Fluidized Bed Reactor PDF

Fluidized Bed Reactor for Catalytic Olefin Polymerization
Kinetics and Fluidization
Gerben B. MEIER
i
CIP-gegevens Koninklijke Bibliotheek, Den Haag
Meier, Gerhardus B.
Fluidized bed reactor for catalytic olefin polymerization
ISBN 90-36514894
Trefw.: fluidized bed reactor, olefin, polymerization, metallocene catalyst, sorption,
particle mixing, segregation, draft tube, modeling
Copyright  2000 by G.B. Meier, Enschede, The Netherlands
No part of this book may be reproduced by any means, nor transmitted, nor translated
into machine language without permission from the author
Referent: Dr. ir. S.M.P. Mutsers
Cover design: L.H.M. Meier and M.G.J.J. Hartgerink
The research described in this thesis was performed at the Twente University, Enschede,
The Netherlands. The investigations have been funded by BRITE-EURAM Project
CATAPOL (BE 96-3022).
ii
FLUIDIZED BED REACTOR FOR CATALYTIC OLEFIN
POLYMERIZATION
PROEFSCHRIFT
ter verkrijging van

de graad van doctor aan de Universiteit Twente,
op gezag van de rector magnificus,
prof. dr. F.A. van Vught,
volgens besluit van het College voor Promoties
in het openbaar te verdedigen
op donderdag 30 november 2000 te 16.45 uur.
door
Gerhardus Bernardus Meier
geboren op 22 april 1972

te Stad Delden
iii
Dit proefschrift is goedgekeurd door de promotor
Prof. dr. ir. W.P.M. van Swaaij
en de assistent-promotor
Prof. dr. G. Weickert
iv
Aan Dynah
v
vi
Contents
Summary 1
Chapter 1: General introduction 5

Outline of the thesis 7
History of the project 8
Chapter 2: Comparison of gas and liquid phase polymarization of 9

propylene with a heterogeneous metallocene catalyst
Abstract 9
Introduction 11
Experimental 11
Sorption of propylene 11
Polymer sample characterization 13
Experimental set up for liquid propylene polymerizations 13
Experimental set up for gas phase polymerizations 14
Catalyst system 15
Liquid phase polymarization procedure 16
Gas phase polymarization procedure 17
Sorption theory 17
Sorption of hydrogen 19
Kinetic model 19
Results from sorption measurements 20
Results of liquid phase experiments 23
Influence of Al/Zr ratio 23
Influence of temperature 23
Influence of hydrogen 25
Results of gas phase experiments 27
vii
Influence of pressure 27
Comparison between liquid and gas phase 29
polymarization kinetics
Conclusions 32
Notation 33
Greek 33
Sub- and superscripts 33
Abbreviations 34
Literature 34
Appendix 36
Chapter 3: Gas phase polymerization of propylene with a 37

heterogeneous metallocene catalyst. The influence
of temperature, pressure and hydrogen on the
reaction kinetics and molecular weight distribution
Abstract 37
Introduction 39
Experimental 39
Kinetic model 40
Molecular weight and molecular weight distribution 41
Results 43
Influence of pressure 50
Influence of hydrogen 52
Interpretation of the acceleration period 55
Molecular weight and molecular weight distribution 56
Conclusions 63
Notation 64
Greek 65
Subscripts 65
viii
Abbreviations 65
Literature 65
Chapter 4: FBR mini-plant for catalytic olefin polymerization: 67

Particle mixing and propylene polymerization
Abstract 67
Introduction 69
Sheeting, elutriation and agglomeration 69
Present work 70
Experimental 71
Fluidized bed reactor set up 71
Catalyst system 73
Catalyst injection system 74
Electrostatics 75
Experimental procedures for mixing and segregation experiments 75
Experimental procedures for semi-batch polymerizations 75
Results 76
Mixing of particles 76
Seggregation of particles 77
Batch polymerization experiments 79
Simplified reactor model 83
Discussion 86
Conclusion 87
Notation 88
Greek 88
Subscripts 88
Abbreviations 89
Literature 89
ix
Chapter 5: FBR mini-plant for catalytic olefin polymerization: 91
Controlled particle mixing, propylene polymerization
and reactor modeling
Abstract 91
Introduction 93
Experimental 94
FBR set up 94
Catalyst system 95
Experimental procedure for solids circulation measurements 96
Experimental procedure for semi-batch polymerizations 96
Results 97
Solids circulation 97
Semi-batch polymerizations 99
Injection of hydrogen 103
Reactor model 105
Modeling results 112
Injection of hydrogen 116
Discussion 119
Conclusion 120
Notation 121
Greek 121
Sub- or superscripts 122
Abbreviations 122
Literature 122
Samenvatting 123
Dankwoord 127
Levensloop 129
x
SUMMARY
Summary
Due to the continuous improvement of catalysts and processes, polyolefins have become
one of the most important plastics in the world. Polyolefins can be produced at low costs
with a variety of end-use properties. Nowadays, the most important propylene
polymerization processes are executed in the liquid or the gas phase or a combination of
both. In contrast to propylene polymerizations in slurry phase, only a few studies have
been published concerning gas or liquid phase polymerization. Especially experimental
investigations of gas phase polymerizations at relevant process conditions, i.e. high
pressure and temperature, are rare. The most widely established industrial gas phase
technology is the fluidized bed reactor operating at 10 – 30 bar. Conversion per pass is
kept low, 1-3%, to diminish concentration and temperature gradients in the reactor, which
both affect the polymer properties. In 1 to 3 hours, polymer particles with a broad size
distribution are obtained. There are no experimental data available in the open literature
about the polymerization in such a reactor.
The study reported in this thesis is concerned with a modified small-scale fluidized bed
reactor to study aspects of the gas phase polymerization of propylene with a
heterogeneous metallocene catalyst at conditions resembling those of industrial units as
well as strongly deviating conditions. Controlled thermal gradients are provoked as they
may be of interest to broaden the molecular weight distribution. To study the
polymerization in such a reactor an experimentally validated kinetic model is required.
The kinetic model, obtained from experiments at isothermal and isobaric conditions, is
used to describe the polymerization at non-isothermal conditions in the fluid bed reactor
with related molecular weight distribution of the polymer. Other important aspects that
will be studied are electrostatic charging, particle mixing and elutriation of fines.
Polymerization kinetics
Propylene has been polymerized in both liquid and gaseous propylene in stirred tank
reactors with Me2Si[Ind]2ZrCl2 / MAO / SiO2(Grace) as metallocene catalyst. Gas phase
polymerizations have been executed in the temperature range of 40 to 80°C and pressures
of 5 to 25 bar. Polymerizations in liquid propylene have been carried out at temperatures
between 40 and 70°C and at hydrogen concentrations between 0 and 2.2% in the gas cap.
To describe the reaction kinetics a simplified kinetic model has been developed, which
assumes first order kinetics with respect to the number of active centers and the monomer
concentration in the polymer. The monomer concentration in the amorphous part of the
semi-crystalline polymer, i.e. near the active center, has been determined experimentally.
At low pressures, Henry’s law can be used to describe the concentration. At higher
pressures, the Flory-Huggins equation is used to fit the sorption isotherms. Decreasing
values for the Flory-Huggins interaction parameter with increasing temperature have
1
SUMMARY
been found. The sorption data have been used to compare the relative reaction rates
observed in gaseous and liquid propylene. Lower relative reaction rates were found in gas
phase compared to the experiments in liquid phase. The activation energies found for the
experiments in both phases are in the same order of magnitude.
In another series of kinetic experiments, propylene have been polymerized in the gas
phase at different temperatures, pressures and hydrogen concentrations using
Me2Si[Ind]2ZrCl2 / MAO / SiO2(PQ) as catalyst. This catalyst is supported on another
support and with a different metallocene loading, compared to the catalyst used for the
experiments described above. The reaction rate curves have been described with a kinetic
model, which respects both the initially increasing polymerization rate and the
deactivation of the catalyst. At high temperatures, pressures and hydrogen concentrations
reduced polymer yields have been found, which was interpreted as a thermal runaway on
particle scale. The polymer samples were analyzed on their molecular weight by Gel
Permeation Chromatography (GPC). The molecular weight and molecular weight
distribution of the polymer samples could be described with a “two-site model”. At
constant temperature, the chain transfer probability of both site 1 and 2 was found to
depend only on the hydrogen concentration divided by the monomer concentration.
Polymerization in a small-scale FBR

At the High Pressure Laboratory of the Twente University, a small-scale fluidized bed
reactor has been constructed for the catalytic polymerization of olefins under pressure.
Also particle mixing and segregation have been studied at increased pressure. It appeared
that the solids mixing is relatively fast compared to the residence time of catalyst
particles in case of a polymerization process. However, the smaller particles accumulated
in the upper zone. Moreover, electrostatic charging caused the forming of a layer of small
particles at the reactor wall with increasing thickness in time. The particles were
redispersed after injection of an anti-static agent. Semi-batch propylene polymerization
experiments at different fluidization velocities showed that the vertical temperature
gradients are created, which are caused by catalyst segregation as the principle factor.
Specially at low gas velocities both segregation and mixing can be different under
reacting conditions compared to non-reacting conditions due to different particle-particle
interactions. Despite the fact that fluidized bed reactors can hardly be scaled-up from
experiments in reactors with diameters below 30 cm, small-scale fluidized bed reactor
experiments can contribute to address and quantify incomplete mixing and electrostatic
charging effects. However, the balance between mixing and segregation cannot be
compared to an industrial sized unit and vertical mixing in this un-modified fluid bed
reactor should be enhanced to be more representative.
2
SUMMARY
Therefore, the small-scale fluidized bed reactor has been equipped with a draft tube and
conical bottom section to control the vertical solids mixing. In this set up, particles are
forced to move upwards in the draft tube section under fast fluidization conditions and
enter the annulus section where they flow as a moving bed. The internal solids circulation
rate is a non-linear function of the gas velocity of the unit. Strongly reduced elutriation
and entrainment have been observed, compared to experiments without draft tube.
Semi-batch propylene polymerizations have been executed at elevated pressures.

