dt
k2  k2 ½PNðr; jÞ þ k3 N 0 ðr; jÞ ð12Þ
Nð0; jÞ þ P ! N 0 ð0; jÞ ð2Þ
dN 0 ðr; jÞ
k2 0 ¼ k2 ½PNðr; jÞ  k3 N 0 ðr; jÞ ðr  0Þ ð13Þ
Nðr; jÞ þ P ! N ðr; jÞ ð3Þ dt
Transformation of poisoned site to active site: dQðrÞ
¼ kfm ½MNðr; jÞ ð14Þ
k3
N 0 ðr; jÞ ! Nðr; jÞ ðr  0Þ ð4Þ dt
In the above, f( j) is the mole fraction of type-j active site.
Chain initiation:
To calculate molecular weight averages, the molecular
ka ð jÞ weight moment equations need to be included in the kinetic
Nð0; jÞ þ M ! Nð1; jÞ ð5Þ
model. The molecular weight moments are defined as
Chain propagation (r  1): follows:
X
1
kp ð jÞ
Nðr; jÞ þ M ! Nðr þ 1; jÞ ð6Þ Yk ð jÞ  r k Nðr; jÞ;
r¼1
Chain transfer to monomer: X
1
Zk ð jÞ  r k N 0 ðr; jÞ;
kfm ð jÞ r¼1
Nðr; jÞ þ M 
! QðrÞ þ Nð1; jÞ ð7Þ
X
1
where N(0, j) is the vacant active site of type j catalytic site Xk ð jÞ  r k QðrÞ ð15Þ
(i.e., Cr2þ( j)), N 0 ðr; jÞ is the poisoned (inactive) vacant site r¼1

of type j with chain length r, N (r, j) is the living polymer Then, the number average and weight average degrees
with chain length r at type j active site, Q(r) is the dead of polymerization are calculated using the following
polymer with chain length r, and P is the poison species. equations:
Here, we ignore any reactions that may lead to the formation
of branched polymers.
n ð jÞ ¼ X1 ð jÞ þ Y1 ð jÞ þ Z1 ð jÞ ;
X
X0 ð jÞ þ Y0 ð jÞ þ Z0 ð jÞ
In the above, it is assumed that temporarily deactivated or
poisoned site (Cr*) recovers its full activity through site X
w ð jÞ ¼ X2 ð jÞ þ Y2 ð jÞ þ Z2 ð jÞ ð16Þ
transformation or reactivation reaction. We also assume that X1 ð jÞ þ Y1 ð jÞ þ Z1 ð jÞ

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 Modeling of Ethylene Polymerization Kinetics over Supported Chromium Oxide Catalysts 173

For computational convenience, the following normal- dZ0 ð jÞ

¼ k2 xp ½Cr6þ 0 Y0 ð jÞ  k3 Z0 ð jÞ ð28Þ
ized variables are used: dt
½Cr6þ  ½P Nðr; jÞ dZ1 ð jÞ
xc  ; xp  ; xðr; jÞ  ¼ k2 xp ½Cr6þ 0 Y1 ð jÞ  k3 Z1 ð jÞ ð29Þ
½Cr6þ 0 ½Cr6þ 0 ½Cr6þ 0 dt
N 0 ðr; jÞ QðrÞ
x0 ðr; jÞ  ; xq ðr; jÞ  ð17Þ dZ2 ð jÞ
½Cr6þ 0 ½Cr6þ 0 ¼ k2 xp ½Cr6þ 0 Y2 ð jÞ  k3 Z2 ð jÞ ð30Þ
dt