Although the draft tube can be used to increase the solids mixing, the emphasis in the
present work is put on the creation of different zones in the reactor. The temperature
gradients in the reactor can be controlled from almost absent to large gradients by
changing the solids circulation rate. Hydrogen injections lead to an instantaneous
increased polymerization rate, probably due to the reactivation of dormant sites. The
irreversible deactivation rates of dormant and active sites seem to be the same. Moreover,
hydrogen appeared to be very effective to broaden the molecular weight distribution. A
compartment model is developed, which is able to describe the temperature profile in the
reactor and related molecular weight distribution of the polymer.
3
CHAPTER 1
4
CHAPTER 1
Chapter 1
General introduction.
Polyolefins are today the major plastics materials in terms of production capacity thanks
to its versatility, low costs and excellent processability. The global polypropylene market
has become one of the fastest growing and the production exceeds 30 million tons in
2000. Since the discovery of the Ziegler-Natta catalysts in the early 1950’s, highly active
and stereo-selective catalysts have been developed. The high catalyst activity accounts
for low catalyst residues in the polymer, which can be left in the final product. Modern
polymerization processes require heterogeneous catalysts to control the morphology of
the polymer powder and to reduce the required amounts of cocatalyst. Thanks to the
continuous development of new types of catalysts and processes, new materials have
been introduced to the market thereby expanding the market share of polyolefins.
Since the 1980’s chiral metallocene catalysts were synthesized, which were able (in
combination with methylaluminoxane) to polymerize olefins with controlled molecular
architectures. The narrow molecular weight distribution of the obtained polymer reflects
the single site behavior of this type of catalyst. Despite of the great potential of the
metallocene catalysts, Ziegler-Natta catalysts are still responsible for the major part of the
polyolefin production.
A clear trend towards gas phase polymerization processes can be observed where solvent
recycling is not required and a larger variety of products can be obtained. The most
widely established industrial gas phase technology is the fluidized bed reactor, see figure
1. Here, the bed is kept in the bubbling regime by recycling the reaction gases with
conversion of 1-3% per pass through the reactor. The heat of reaction is removed by
cooling the circulating gas and sometimes by a partial condensation in order to use the
heat of evaporation of the condensates (condensed mode). The reactor is operated at
constant pressure, in general between 10 and 30 bar.
5
CHAPTER 1
Catalyst fragments
surrounded by
polymer
Heat
exchanger
Cyclone
Compressor
Catalyst
injection
Product
Mass transfer removal
from bulk
Heat transfer
to bulk
Monomer
Catalyst
particle
Figure 1: Several characteristic length scales in a fluid bed reactor for catalytic olefin
polymerization. The reactor diameter is on the order of meters, the particles are tens to
hundreds of microns and the sub fragments on the order of hundreds of nanometers.
Polymer properties like the molecular weight distribution of the polymer are influenced
by the type of catalyst, temperature, monomer concentration and hydrogen concentration.
Temperature and concentration gradients in fluidized bed reactors are a strong function of
the solids mixing and segregation rates inside the reactor, which are directly related to the
reactor scale. At an industrial scale, bubbles rising from the distributor plate tend to
accumulate in the center of the reactor, causing an upward “gulf stream” of polymer
powder. Depending on the H/D a single or more mixing cells may occur. This strong
mechanism of solids mixing reduces temperature and concentration gradients in fluid
beds. In a small-scale unit, axial mixing is lower and “gulf streaming” is less prominent
or absent.
In the open literature on olefin polymerization there are no experimental data available on
the fluidized bed reactor, probably because of the knowledge protection by industries.
Moreover, the investment and operation costs for a pressurized experimental facility of
acceptable size are high. A kinetic model based on experiments at relevant process
conditions, i.e. same pressure and temperature range, is crucial for studying the
polymerization in a fluidized bed reactor.
6
CHAPTER 1
Outline of the thesis

The objective of the work presented in this thesis is to study the important aspects of the
polymerization of propylene with a heterogeneous metallocene catalyst in kinetic and
fluid bed reactors. Some key aspects are the applicability of kinetic models derived from
experimental data measured in stirred tank reactors for small-scale fluidized bed reactors,
the influence of particle mixing and segregation on the temperature profile in fluidized
bed reactors and how to scale-down a fluidized bed reactor for olefin polymerization.
Using a modified fluidized bed reactor, the polymerization of olefins is studied at
conditions resembling those of industrial fluidized beds as well as strongly deviating
conditions with controlled thermal gradients. The latter may be of interest for a controlled
broadening of the molecular weight distribution.
At present heterogeneous metallocene catalysts, which are able to produce polyolefins

with a high molecular weight at high production rates, are not commercially available.
The heterogeneous metallocene catalyst used in the present work is the well-known
metallocene rac-Me2Si[Ind]2ZrCl2 / MAO / SiO2. This catalyst produces polyolefins with
a narrow molecular weight distribution but with a low molecular weight.
Chapter 2 describes the gas and liquid phase polymerization of propylene using the
heterogeneous metallocene catalyst in a 0.5 and 5 liter stirred tank reactor, respectively.
The influence of temperature and pressure on the reaction rate has been investigated and
is fitted with a relatively simple kinetic model. Sorption measurements have been carried
out to determine the concentration of monomer in the polymer as a function of process
conditions. Using the sorption data, the obtained kinetic data in gas and liquid phase have
been compared.
Chapter 3 presents the results of a kinetic study with the same metallocene catalyst but on
a different silica support. Gas phase polymerizations at different temperatures, pressures
and hydrogen concentrations have been executed and described with a kinetic model,
which considers both the activation and deactivation of the catalyst. The molecular
weight and molecular weight distribution of the obtained polymer samples have been
measured by Gel Permeation Chromatography (GPC).
Chapter 4 describes the small-scale fluidized bed reactor as built up in the High Pressure
Laboratory of the Twente University. Mixing and segregation experiments have been
executed, which have been used to quantify the effects on the temperature profile
observed during polymerization experiments.
Chapter 5 describes the controlled mixing in the small-scale fluidized bed by installation
of a draft tube and conical bottom section in the reactor. Now, particles are forced to
7
CHAPTER 1
move upwards in the draft tube section under fast fluidization conditions and enter the
annulus section where they move in a densified form under the action of gravity. In this
way a solids circulation is set up, which can be controlled by the inlet gas velocity.
Because the draft tube and annulus are generally operated at different gas velocities, both
sections have different heat transport properties, temperatures and temperature gradients.
Therefore, for a particle circulating through the reactor an oscillating particle temperature
may occur along the particle trajectory resulting in a broadening of the molecular weight
distribution. A reactor model has been developed that describes the temperature and
concentration gradients inside the reactor with the related molecular weight distribution
of the polymer.
Each chapter has been submitted for publication and therefore has been written in such a
way that it can be read independently of the other chapters.
History of the project

This project was started in 1996 under supervision of Prof. Dr. Ir. K.R. Westerterp and
Prof. Dr. Ing. G. Weickert. After the retirement of Prof. Westerterp in 1998 the
supervision was taken over in 1999 by Prof. Dr. Ir. W.P.M. van Swaaij and Prof.
Weickert. The work has been done as part of a BRITE-EURAM project named Catapol
(BE 3022). This project is a cooperation between 4 European universities and 4 industrial
companies and is financially supported by the European Community and the participating
companies. The final results of the project were presented during the first European
conference on the reaction engineering of polyolefins (ECOREP), July 2000 in Lyon.
8
CHAPTER 2
Chapter 2
Comparison of gas and liquid phase polymerization of

propylene with a heterogeneous metallocene catalyst.
Abstract
Sorption measurements are executed to study the sorption behavior of propylene in the
semi-crystalline polymer. Decreasing values for the Flory-Huggins interaction parameter
with increasing temperature are obtained. Large deviations are found, especially at
higher temperatures, compared to data from literature. Propylene is polymerized in both
liquid and gaseous propylene with rac-Me2Si[Ind]2ZrCl2 / MAO / SiO2(Grace) as
metallocene catalyst. Lower relative reaction rates are found in gas phase compared to
the experiments in liquid phase. The activation energies found for the experiments in both
phases are in the same order of magnitude. However, the sorption data used, literature
vs. experimental, have a large effect on the determined kinetic parameters.
9
CHAPTER 2
10
CHAPTER 2
Introduction
In comparison with the conventional Ziegler-Natta catalyst systems, metallocene
catalysts offer a higher versatility and flexibility for the synthesis and control of
polyolefin polymers. Despite all the development efforts in the area of synthesis of new
catalyst compounds, few experimental studies are found in the open literature concerning
the kinetic behavior of these metallocene systems at relevant process conditions.
Especially kinetic data for gas and liquid phase, i.e. liquid propylene, polymerizations are
scarce. Moreover, only a few studies are known in which the kinetics in both phases are
compared. For modern propylene polymerization processes, which contain both liquid
and gas phase steps, heterogeneous catalysts are required to obtain polymer particles with
a narrow particle size distribution and high bulk density. However, it is well known that
the catalyst behavior depends on the carrier and the supporting technique. In general,
lower activities and higher molecular weights were found using heterogeneous analogues.
Propylene polymerization with a heterogeneous catalyst is a complex process, involving

both chemical and physical effects. In order to reach the active centers, monomer
molecules have to absorb into the amorphous part of the semi-crystalline material, then
diffuse to the active centers. On the kinetic level, the reaction is based on the rates of
activation, propagation and deactivation processes, all dependent on various process
conditions. However, the reaction mechanism is independent of the reaction phase, i.e.
the local polymerization rate depends on the local reaction conditions like temperature
and monomer concentration. Hutchinson et al.1 and Samson et al.2 showed that the
kinetics can be unified by calculating the monomer concentration on the basis of polymer
solution thermodynamics.
In this paper, results from gas and liquid phase polymerizations are reported using rac-
Me2Si[Ind]2ZrCl2/MAO/TIBA/silica (Grace) as catalyst system. Sorption experiments
were carried out to determine the monomer concentration near the active center. The
results of the kinetic experiments are compared to check whether the kinetics are
independent of the reaction phase.
Experimental
Sorption of propylene
Sorption of propylene into polypropylene has been measured using a gravimetric method.
By adding propylene gas to a vessel filled with polypropylene, the increase in weight has
been used to calculate the sorption of propylene in the amorphous part of the semi-
crystalline material, see figure 1.
11
CHAPTER 2
PI VENT
ARGON
NC
VACUUM
PI
PI TI
5
TI
1
4
2
3
NC 1 Propylene vessel
Control Valve Check Valve 2 Water bath
Valve 3 Balance
Relief Valve
4 Sorption vessel
PI
Pressure Reducer 5 Capillary
Figure 1: Experimental set up for sorption measurements.

The sorption vessel (4), which has a volume of 218 ml, is filled with 75 grams of polymer
and is placed on a balance (3). All tubes containing propylene gas are electrically heated
to prevent condensation. The temperature inside the sorption vessel itself, also heated
electrically, is controlled with an Eurotherm PID controller. To reduce any manual
handling during the measurements, an actuated valve is installed to add the propylene
automatically. Before starting the addition of propylene, the sorption vessel is evacuated
for one hour. Prior to the addition of propylene, the weight of the vessel is measured and
monitored for half an hour to ensure that the balance stabilized. After stabilization, the
computer will start the propylene addition by opening the actuated valve. The valve is
closed when the desired pressure has been reached. After the propylene addition the
computer program waits until the pressure, temperature and sample mass are stabilized
and saves the data to disc. The procedure necessary to calculate the sorption data is given
in the appendix.
12
CHAPTER 2
Polymer sample characterization

The polymer used for the sorption experiments is a product of a liquid pool experiment at
60°C, using the same catalyst system as has been used for the present kinetic
measurements, see below. The density (pores excluded), crystallinity and porosity have
been determined, see table 1. The porosity is determined by mercury intrusion,
considering a pore size between 0.1 and 10 µm. To verify that these characteristics do not
change during the experiments, the product has been analyzed prior and after the
experiments. From DSC curves, it could be concluded that the crystallinity does not
change in the whole range in which measurements have been executed.
Table 1: Some characteristics of the polymer used for the sorption experiments.
Polymer Density Crystallinity Porosity
[g/ml] [%] [%]
Prior to measurements 0.91 43.5 22

After experiments 0.91 43.7 20
Experimental set up for liquid propylene polymerizations

Liquid phase polymerizations have been executed in the same set up as was used by
Samson et al.3. The set up comprises a 5 liter jacketed reactor, catalyst injection system
and purification systems for propylene, hydrogen, nitrogen and hexane. Additionally, the
reactor is equipped with a helical stirrer and a sampling system, see also Shimizu et al.4.
Batch experiments have been carried out at isothermal conditions. The reaction rate has
been determined by a calorimetric method assuming a constant heat transfer coefficient
during the experiment.
13
CHAPTER 2
Experimental set up for gas phase polymerizations

The experimental set up for gas phase polymerizations is schematically shown in figure
2.
PI
Hydrogen
4
PI TI
3
NC
NC
2 5
NO
85 C
1 VACUUM
PURGE
TI
PI
PC
1 Reactor
NC
Control Valve, NC Rupture Disk 2 Catalyst injection
3 Hydrogen injection
NO
Control Valve, NO Relief Valve 4 Evaporation vessel
PI
5 Traced mass flow
Valve Pressure Reducer
controller
Figure 2: Experimental setup for gas phase polymerizations.
The set up is based on the set up described by Samson et al.2. Some adjustments, see
below, have been carried out in order to operate at higher pressures and to handle a
different catalyst. The set up consists of a stainless steel 0.5 liter Büchi reactor for
pressure up to 40 bar, a catalyst injection system, a small vessel to inject a certain amount
of hydrogen, an evaporation vessel and a temperature control system.
14
CHAPTER 2
By keeping the temperature and pressure constant during the experiment, the reaction rate
can be calculated from the feed rate required to keep the reactor pressure constant.
Propylene gas, evaporated in the evaporation vessel, is fed into the reactor via a traced
mass flow controller. The liquid propylene in the evaporator is kept at a temperature of
70°C, to be able to execute experiments up to 25 bar. To prevent condensation of
propylene, all tubes of the monomer feed system are traced at 85°C.
A special helical stirrer has been used to enforce good mixing inside the reactor.
Moreover, 50 grams of inert sodium chloride have been used for every experiment to
prevent catalyst particles from sticking to each other and to the reactor wall. The sodium
chloride also improves the heat transfer from the reacting particles to the reactor wall.
The stirrer forces the powder mixture to move upwards along the reactor wall, and
downwards along the stirrer shaft under the influence of gravity. A lower propeller stirrer
has been mounted to whirl up the powder on the bottom of the reactor. The temperature
inside the reactor, used to control the temperature within 0.1°C, is measured just above
the stirrer, but in direct contact with the powder flow.
To inject a dry catalyst powder, a new catalyst injection system has been developed. The
catalyst is prepared under nitrogen atmosphere in a glove box and mixed with 50 grams
of sodium chloride. Local high concentrations of catalyst in the reactor are avoided this
way, which may lead to local hot spots. The catalyst mixture is brought into an injection
vessel, which is connected to the reactor set up. Shortly before start-up, the catalyst
mixture is injected via a valve into the evacuated reactor. After the experiment, the
injection vessel is checked for catalyst losses, but they were never found.
Catalyst system
The metallocene catalyst used for the gas and liquid phase polymerizations is rac-
Me2Si[Ind]2ZrCl2, see figure 3. Several groups5,6 studied the polymerization behavior of
this well-known system. Spaleck et al.5 reported a rather low molecular weight (Mw =
36000 g/mol) of the polymer obtained after polymerization in liquid propylene at 70°C in
the absence of hydrogen. Bonini et al.7 studied the heterogeneous analogue in slurry at
low pressure (2 bar) and low temperature (40°C). The system used for this study, was
kindly supplied by Witco Co. Bergkamen (Germany). It is supported on Grace silica with
a concentration of 1 wt%. The MAO/SiO2 – support used for immobilization of the
metallocene contained 25 wt% of alumina, giving a [Al]/[Zr] ratio of 386. The average
particle size of the silica used (SD3216-30, 10 – 110 µm) is 51 µm. A SEM photo of the
morphological structure of one catalyst particle is given in figure 4.
It is well known that the polymerization rate can substantially be increased by adding
small amounts of aluminum alkyls7, especially triisobuthylaluminium (TIBA). To be able
15
CHAPTER 2
to compare the results of gas and liquid phase experiments, the catalyst was precontacted
with TIBA (Akzo Nobel) for 30 minutes prior to injection. The amount of TIBA used for
precontacting has been kept constant resulting in a total [Al]/[Zr] ration of 750.
Me2Si ZrCl2
Figure 3: Catalyst used for the kinetic Figure 4: SEM photo of the catalyst
experiments in liquid and gas phase. morphology.
Liquid phase polymerization procedure

Before each experiment, the evacuated reactor is filled with 1 liter of liquid propylene
and heated to a temperature of 60°C. Next, 200 mg of TIBA is injected to scavenge all
impurities. After one hour of stirring at 1000 rpm, the reactor content is purged through
the drain. Then the prescribed amount of hydrogen and 2.6 liters (at 20°C) of liquid
propylene are added. The hydrogen concentration in the gas cap above the liquid at
reaction conditions has been calculated by calculating the volume of this gas cap and
compensating for the amount sorbed into the liquid propylene. Mizan et al.8 reported
about the solubility of hydrogen in liquid propylene and found a Henry type of sorption,
see equation 1.
C LH 2 = k H PH 2 (1)
Here kH is the Henry coefficient and PH 2 the partial pressure of hydrogen.