Then, the kinetic modeling equations are expressed as: dX0 ð jÞ

¼ kfm ð jÞ½MY0 ð jÞ ð31Þ
dxc dt
¼ k1 xc ½M2 ð18Þ
dt
! dX1 ð jÞ
Xm X1 ¼ kfm ð jÞ½MY1 ð jÞ ð32Þ
dxp dt
¼ 2k1 xc ½M2  k2 xp ½Cr6þ 0 xðr; jÞ ð19Þ
dt j¼1 r¼0
dX2 ð jÞ
¼ kfm ð jÞ½MY2 ð jÞ ð33Þ
dxð0; jÞ dt
¼ k1 xc ½M2 fð jÞ  ka ð jÞ½Mxð0; jÞ
dt
 k2 xp xð0; jÞ½Cr6þ 0 þ k3 x0 ð0; jÞ ð20Þ These molecular weight moment equations are solved
together with the kinetic Equation (18)–(24).
dxð1; jÞ
¼ ka ð jÞ½Mxð0; jÞ  k2 xp xð1; jÞ
dt
þ k3 x0 ð1; jÞ  kp ð jÞ½Mxð1; jÞ Results and Discussion
!
X
1 The above model is quite general in that there is no
þ kfm ð jÞ½M xðr; jÞ  xð1; jÞ ð21Þ limitation in the number of active site types. In theory, it is
r¼1
not difficult to illustrate through model simulations that the
dxðr; jÞ MWD broadening can be indeed predicted using the multi-
¼ k2 xp xðr; jÞ þ k3 x0 ðr; jÞ
dt site kinetic model. However, when it comes to finding or
þ kp ð jÞ½Mðxðr  1; jÞ  xðr; jÞÞxð1; jÞ determining the relevant kinetic parameters for a given
‘‘multi-site catalyst’’ system, one immediately faces a pro-
 kfm ð jÞ½Mxðr; jÞ ðr  2Þ ð22Þ
blem of identifying and characterizing the different active
sites. Although the model structure is developed for
dx0 ðr; jÞ multiple active site catalyst, the model would be useless if
¼ k2 xp xðr; jÞ½Cr6þ 0  k3 x0 ðr; jÞ ðr  0Þ ð23Þ
dt the relevant model parameters cannot be measured or
estimated using available data. Currently, no theoretical or
dxq ðrÞ experimental technique has been developed to identify the
¼ kfm ½Mxðr; jÞ ð24Þ
dt nature and the characteristics of different catalytic active
The molecular weight moment equations take the follow- sites in either supported chromium oxide or Ziegler-type
ing form in terms of these normalized variables: olefin polymerization catalysts.
In general, polymer yield (or polymerization rate) and
dY0 ð jÞ polymer molecular weight properties are measured; how-
¼ ka ð jÞ½Mxð0; jÞ þ k3 Z0 ð jÞ  k2 xp ½Cr6þ 0 Y0 ð jÞ
dt ever, this data does not provide any information about how
ð25Þ each different catalytic site contributes to the overall yield
and properties. In other words, it is not possible to extract
dY1 ð jÞ
¼ ka ð jÞ½Mxð0; jÞ þ k3 Z1 ð jÞ something out of nothing. Therefore, some simplifying
dt assumptions are necessary to develop a workable model,
þ ðkp ð jÞ þ kfm ð jÞÞ½MY0 ð jÞ which will then be an approximate model.
 ðk2 xp ½Cr6þ 0 þ kfm ð jÞ½MÞY1 ð jÞ ð26Þ A broad molecular weight distribution can be fitted with a
multi-site model in which each active site produces a
dY2 ð jÞ polymer that has the most probable chain length distribu-
¼ ka ð jÞ½Mxð0; jÞ þ k3 Z2 ð jÞ tion. Although the numerical deconvolution technique can
dt
þ ðkp ð jÞ þ kfm ð jÞÞ½MY0 ð jÞ þ 2kp ð jÞ½MY1 ð jÞ be used with experimental weight chain length distribution
data, it is still difficult to determine the kinetic parameters
 ðk2 xp ½Cr6þ 0 þ kfm ð jÞ½MÞY2 ð jÞ ð27Þ for each catalytic site.[11] In this work, we simplify the

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174 K. Y. Choi, S. Tang, W. J. Yoon

multi-site model by assuming that there are only two diffe- Table 1. Semibatch liquid slurry polymerization data with silica
rent types of catalytic sites (i.e., two-site model). To model supported chromium oxide catalyst.
the polymer molecular weight distribution, we make the Run No. Polymerization Ethylene Rp,ssa) t1/2
following assumptions: (i) the polymerization (propaga- temperature T concentration
tion) activities of these two sites are identical; (ii) but each ([M]*)
site differs in its chain transfer capability with monomer: 8C mol  L1 g  min1 min
one of the two catalytic sites produces much longer dead
polymer chains than the other. It should be noted that the 1 80 0.6709 2.5 190
3 90 0.6275 12.0 145
first assumption is not based on accurate experimental
4 100 0.5730 17.0 140
observations or data. The second assumption is employed to 5 105 0.5380 18.0 70
model the broad polymer chain length distribution.
a)
Then, the two key parameters in the two-site kinetic Rp,ss: stationary polymerization rate.
model are the mole fraction of each catalytic site and
the monomer chain transfer rate constant for each site.
These parameters are adjusted or optimally estimated by The poisoning and site transformation rate constants k2
fitting the experimental data of polymerization rate and and k3 are determined by fitting the model with experi-
molecular weight averages. Since we have assumed that mental data and the two estimated rate constants, k1 and k2.
each catalyst site has the same propagation activity, a single To evaluate the kinetic model developed in this study, we
site kinetic model is used to determine the kinetic constants used the experimental data obtained at an industrial
(k1
k4) that affect polymer yield or polymerization rate. laboratory using a semi-batch liquid slurry polymerization
We also assume that ka ð jÞ  kp ð jÞ. It should be unders- reactor (Note: Specific details of the supported chromium
tood that the resulting kinetic parameters obtained by fitting oxide catalyst are not given here because of proprietary
the experimental data are not the true intrinsic kinetic para- reason. But the laboratory polymerization procedure is very
meters but the effective kinetic parameters that are valid similar to that used by other workers reported in literature).
only with the assumptions made in this modeling. Table 1 shows the stationary ethylene polymerization rates
In a typical semi-batch polymerization (gas phase or obtained at four reaction temperatures in liquid slurry
liquid slurry phase), monomer concentration is kept cons- ethylene polymerization. For a given ethylene pressure in
tant by maintaining the reactor pressure (or ethylene partial the reactor, the molar concentration of ethylene dissolved in
pressure) constant. To determine the propagation rate the diluent liquid phase was calculated using the Peng-
constant (k4 ¼ kp) at constant temperature, we use the sta- Robinson equation of state. The interfacial and intraparticle
tionary polymerization rate (Rp,ss in g  min1): mass transfer resistances were assumed to be negligible.
Figure 1 shows the Arrhenius plots of the rate constants
Rp;ss ¼ k4 Wcat ½Cr2þ ss ½Mwm ð34Þ estimated from the data shown in Table 1. Notice that the
where Wcat ¼ g-catalyst charged into the reactor, wm ¼ mo- poisoning reaction rate constant k2 is several orders of
molecular weight of ethylene (g  mol1), [M] ¼ monomer magnitude larger than the reduction rate constant (k1) and
(ethylene) concentration (mol  L1), and [Cr2þ] ¼ total the reactivation rate constant (k3). The activation energy for
active chromium (mol  (g-cat)1). Since the actual con- k2 is the largest (19.18 kcal  mol1), indicating that
centration of active sites is not measured we assume that as
the polymerization rate reaches a stationary value, Cr6þ
sites are completely reduced to catalytically active Cr2þ
(i.e., [Cr2þ]ss  [Cr6þ]0). Then, the propagation rate con-
stant can be determined from the stationary polymerization
rate data using Equation (34). The reaction rate constant
(k1) for the reduction of Cr6þ to Cr2þ can be estimated from
Equation (8): at constant monomer concentration, Equation
(8) is solved to

½Cr6þ  ¼ ½Cr6þ 0 expðk1 ½M2 tÞ ð35Þ

Assuming that [Cr6þ] ¼ 0.5 [Cr6þ]0 at t1/2 ¼ 0.5 tss

(tss ¼ time to reach Rp,ss (stationary polymerization rate)),
we can determine the k1 value from Equation (35) as
Figure 1. Arrhenius plot of rate constants for ethylene
ln 2 polymerization with supported chromium oxide catalysts (^,
k1 ¼ ð36Þ k1 (L2  (mol2  min)1); ~, k2 (L  (mol2  min)1); &, k3
½M2 t1=2 (1  min1)).