In table 2 some relevant data for calculation of the hydrogen concentration in the gas cap
of the liquid phase reactor is given. Data about the density of liquid propylene and the
vapor density have been taken from the VDI-Wärmeatlas9.
16
CHAPTER 2
Table 2: Some relevant data required to calculate the hydrogen concentration in the gas
cap of the liquid phase reactor.
T kH ρG C Lm VG VL
[°C] [mol/l.bar] [kg/m3] [kg/m3] [l] [l]
40 0.0205 33.96 475.50 2.39 2.61

50 0.0245 43.18 454.58 2.32 2.68
60 0.0289 55.27 431.00 2.23 2.77
70 0.0334 72.98 403.17 2.13 2.87
Before catalyst injection, the reactor content is brought to the desired temperature. During
the experiment, the temperature of the reactor and the coolant at the in- and outlet of the
reactor jacket are measured every 20 seconds. The calorimetric method introduced by
Samson et al.3 has been used to calculate the reaction rate in time. After 75 minutes, the
reaction is terminated by fast purging of the reactor. Due to evaporation of the liquid
propylene, the temperature drops rapidly reducing the amount of polypropylene produced
during the non-isothermal phase. The obtained polymer product is removed from the
reactor and dried under vacuum overnight.
Gas phase polymerization procedure

Before each experiment, the reactor is heated to 90°C under vacuum for 30 minutes
followed by flushing with nitrogen. Next, the reactor is brought to the desired
temperature. The hydrogen injection vessel is pressurized with the desired amount of
hydrogen. To prevent initial direct contact of the catalyst with pure hydrogen, the
hydrogen injection vessel is pressurized with propylene up to 9 bar. Then the catalyst/salt
mixture is injected into the evacuated reactor. A computer program written in HP VEE
starts filling of the reactor to the desired pressure. Due to the automation of the set up,
operation is simplified to a large extend. During the reaction, the operator can control the
set up from outside a concrete bunker. The reaction rate is obtained by measuring the
monomer mass flow required to keep the pressure constant during the experiment. After
60 minutes the reactor content is purged to stop the reaction. The polymer product is
washed with water to separate the sodium chloride and dried under vacuum overnight.
Sorption theory
In case the amount of sorbed monomer is sufficiently small, i.e. low monomer-polymer
interaction, Henry’s law can be used to describe the sorption in the amorphous part of a
semi-crystalline polymer.
17
CHAPTER 2
cm = k H P (2 )
The volume fraction of penetrant inside the amorphous part can be calculated with:
k H PM m
φ= (3 )
C Lm
At higher monomer concentrations, the interaction between monomer and polymer

increases. For this situation the Flory-Huggins equation is often used, see equation 4.
P
ln = ln φ + (1 − φ ) + χ (1 − φ ) 2 (4 )
P0
Here P and P0 are the partial pressure and saturation pressure of the monomer,
respectively, and χ is the Flory-Huggins interaction parameter.
Samson et al.3 estimated the Flory-Huggins interaction parameter χ with the Laar-
Hildebrand equation10, see equation 5.
νm
χ= (δ m − δ p )2 + χ s (5)
RT
Here νm is the molar volume of the monomer, δm and δp are the solubility parameters of
the monomer and polymer, respectively, and χs is the correction for entropic interaction.
The solubility parameter δ is a function of temperature, but νm/R(δm-δp)2 and χs are often
nearly independent of temperature11. Therefore, the Flory-Huggins parameter should
decrease with increasing temperature, according to equation 6, which is in contrast to
Samson et al.3.
A
χ= +B (6)
T
Moreover, the Flory-Huggins parameter may depend on the concentration, depending on
the interaction between the solvent, amorphous and crystalline part of the polymer. The
Flory-Huggins equation appears to be very useful when used as a correlative method, but
cannot be used in a predictive way if reasonable accuracy is required. From various
experiments, e.g. Favre et al.12, it has been concluded that the Flory-Huggins interaction
parameter remains an empirical fitting parameter.
The monomer concentration inside the polymer used for kinetic modeling has been
estimated by the following equation:
C m = φ ⋅ C Lm (7)
18
CHAPTER 2
Here C Lm is the concentration of liquid monomer for a given temperature9.
Sorption of hydrogen
It is well known that hydrogen not only influences the molecular weight of the polymer
product but also affects polymerization kinetics. Knowledge of the sorption behavior of
hydrogen as function of process conditions is therefore as important as monomer sorption
behavior. However, for sparingly soluble penetrants sorption can be described by Henry’s
law. For our system the situation is more complicated, because large amounts of
propylene are sorbed into the amorphous part of the semi crystalline material. If Henry’s
law is still valid for the sorption of hydrogen in a polymer matrix swollen with propylene,
polymerization experiments in liquid phase should be executed with the same amount
(mol%) of hydrogen in the gas cap as used for the gas phase experiments when the results
are to be compared later on.
Kinetic model
The propagation rate is dependent on monomer concentration and the number of active
sites. For propylene polymerizations with zirconocenes at low monomer concentration,
several authors13,14 reported the reaction order with respect to monomer concentration to
be higher than one, see equation 8. Fait et al.15 postulated a kinetic model based on the
presence of a single-center, two-state catalyst system, in which both states differ in
propagation rate. According to the proposed mechanism, interconversion between the two
states will lead to a lower concentration of the slow state at higher monomer
concentration leading to an overall order of reaction in the monomer larger than one.
R p = k p C * C nm (1<n<2) (8)
In the simple power law equation 8 kp=kp,0exp(-Eact,p/RT), where kp is the propagation

rate constant and Eact,p the activation energy for propagation. Further, C* is the number of
active centers per gram of catalyst and Cm the monomer concentration based on the
sorption equations presented before.
The decay in polymerization rate generally observed after the built-up period has been
discussed in literature intensively. It is generally believed16 that this loss of activity in
time cannot be explained by intra-particle monomer diffusion limitation through the
growing polymer layer. Most of the experimental results can be analyzed according to a
decreasing number of active centers in time due to chemical deactivation. We have
chosen to describe the deactivation by a simple first order relation:
19
CHAPTER 2
dC * (9)
= −k d C *
dt
Here kd=kd,0exp(-Eact,d/RT), where kd is the deactivation constant and Eact,d the activation
energy for deactivation.
Integration of equation 9 will lead to the number of active sites as a function of time.
C* = C *max e − k d t (10)
with C*max the maximum number of active centers per gram of catalyst.
Substitution into equation 8 leads to:
R p = k p C m C *max e − k d t = R p , max e − k d t (11)
with Rp,max the maximum reaction rate. Note that equation 11 is valid after the built-up
period.
Results from sorption measurements

Propylene sorption experiments have been done at different temperatures (41, 52, 62 and
73°C) and pressures (5 – 25 bar). In figure 5, the results of the sorption experiments are
given, together with a best fit according to Henry’s law. The results are summarized in
table 3. These fits are only based on the sorption measurements at low volume fractions
of.propylene. The data at low volume fractions could be fitted with Henry’s law, but fails
for higher values.
0.35
41°C
0.3
52°C
62°C
0.25
73°C
0.2
φ [-]
0.15
0.1
0.05
0
0 5 10 15 20 25 30
P [bar]
Figure 5: Fitting the sorption measurements with Henry’s law.
20
CHAPTER 2
Table 3: Henry constants at different temperatures used to fit the experimental data at
low volume fractions.
Temperature kH Temperature kH
[°C] [mol/l⋅bar] [°C] [mol/l⋅bar]
41 0.141 62 0.095
52 0.115 73 0.075
For every data point, the Flory-Huggins interaction parameter χ has been determined.
The error in the determined interaction parameter is about 5% for the measurements at
41°C and increases to about 9% for the measurements at 73°C. In figure 6, each
temperature series have been fitted with an average value for the interaction parameter. In
figure 7, the experimental data are fitted using interaction parameters given by Samson et
al.3. The experimentally determined values for the Flory-Huggins interaction parameter
together with the literature values are summarized in table 4. The measured value for the
Flory-Huggins interaction parameter decreases with increasing temperature, whereas the
values given by Samson et al.3 are increasing dramatically with temperature.
0.35
41°C
0.3 52°C
62°C
0.25 73°C
0.2
φ [−]
0.15
0.1
0.05
0
0 5 10 15 20 25 30
P [bar]
Figure 6: Fitting measurements with the Flory-Huggins equation.
21
CHAPTER 2
0.35
41°C 41°C 52°C
0.3
52°C
0.25 62°C
73°C
0.2 62°C
φ [-]
Literature
0.15
0.1 73°C
0.05
0
0 5 10 15 20 25 30
P [bar]
Figure 7: Comparison of sorption measurements with literature data.
0.85
0.8
0.75
0.7
χ [-]
0.65
0.6
0.55
0.5
0.00285 0.0029 0.00295 0.003 0.00305 0.0031 0.00315 0.0032
1/T [K-1]
Figure 8: Measured Flory-Huggins parameters vs. the reciprocal temperature.
22
CHAPTER 2
Table 4: Flory-Huggins interaction parameter as function of temperature; literature vs.

experimental data.
Temperature Interaction parameter Average measured
[°C] given by Samson et al.3 value
41 0.86 0.82
52 0.99 0.75
62 1.16 0.69
73 1.45 0.61
Based on equation 6, a linear relation between the measured interaction parameter and the
reciprocal temperature is expected, see figure 8. Equation 12 represents the best fit.
730.43
χ= − 1.501 (12)
T
All experiments have been executed using the same polymer made in liquid propylene at
60°C with a heterogeneous metallocene catalyst. Care should be taken when using the
absolute values, since the Flory-Huggins interaction parameter may e.g. depend on the
degree of crystallinity of the polymer.
Results of liquid phase experiments

Influence of Al/Zr ratio
The sensitivity towards the amount of TIBA have been tested during three different
polymerization experiments at different Al/Zr ratios, see figure 9. All experiments have
been carried out at 60°C and 2% hydrogen in the gas cap. The polymerization rate has
been calculated as the amount of polypropylene per gram of metallocene on the silica
support per hour, kg/gmet.hr. This is to compare the results later on with catalysts with
different metallocene loading. The large initial fluctuations in polymerization activity do
not depict real fluctuating reaction rates, they are caused by the PID controller. Although
the temperature can be controlled within 0.2°C, the cooling water temperature does show
some small oscillation in the beginning of an experiment, which directly influences the
apparent polymerization rate. The experiments at different Al/Zr ratios show only minor
deviations with each other. This indicates that in this range, a variation in the ratio does
not influence the polymerization rate too much.
Influence of temperature
The influence of temperature on the reaction rate has been studied by varying the
temperature from 40 to 70°C, see figure 10. Table 5 gives an overall summary of the
experiments, presenting the reaction conditions and some fitted kinetic parameters. Note
23
CHAPTER 2
the large differences between the values for the monomer concentration based on
theoretical literature sorption data and the values based on the measured sorption data,
especially at higher temperatures. At 70°C, the measured monomer concentration is about
4 times higher than the concentration calculated by Samson et al.3.
1000
800
Rp [kg PP/gr met hr]
600
Al/Zr = 2091
400 Al/Zr = 700

Al/Zr = 1070
200
0
0 10 20 30 40 50 60 70
Time [min]
Figure 9: Influence of Al/Zr ratio on the polymerization rate during liquid phase
polymerization.
1000
800
Rp [kg PP/gr met hr]
600
70 °C 60 °C 50 °C 40 °C
400
200
0
0 10 20 30 40 50 60 70
Time [min]
Figure 10: Influence of temperature on the polymerization rate during liquid
phase polymerizations.
24
CHAPTER 2
Table 5: Summary of the liquid phase experiments at different temperatures.

T H2 gas cap H2 liquid Cm Cm Rp,max kd
[°C] [mol%] [mol%] [kg/m3] [kg/m3] [kg PP/gmet.hr] [min-1]
This work Samson et al.3
40 2.45 0.028 208.8 200.3 125.8 0.0088

50 2.38 0.043 233.0 156.5 232.5 0.0096
60 2.22 0.064 257.9 111.0 377.5 0.0179
70 2.05 0.086 276.1 70.4 578.0 0.0266
The experiment at 70°C showed the presence of a critical polymer concentration after
about 20 minutes, i.e. a propylene conversion above 40 to 50% causing a sharp decrease
of the heat transfer coefficient manifest from the temperature recordings, see also Samson
et al.3. The observed transition in heat transfer is ascribed to a changing flow behavior of
the reactor content, see Samson et al.3.
Influence of hydrogen
The influence of hydrogen on the polymerization kinetics has been investigated at 60°C
in liquid phase. Experiments have been executed between 0 and 2.2% hydrogen in the gas
cap. This relatively small range has been chosen because the sensitivity of metallocene
catalysts towards hydrogen, related to the molecular weight of the polymer, is large
compared to classical Ziegler-Natta catalysts17. The maximum reaction rate Rp,max and
deactivation constant kd have been determined by fitting the reaction rate curves to
equation 11. In figure 11 and 12, the maximum reaction rate and deactivation constant are
given as a function of the hydrogen concentration. A linear relation is obtained between
the maximum reaction rate and the hydrogen concentration in the gas cap. No saturation
effect, as shown by Samson et al.18, was found for the range in which the experiments
have been executed. However, the increasing trend for the deactivation constant with the
hydrogen concentration, observed at higher hydrogen concentrations, was also found by
Samson et al.18. In general, a higher deactivation rate is observed at higher reaction rates,
either caused by higher temperatures or hydrogen. No deactivation phenomena were
found for the experiment without hydrogen associated with a low reaction rate.
Several possible explanations for the increased catalyst activity in the presence of
hydrogen are given in literature18. One possibility may be the shortcutting of slow
propagation steps, which occur after isolated secondary insertions (2-1 insertions).
25
CHAPTER 2
400
350
300
Rp,max [kg PP/gmet hr]
250
200
150
100
50
0
0 0.5 1 1.5 2 2.5
H2 [%]
Figure 11: Influence of hydrogen on the maximum polymerization rate.

0.02
0.016
0.012
kd [min-1]
0.008
0.004
0
0 0.5 1 1.5 2 2.5
H2 [%]
Figure 12: Influence of hydrogen on the deactivation constant kd.
26
CHAPTER 2
Results of gas phase experiments

The influence of temperature on the polymerization rate has been studied at temperatures
between 40 and 70°C at 10 bar pressure and 2 mol% of hydrogen. As can be seen in
figure 13, the reaction rate as well as the deactivation rate increases with increasing
temperature. In contrast to the experiments in liquid phase, the catalyst does not show
activity directly after injection. Especially at lower temperatures some time is required to
reach maximum polymerization activity. The model presented earlier does not take any
induction period or activation processes into account.
50
70 °C
40
60 °C
Rp [kg PP/gmet hr]
30
20 50 °C
10 40 °C
0
0 10 20 30 40 50 60 70
Time [min]
Figure 13: Influence of temperature on the polymerization rate during gas phase
polymerization at 10 bar pressure.
Influence of pressure
The influence of pressure has been studied between 5 and 25 bar at 70°C. Figure 14
shows that the maximum reaction rate increases more or less linear with the monomer
concentration in the amorphous part of the polymer, reflecting the first order reaction
kinetics. Cm has been calculated according to the experimental sorption data presented
earlier in this paper. Fitting the data at low concentration, below 15 bar, a trend line with
an intercept not equal to zero is obtained, line b in figure 14. This supports the theory of a
reaction order of higher than one discussed before. Another possible explanation may be
a less accurate estimate of the monomer concentration at low pressures.
27
CHAPTER 2
In figure 15 the deactivation rate constant kd is given as function of the monomer

concentration. Again a linear relation is obtained. According to the model the
deactivation rate should not depend on the monomer concentration, however this
dependency has been found before. Kohara et al.19 also obtained a linear relation between
the deactivation constant and the monomer concentration using a Ziegler-Natta catalyst.
350
300 a
Rp,max [kg PP/grmethr]
250
200
b
150
100
50
0
0 20 40 60 80 100 120 140
Cm [kg/m3]
Figure 14: Influence of monomer concentration on maximum polymerization rate

during gas phase polymerization rate at 70°C. a: Fit of all data, b: Fit at low
concentrations; below 15 bar.
0.35
0.3
0.25
kd [min ]
0.2
-1
0.15
0.1
0.05
0
0 20 40 60 80 100 120 140
Cm [kg/m3]
Figure 15: Influence of monomer concentration on the deactivation constant during
gas phase polymerization at 70°C.
28
CHAPTER 2
Comparison between liquid and gas phase polymerization kinetics

The main difference between the gas and liquid phase experiments seems to be the
monomer concentration near the active center. One would expect that the same reaction
mechanism holds for both phases and the same relative polymerization rate (Rp/Cm)
should be obtained. In figure 16 and 17, the Arrhenius plots are given of the gas and
liquid phase experiments based on the measured and (theoretical) literature3 sorption
data, respectively. The constants for the kinetic model, based on both sorption data sets,
are summarized in table 6.
Table 6: The constants for the kinetic model for the gas and liquid phase
polymerizations.
Liquid phase Gas phase
Sorption data set This work Literature3 This work Literature3
sorption data sorption data
k p 0 C*max [m3/hr.gmet] 8.67· 105 3.17· 1012 4.69· 109 1.94· 1011
Eact,p [kJ/mol] 36.8 76.2 48.0 69.7
kd0 [min-1] 5.09· 103 7.95· 103
Eact,d [kJ/mol] 35 31
1
Liquid phase
0.8
0.6 Gas phase
0.4
ln(Rp,max/Cm)
0.2
-0.2
-0.4
-0.6
-0.8
-1
2.9 2.95 3 3.05 3.1 3.15 3.2 3.25
-1
1000/T [K ]
Figure 16: Arrhenius plots (propagation) of gas and liquid phase experiments using
the measured sorption data.
29
CHAPTER 2
2.5
Liquid phase
2 Gas phase
1.5
ln(Rp,max/Cm)
0.5
-0.5
-1
2.9 2.95 3 3.05 3.1 3.15 3.2 3.25
-1
1000/T [K ]
Figure 17: Arrhenius plot (propagation) of the gas and liquid phase experiments
using the sorption data given by Samson et al.3.
-1.5
Liquid phase
-2
Gas phase
-2.5
-3
ln kd
-3.5
-4
-4.5
-5
-5.5
2.9 2.95 3 3.05 3.1 3.15 3.2 3.25
-1
1000/T [K ]
Figure 18: Arrhenius plot (deactivation) for the gas and liquid phase experiments.
30
CHAPTER 2
In general lower relative reaction rates, Rp,max/Cm, have been found in gas phase, which is
in agreement with the results of Samson et al.2. Our simplified kinetic model does not
take activation of the catalyst into account, although a clear initial increase in
polymerization activity has been observed during all gas phase experiments. The time
required to reach the maximum polymerization activity is for a gas phase experiment
about 3-5 minutes. In this time, deactivation processes are already influencing the
polymerization rate, causing a lower maximum polymerization rate. This may explain the
lower relative activity observed for the gas phase experiments. An alternative method
could be to use the initial reaction rate instead of the maximum polymerization rate by
extrapolation to time zero. However, such extrapolations would lead to unrealistic values
of the initial reaction rates. This effect is enhanced by the higher deactivation rate
observed for the gas phase experiments, see figure 18. Samson et al.2 also found higher
deactivation rates during gas phase polymerizations. An arrhenius plot for the gas and
liquid phase experiments based on the initial reaction rate is given in figure 19.
1.5
Liquid phase
1 Gas phase
ln(Rp0/Cm)
0.5
-0.5
-1
2.9 2.95 3 3.05 3.1 3.15 3.2 3.25
-1
1000/T [K ]
Figure 19: Arrhenius plot (propagation) of the gas and liquid phase experiments
using the measured sorption data. Rp0 is determined by extrapolation to time zero.
31
CHAPTER 2
The activation energies found for the liquid and gas phase experiments are in the same
order of magnitude, see table 6. However, the sorption data used, literature vs.
experimental, have a large effect on the determined kinetic parameters. The temperature
series in liquid phase was unfortunately not executed at completely constant hydrogen
concentration in the gas cap. The concentration dropped from 2.45% at the lowest
temperature to 2.05% at the highest temperature, see table 5. The experiments in liquid
phase, in which the hydrogen concentration in the gas cap was varied, show that this
variation in hydrogen concentration will affect the maximum reaction rate. So, the
determined activation energy for propagation for the liquid phase experiments is in fact
too low, about 10%. This may explain the slightly lower activation energy (based on
experimental sorption data) found for the liquid phase experiments. However, the
sorption behavior of hydrogen in a polymer may depend on the amount of propylene
sorbed in the polymer. Such information may help to explain the differences between the
gas and liquid phase kinetic data.
Conclusions
Sorption data of propylene in polypropylene have been measured using a gravimetric
method. At low pressures, sorption could be described with Henry’s law, at higher
concentrations the Flory-Huggins equation appeared to be a useful fitting equation.
Decreasing values of the Flory-Huggins parameter were measured with increasing
temperature, which is in contrast to data given by Samson et al.3 but in line with
theoretical expectations. Polymerizations have been executed in both gaseous and liquid
propylene at different temperatures, pressures and hydrogen concentrations. Hydrogen
appeared to have a large influence on the reaction and deactivation rate. In general, a
higher deactivation rate is observed at higher reaction rates, either caused by higher
temperatures or hydrogen.
The influence of the monomer concentration was studied at 70°C in gas phase. At low
concentrations, below 15 bar, a reaction order above one is obtained. This supports the
theory of a single-center, two-state catalyst postulated by Fait et al.15.
The sorption data of propylene have been used to compare the results of the gas and
liquid phase polymerizations. Lower relative reaction rates have been found for gas phase
polymerizations. The activation energies found for liquid and gas phase experiments are
comparable. The sorption data used, either data from literature or experimental data, have
a large effect on the estimated kinetic parameters.
For a correct comparison between gas and liquid phase kinetic data, not only adequate
monomer sorption data are required, but also hydrogen sorption data. Unfortunately, the
32
CHAPTER 2
sorption behavior of hydrogen in polypropylene swollen with propylene is unknown and

difficult to determine exactly.
Acknowledgement - This work has been funded by BRITE-EURAM Project CATAPOL (BE 96-3022). We
greatly acknowledge K. van Bree and F. ter Borg for the construction of the experimental set ups and
technical assistance. G.H. Banis is acknowledged for his technical support and W.R. Smit, B.G.C.J. Wijers
and S.N. Kuper for their assistance in the experimental part.
Notation
C* Number of active sites mol/gmet
cm Monomer concentration mol/l
Cm Monomer concentration kg/m3
CH2 Hydrogen concentration mol/l
Eact Activation energy J/mol
kd Deactivation rate constant min-1
kH Henry constant mol/l.bar
kp Propagation rate constant m3/mol.hr
m Mass kg
Mm Molecular weight kg/mol
P Pressure bar
P0 Saturation pressure bar
R Gas constant J/mol.K
Rp Reaction rate kg/gmet.hr
t Time min
T Temperature K
V Volume m3
X Crystallinity -
Greek
χ Flory-Huggins interaction parameter -
δ Solubility parameter (J/cm3)0.5
φ Volume fraction -
ν Molar volume cm3/mol
ρ Density kg/m3
Sub- and superscripts

G Gas phase
H2 Hydrogen
L Liquid phase
33
CHAPTER 2
m Monomer
Max Maximum condition
n Reaction order
p Polymer
p Polymerization, propagation
PP Polypropylene
0 Initial condition
Abbreviations
Al Aluminium
MAO Methylaluminoxane
TIBA Tri-isobuthylaluminium
Zr Zirconium
Literature
1. Hutchinson, R.A., Ray, W.H., J. Appl. Polym. Sci., 41, 51-81, (1990)
2. Samson, J.J.C., van Middelkoop, B., Weickert, G., Westerterp, K.R., AIChE J.,
45(7), 1548-1558, (1999)
3. Samson, J.J.C., Weickert, G., Heerze, A.E., Westerterp, K.R., AIChE J., 44(6), 1424-
1437, (1998)
4. Shimizu, F., Pater, J.T.M., Weickert, G., submitted to J. Appl. Pol. Sci., (2000)
5. Spaleck, W., Aulbach, M., Bachmann, B., Küber, F., Winter, A., Macromol. Symp.,
89, 237-247, (1995)
6. Carvill, A., Tritto, I., Locatelli, P., Sacchi, M.C., Macromolecules, 30, 7056-7062,
(1995)
7. Bonini, F., Fraaije, V., Fink, G. J., Polym. Sci. Part A: Polym. Chem., 33, 2393-
2402, (1995)
8. Mizan, T.I., Li, J., Morsi, B.I., Chang, M.Y., Maier, E., Singh, C.P.P., Chem. Eng.
Sci., 49(6), 821-830, (1994)
9. VDI-Wärmeatlas; VDI-Gesellschaft Verfahrenstechnik und Chemieingenieurwesen
(GVC), 6th edition, (1991)
10. Barton, A.F.M., CRC Handbook of polymer-liquid interaction parameters and
solubility parameters, CRC Press, Boca Raton, 284-292, (1990)
11. Prausnitz, J.M., Lichtenthaler, R.N., de Azevedo, E.G., Molecular thermodynamics
of fluid-phase equilibria, Englewood Cliffs, N.J: Prentice-Hall, 2nd edition, (1986)
12. Favre, E., Nguyen, Q.T., Schaetzel, P., Clément, R., Néel, J. J., Chem. Soc. Faraday
Trans., 89(24), 4339-4346, (1993)
13. Fink, G., Herfert, N., Montag, P., Ziegler Catalysts, Springer-Verlag, 159-179,
(1995)
34
CHAPTER 2
14. Jüngling, S., Mülhaupt, R., Stehling, U., Brintzinger, H.H., Fischer, D., Langhauser,
F. J., Polym. Sci., Part A: Polym. Chem., 33, 1305-1318, (1995)
15. Fait, A., Resconi, L., Guerra, G., Corradini, P., Macromolecules, 32, 2104-2109,
(1999)
16. Kim, I., Woo, S.I., Korean J. of Chem. Eng., 7(2), 95-99, (1990)
17. Blom, R., Dahl, I.M., Macromol. Chem. Phys., 200, 442-449, (1999)
18. Samson, J.J.C., Bosman, P.J., Weickert, G., Westerterp, K.R., J. Pol. Sci., Part A:
Polym. Chem., 37(2), 219-232, (1999)
19. Kohara, T., Shinoyama, M., Doi, Y., Keii, T., Makromol. Chem., 180, 2139-2151,
(1979)
35
CHAPTER 2
Appendix
Calculation procedure for sorption measurements
The weight increment from a sorption experiment has been calculated from the measured
mass before and after the addition of propylene gas.
∆m = m 2 − m 1 = m G + m sorbed (13)
The volume of the vessel is used to calculate the volume of the gas not sorbed in the
amorphous part of the polymer, i.e. gas between polymer particles and gas in the pores of
the polymer.
mp (14)
VG = Vvessel − Vp = Vvessel −
ρp
Multiplying this volume by the gas density results in the mass of gas, see equation 15.
m G = VG ρ G (15)
Using the density of liquid propylene the volume of sorbed propylene can be calculated.
∆m − m G
Vsorbed = (16)
C Lm
The volume fraction of the monomer in the amorphous parts of the polymer, φm, can be
calculated with:
Vsorbed Vsorbed
φ= = (17)
Vsorbed + Vp,amorph , 0 Vsorbed + (1 − X )Vp, 0
Swelling of the polymer results in an increase of the polymer volume:
Vp = Vp , 0 + Vsorbed (18)
The calculated polymer volume Vp in turn changes the volume of the gas not sorbed into
the polymer, which influences the volume fraction of monomer sorbed into the polymer,
etc. This step has to be repeated until the volume fraction φ has converged.
36
CHAPTER 3
Chapter 3
Gas phase polymerization of propylene with a heterogeneous

metallocene catalyst. The influence of temperature, pressure
and hydrogen on the reaction kinetics and molecular weight
distribution.
Abstract
Gas phase polymerizations have been executed at different temperatures, pressures and
hydrogen concentrations using rac-Me2Si[Ind]2ZrCl2 / MAO / SiO2(PQ) as catalyst. The
reaction rate curves have been described with a kinetic model, which takes the initially
increasing polymerization rate into account. The monomer concentration in the polymer
has been calculated with the Flory-Huggins equation. The kinetic parameters have been
determined by fitting the reaction rate curves with the model. At high temperatures,
pressures and hydrogen concentrations, a runaway on particle scale may occur leading
to reduced polymer yields. The molecular weight and molecular weight distribution of the
polymer samples could be described with a “two-site model”. At constant temperature,
the chain transfer probability of site 1 and 2 depends only on the hydrogen concentration
divided by the monomer concentration.
37
CHAPTER 3
38
CHAPTER 3
Introduction
Despite the rapid developments in the field of metallocene catalysts, only a few papers
provide kinetic data based on experiments in gaseous monomer, although most
commercial polypropylene processes are carried out in gas phase. These processes are
operated at elevated pressure, e.g. 25 bar, using heterogeneous catalysts. Resconi et al.1
showed that both molecular weight and degree of isotacticity are strongly influenced by
the monomer concentration. In this paper, the gas phase polymerization of propylene with
a heterogeneous metallocene catalyst is described together with the related molecular
weight and molecular weight distribution of the product. The catalyst system used in this
study is rac-Me2Si[Ind]2ZrCl2 with methylaluminoxane (MAO) as cocatalyst. Both
components are supported on Pennsylvania Quarts (PQ) silica.
Experimental
The experimental set up consists of a 0.5 liter jacketed Büchi reactor, a helical stirrer,
injection system for dry catalyst powder and an evaporation vessel for monomer supply.
The set up has been described in detail in a previous paper2. Polymerization reactions
have been executed at constant temperature, pressure and hydrogen concentration. The
reaction rate is calculated from the feed rate required to keep the pressure constant, and
measured by a mass flow controller. The catalyst used, is the well-known metallocene
rac-Me2Si[Ind]2ZrCl2. The catalyst, kindly supplied by Witco Co. Bergkamen
(Germany), is supported on PQ silica with a concentration of 0.79 wt%. The MAO/SiO2
– support used for immobilization of the metallocene contained 19.1 wt% of alumina.
Tri-isobuthylaluminium (TIBA) has been used to increase the polymerization activity.
The amount of TIBA and the precontact time has been kept constant for all experiments.
Some characteristics of the silica carrier (PQ MS3040) are summarized in table 1. Note
the quite large average particle diameter (108µm). The exact polymerization procedure
for the gas phase polymerizations has been described in a previous paper2.
Table 1: Pore size and particle size distribution of the PQ silica carrier.
Minimum Average Maximum
[µm] [µm] [µm]
Pore diameter 0.004 0.2 5
Particle size 27 108 170
The polypropylene samples were characterized on their molecular weight and molecular
weight distribution by Gel Permeation Chromatography (GPC). These GPC
39
CHAPTER 3
measurements were carried out at DSM Research (The Netherlands) on a Waters M150C
apparatus with TSK columns at 140°C using 1,2,4-trichlorobenzene as solvent.
Kinetic model
The polymerization rate in gas phase obtained with the type of catalyst used in this work,
clearly shows an acceleration and deactivation stage in time2,3. The nature of both the
acceleration and deactivation stage has been discussed by many authors before. Kim et
al.4 explained the acceleration stage for a highly active Ziegler-Natta catalyst with the
kinetics of absorption of the cocatalyst. Bonini et al.3 excluded chemical activation
processes, because their metallocene catalyst was preactivated by MAO during the
supporting procedure. They explained the acceleration by diffusion limitations of the
monomer inside the catalyst particle. Their postulated particle growth model accounts for
the shell by shell fragmentation from outside and a final multigrain structure of the
particle.
ki kp
C C* C*-Pj
kd kd
Deactivated catalyst
Scheme 1: Activation, propagation and deactivation of the catalyst.

To formulate a model to describe the complex physical and chemical effects, we have
chosen to describe the reaction rate by empirical relations. Scheme 1 gives a schematic
representation of the activation, propagation and deactivation processes. The non-
activated catalyst, C, is activated by a first order relation to an activated catalyst system
C*, see equation 1.
dC
= −k i C (1)
dt
Here ki=ki,0exp(-Eact,i/RT), where ki is the activation rate constant and Eact,i the activation
energy for activation.
Deactivation is described by a decreasing number of active sites, again using a first order
relation, see equation 2.
dC * (2)
= k i C − k d C*
dt
C* stands for the overall number of active sites including the C*-Pj species from scheme
1. Furthermore, it is assumed that all active sites deactivate with the same rate,
independently whether a chain is attached to it or not.
40
CHAPTER 3
In equation 2, kd=kd,0exp(-Eact,p/RT) where kd is the deactivation rate constant and Eact,d

the activation energy for deactivation. In a previous paper2 it was observed that at
relatively high monomer concentrations, above 15 bar, the polymerization reaction is first
order with respect to the number of active sites and the monomer concentration in the
amorphous part of the polymer.
R p = k p C *C m (3)
Here kp=kp,0exp(-Eact,p/RT), where kp is the propagation rate constant and Eact,p the
activation energy for propagation. The monomer concentration in the polymer has been
calculated with the Flory-Huggins equation. The Flory-Huggins interaction parameter is
based on the experimental data published before2.
Integration and substitution, under isothermal conditions, of equations 1 and 2 leads to:
C* = C 0
ki
kd − ki
(
e −ki t − e −k dt ) (4)
Here C0 is the initial amount of non-activated catalyst.

Substitution into equation 3 leads to:
R p = k p C m C0
ki
kd − ki
(
e− k i t − e− k d t ) (5)
Molecular weight and molecular weight distribution

The molecular weight and molecular weight distribution are important parameters for the
physical, mechanical and rheological behavior of polymers. As a result of the uniform
catalytically active sites of a metallocene catalyst, it is possible to control the molecular
weight and molecular weight distribution. At constant temperature, pressure and gas
composition, the instantaneous molecular weight distribution of a polymer synthesized
with a single-site catalyst can be described with a Schulz-Flory distribution, see equation
6.
y dj = jq 2e − jq (6)
Here, yjd is the density function of the instantaneously formed molecular weight
distribution. This equation depends only on the chain termination probability q. This
parameter is dependent on the type of catalyst and the process conditions, like
temperature, pressure and the hydrogen concentration. Different types of chain transfer
reactions have been observed, e.g. β-hydrogen transfer to the metal and monomer, chain
transfer to aluminium, chain transfer with hydrogen and chain transfer with the monomer.
41
CHAPTER 3
Chain transfer with hydrogen is in general the most effective one, and is often used to
control the molecular weight of polypropylenes under industrial conditions. The
molecular weight of a polymer sample depends on the ratio between the overall
propagation rate and the total chain transfer rates and is in general independent of the
polymerization activity. Combining chain transfer and chain growth reactions, one can
derive:
k m Cm + k H 2 CH 2 + k x (7)
q=
k p Cm + k m Cm + k H 2 CH 2 + k x
Here, km, k H 2 and kx are the rate constants for chain transfer to monomer, hydrogen and
all other chain transfer mechanisms, respectively. During polymerization, high molecular
weight polymers are formed; therefore it can be assumed that:
k p Cm >> k mCm + k H 2 CH 2 + k x (8)
Furthermore, we expect chain transfer reactions with hydrogen and monomer to be much
more important than other chain transfer mechanisms. This leads to equation 9, which
corresponds to the well-known Mayo equation.
k m k H 2 CH 2 (9)
q= +
kp k p Cm
Note that C H 2 , Cm and the temperature are constant during the experiment, which means
that the instantaneous molecular weight distribution corresponds to the integral
distribution obtained after the experiment. In this case we neglect the possible change in
concentration of other components, e.g. MAO or TIBA. It may be possible that these
components are diluted because of the production of polymer.
Data from the GPC analyses can help to calculate the chain transfer probability, see
equation 10.
Mm M
q= =2 m (10)
Mn Mw
Here, Mm is the molecular weight of the monomer, Mn is the number average molecular
weight and Mw is the weight average molecular weight of the polymers, see Weickert5.
The equations presented above are in general only valid for a single site catalyst, where
Mw/Mn = 2, in case of dominating transfer reactions for chain growth termination.
42
CHAPTER 3
Results
The influence of temperature, pressure and hydrogen on the polymerization kinetics have
been studied by using the kinetic model described earlier in this paper. An example of an
experiment together with a fit of the model is shown in figure 1. Fitting is done by
minimizing the deviations between the experimental and model curve. In this figure, also
a fit with the classical model without activation is given. It is obvious that the model
without activation is not able to describe the reaction rate during the first couple of
minutes of the experiment. After about 10 minutes the two different models, both using a
first order deactivation, coincide. Note that an induction period, in general about 1-2
minutes, is not taken into account. Therefore, t = 0 is defined when Rp increases from
zero.
160
140 Model without activation
120
Model with activation
Rp [kg PP / gmet. hr]
100
80
60
40
20
0
0 10 20 30 40 50 60
Time [min]
Figure 1: Fitting an experiment with the kinetic model with and without activation.
For each experiment, the measured reaction rates have been fitted to the model with
activation. The values obtained for the activation constant ki, the deactivation constant kd
and the kinetic parameter kpC0 have been used to analyze the various process parameters
in a qualitative and quantitative manner. Table 2, 3 and 4 give an overall summary of the
experiments, presenting the process conditions and determined kinetic parameters.
43
CHAPTER 3
Table 2: Summary of the experiments; temperature and pressure series.

T p Cm CH
2
kpC0 kd ki Rp,max
3 3 3 -1 -1
[°C] [bar] [kg/m ] [kg/m ] [m /gmet.hr] [min ] [min ] [kg/gmet.hr]
50 15 92.4 0.011 1.031 0.033 0.191 65.9

60 15 67.1 0.011 1.481 0.038 0.320 74.6
60 15 67.1 0.011 1.393 0.040 0.349 70.6
70 15 49.8 0.011 2.563 0.048 0.440 98.8

70 15 49.8 0.011 2.630 0.049 0.424 100.5
75 15 44.0 0.011 2.348 0.046 0.290 73.1
75 15 44.0 0.011 2.201 0.044 0.315 70.4
80 15 38.2 0.011 2.149 0.050 0.311 57.9

70 5.1 14.2 0.011 1.211 0.072 0.256 9.3
70 10.1 30.7 0.011 2.374 0.070 0.187 35.5
70 14.9 49.7 0.011 2.541 0.077 0.290 71.3
70 17.9 64.9 0.011 2.766 0.079 0.300 100.8
70 19.5 73.8 0.011 3.022 0.087 0.349 128.5
70 22.6 95.5 0.011 2.509 0.099 0.719 164.6
70 24.6 113.4 0.011 1.801 0.144 1.147 145.8
44
CHAPTER 3
Table 3: Summary of the experiments; hydrogen series at 70°C and 15 bar.

Cm CH 2
kpC0 kd ki Rp,max
3 3 3 -1 -1
[kg/m ] [kg/m ] [m /gmet.hr] [min ] [min ] [kg/gmet.hr]
50.7 0 0.520 0.040 0.146 16.2

50.7 0 0.600 0.028 0.210 22.3
50.5 0.0034 1.204 0.056 0.362 43.3

50.4 0.0037 1.131 0.060 0.348 48.2
50.3 0.0053 1.384 0.053 0.305 46.9
50.3 0.0054 1.371 0.067 0.355 65.1
50.0 0.0109 1.760 0.061 0.477 60.4

50.0 0.0107 1.752 0.061 0.345 69.7
49.9 0.0116 1.908 0.067 0.495 88.0
49.3 0.0214 2.276 0.069 0.744 103.3
49.2 0.0322 2.551 0.080 1.218 87.7
49.0 0.0324 2.136 0.069 1.167 104.4
48.6 0.0443 2.534 0.064 1.200 120.1
46.2 0.0684 3.175 0.074 1.544 126.1
45
CHAPTER 3
Table 4: Summary of the experiments; temperature series without hydrogen at 15 bar.

T Cm kpC0 kd ki
[°C] [kg/m3] [m3/gmet.hr] [min-1] [min-1]
50 91.8 0.165 0.050 0.428

50 91.8 0.152 0.042 0.405
60 66.9 0.311 0.035 0.440

60 66.9 0.366 0.043 0.588
70 50.6 0.600 0.028 0.210
70 50.6 0.520 0.040 0.146
80 38.2 1.305 0.069 0.288

80 38.2 1.077 0.065 0.325
The influence of temperature has been investigated at 15 bar at temperatures between 50
and 80°C. The hydrogen concentration has been kept constant at 0.011 kg/m3, which is
about 1 vol%. In figure 2 the Arrhenius plot for propagation is given, showing a linear
behavior for temperatures between 50 and 70°C. The experiments at 75 and 80°C showed
a considerable lower activity. In figure 3 and 4 the Arrhenius plots for deactivation and
activation are given respectively, showing again a more or less linear relation between 50
and 70°C, and a deviating behavior above 70°C. The determined kinetic parameters are
summarized in table 5.
Table 5: Summary of the determined kinetic parameters.

Model parameters
Eact,p 43.9 kJ/mol

Eact,d 17.4 kJ/mol
Eact,I 35.6 kJ/mol
kp0C0 1.20⋅107 m3/gmet.hr
kd0 21.3 min-1
ki0 1.19⋅105 min-1
Validity range 50 – 70 °C
46
CHAPTER 3
T [°C]
80 75 70 60 50
1.2
Standard experiment
1
7 min prepolymerization
0.8
5 min prepolymerization
ln(kpC0)
0.6 3 min prepolymerization
0.4
0.2
-0.2
2.8 2.9 2.9 3.0 3.0 3.1 3.1 3.2
-1
1000/T [K ]
Figure 2: Arrhenius plot for propagation. The open dots represent the prepolymerization
experiments.
-2.9
-3
-3.1
ln(kd)
-3.2
-3.3
-3.4
-3.5
2.8 2.9 2.9 3.0 3.0 3.1 3.1 3.2
-1
1000/T [K ]
Figure 3: Arrhenius plot for deactivation.
47
CHAPTER 3
The activation energy for propagation, 43.9 kJ/mol, is quite close to the value found
previously2, 48.0 kJ/mol, where the same metallocene on a different support was used for
gas phase polymerizations at 10 bar pressure. Note that in our previous work the
activation energy was determined based on a model without activation.
-0.6
-0.8
-1
ln(ki)
-1.2
-1.4
-1.6
-1.8
2.8 2.9 2.9 3.0 3.0 3.1 3.1 3.2
-1
1000/T [K ]
Figure 4: Arrhenius plot for activation.

The possibility of particle overheating at the start of the reaction, where the highly
concentrated catalyst particles still have a small external surface, has been the subject of
many discussions in literature6-8. The elevated particle temperature may lead to chemical
reactions between the various catalyst components, especially the stability of MAO at
higher temperatures is questionable. The particle temperature is dependent on the heat
transfer coefficient, the heat transfer area and the difference between bulk and particle
temperature. The internal temperature gradients are in general small. Samson et al.9 found
for both gas and liquid phase polymerization with a Ziegler-Natta catalyst, rapid catalyst
deactivation above a certain temperature. The absolute polymerization rate, per gram of
catalyst (including support), are in the same order of magnitude as observed in this work;
1-3 kg PP/(gcat.hr). Prepolymerizations were executed by Samson et al.9 to prevent a
thermal runaway on particle scale. Prepolymerization may help to prevent a thermal
runaway on particle scale. As the reaction rate is much lower in prepolymerization step
compared to the main polymerization, particles have time to grow in a controlled way to
a size where the external surface is large enough to remove all the reaction heat. The
observed reaction rates by Samson were significantly higher than without
prepolymerization. The prepolymerizations were carried out at low temperatures in either
liquid propylene or pentane slurry. In order to test the same procedure for a
48
CHAPTER 3
heterogeneous metallocene catalyst, prepolymerizations have been executed in gaseous

propylene at 40°C and 5 bar monomer pressure. The prepolymerization time has been
varied between 3 and 7 minutes, after this the temperature and pressure have been raised
to 80°C and 15 bar, respectively. As can be seen in figure 2, prepolymerization of the
catalyst results in a higher reaction rate for the main polymerization reaction. However, a
large deviation with the Arrhenius plot still exists, even for prepolymerization time of 7
minutes. Obviously, there are more effects than only initial particle overheating to be
taken into account.
In a next series, the influence of temperature in the absence of hydrogen has been
investigated at 15 bar and temperatures between 50 and 80°C. In figure 5 the Arrhenius
plot is given, showing a linear behavior in contrast to the temperature series with
hydrogen. No discrepancy was found at temperatures above 70°C. Because of the low
reaction rate in absence of hydrogen, the chance of a runaway is small, even at 80°C. The
activation energy for propagation derived for this case is 58.9 kJ/mol. This value is higher
compared to the value obtained in the presence of hydrogen (43.9 kJ/mol). A possible
explanation for this may be that the catalyst applied is not completely single site, and
certain sites have different sensitivity towards hydrogen. For further discussion on a
possible non-single site behavior of the heterogeneous metallocene catalyst, see below.
0.5
-0.5
ln(kpC0)
-1
-1.5
-2
2.8 2.85 2.9 2.95 3 3.05 3.1 3.15
-1
1000/T [K ]
Figure 5: Arrhenius plot for propagation in the absence of hydrogen.
49
CHAPTER 3
Influence of pressure
The influence of pressure has been investigated in the range between 5 and 25 bar at
70°C. The hydrogen concentration has been kept constant at 0.011 kg/m3, which is the
same value as used for the