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 Modeling of Ethylene Polymerization Kinetics over Supported Chromium Oxide Catalysts 175

Table 2. Molecular weight data.

Run T Mw PDIa) Reaction Induction

No. time time
8C min min
1 80 566 000 44.6 331 90
2 90 345 000 36.4 114 4
3 90 375 000 30.2 209
4 100 288 000 22.3 286 2.5
5 105 180 000 14.8 94 1
a)
PDI ¼ M w =M n .

Figure 2. Polymerization rates at different reaction tempera-
tures: symbols – data, lines – model simulations.
induction time becomes shorter at higher temperatures. In
our simulations, it was observed that the duration of
induction time was most strongly affected by the reactiva-
tion rate constant (k3). Figure 2 shows the experimentally
measured and the model-predicted polymerization rate
profiles at 80, 90, 100, and 105 8C. Both experimental data
and the model calculations show that indeed the induction
period becomes shorter at higher polymerization tempera-
tures. Some discrepancies between the model predictions
and the experimental data are present but the agreement
between the two seems quite reasonable, supporting the
validity of the proposed kinetic model for the experimental
conditions employed in this work.
We have also calculated the concentrations of various
chromium species and the poison species. Figure 3 shows
the normalized concentration profiles at 90 8C. Notice that
Figure 3. Normalized concentration profiles of various chro-
mium species (Cr*: poisoned chromium site) at 90 8C.
the concentration of active Cr2þ sites remains very low
in the first 20–30 min as the concentration of poisoned sites
(Cr*) increases. After the inactive site concentration (Cr*)
reaches a peak at about 40 min, it decreases slowly even in
the absence of poison species because the reactivation
reaction occurs very slowly.
To determine the chain transfer rate constants, experi-
mental data of weight average molecular weight (M w ) and
polydispersity (PDI) shown in Table 2 are used (Note:
Although the polydispersity values were very large, uni-
modal MWD curves were observed). Figure 4 shows the
effect of reaction temperature on the molecular weight
profiles (symbols). We make the following observations:
(i) Molecular weight averages are moderately tempera-
ture dependent;
(ii) Experimentally measured molecular weight increases
gradually with time during the early reaction period
and then levels off;
(iii) Molecular weight distribution represented by poly-
dispersity (PDI ¼ M w =M n ) is very broad;
(iv) Polydispersity tends to increase as temperature is
decreased.
The increase of polymer molecular weight with
reaction time seems to be caused by the slow and steady
increase of polymerization rate after the induction period.
For example, at 80 8C, the model calculated molecular
weight (M w ) remains low until t ¼ 50 min; however, as
polymerization rate starts to increase, M w also increases
accordingly. Also, observed high polydispersity values
strongly suggest the presence of multiple types of active
sites.
The data shown in Figure 2 and 4 are used to determine
the mole fractions of the two catalytic sites (f1 and f2) and
the monomer chain transfer rate constants. We used a
numerical optimization technique, FSQP (feasible sequen-
tial quadratic programming), which is for the minimization
of the maximum of a set of smooth objective functions sub-
ject to general smooth constraints. Of course, other standard
optimization packages can also be used. At 100 8C, we
obtained the following rate constants for the two-site model

Macromol. Theory Simul. 2004, 13, 169–177 www.mts-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
176
Figure 4. Effect of reaction temperature on polymer molecular
weight averages and polydispersity: symbols – data ( (80 8C), *
(90 8C), * (100 8C), ~ (105 8C)), lines – model simulations.
proposed in this work:


13 19; 180
Site 1 : kfm ð1Þ ¼ 1:834 10 exp 
RT
L  ðmol  minÞ1 ; f1 ¼ 0:55


31; 017
18
Site 2 : kfm ð2Þ ¼ 4:235 10 exp 
RT
L  ðmol  minÞ1 ; f2 ¼ 0:45
Notice that the two sites are present approximately in
equal proportions but the monomer chain transfer rate
constants are quite different; e.g., at 100 8C, kfm(1) ¼ 105.8
whereas kfm(2) ¼ 2.8. In other words, site 2 produces much
longer polymer chains than site 1. Also, the monomer chain
transfer rate at site 2 is much more sensitive to temperature
than that of site 1. The model simulation results are shown
in Figure 4 (solid lines). The model predictions of M w
(weight average molecular weight) look quite good. There
are some discrepancies between the model predictions and
the experimental data in M n (number average molecular
weight) values during the first 100 min of reaction.
Macromol. Theory Simul. 2004, 13, 169–177 www.mts-journal.de
K. Y. Choi, S. Tang, W. J. Yoon
Figure 5. Effect of ethylene concentration on molecular weight
averages and polydispersity at 100 8C: symbols – data (*, 10%;
*, 8%; , 5%), lines – model simulations.
The effect of ethylene concentration on polymer molec-
ular weight averages at 100 8C is shown in Figure 5. It
appears that the ethylene concentration effect is almost
insignificant within the range of ethylene concentration
employed in the experimental study (5–10 mol-%). This is
in agreement with the literature reports.[3] Again, the
proposed model predicts that M w increases much more
slowly than M n , which is in agreement with experimental
data.
Conclusion
The ethylene polymerization over silica supported chro-
mium oxide catalyst is often characterized by the presence
of an induction period followed by a steady increase in
polymerization rate. The molecular weight distribution is
also quite broad. In this paper, a general multi-site kinetic
model is derived and reduced to a two-site kinetic model for
the modeling of polymerization rate and molecular weight
distribution. The initial induction period is modeled by the
catalyst poisoning effect where reactivation of the poisoned
site is assumed to be the rate controlling process. To model
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Modeling of Ethylene Polymerization Kinetics over Supported Chromium Oxide Catalysts
the molecular weight distribution broadening, each active
chromium site is assumed to have the same chain propa-
gation activity but different monomer chain transfer ability.
The experimentally observed polymerization rate and
molecular weight average data were used to determine
the model parameters including the site fraction of each
catalytic site and their monomer chain transfer rate cons-
tant. The experimental data of semibatch liquid slurry
polymerization of ethylene are compared with the model
simulations and a quite satisfactory agreement has been
obtained for the polymerization conditions employed. In
particular, the presence of an induction period is quite
reasonably well predicted by the model. It should be noted
that the kinetic parameters estimated in this work are valid
only with the assumptions we employed in developing a
kinetic model. It is possible that the two-site model can be
expanded to a multi-site model to improve the accuracy of
model predictions, but at this point, no analytical techni-
ques are available to identify the type of active sites and
their catalytic activities. Therefore, the two-site kinetic
model is viewed as a practical compromise. Although the
proposed kinetic model offers a simplified view of the much
more complex polymerization kinetics of chromium oxide
catalyzed ethylene polymerization, the model is the first to
show the quantitative predictions of the time-delayed
polymerization rates and broad MWD. We believe that
the proposed model would be useful in developing a macro-
scopic reactor model for a large-scale process simulation.
To improve the kinetic model in the future, a better quan-
titative understanding of the site activation process and
branching reactions would be necessary. In our model, we
assumed that the effects of particle heterogeneity such as
Macromol. Theory Simul. 2004, 13, 169–177 www.mts-journal.de
177
monomer diffusion resistance or catalyst fragmentation
were negligible. Certainly, these factors may have to be
incorporated into a future modeling work to improve the
accuracy of the model.
Acknowledgement: This work was carried out in collaboration
with Solvay s.A., Brussels, Belgium. Helpful discussions with
Mr. T. Servais, Mr. M. Hanquet and Dr. R. Liegeois are gratefully
acknowledged. One of the coauthors (WJY) also acknowledges
the support by Kyungwon University during his sabbatical leave at
University of Maryland to participate in the completion of this
paper.
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ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim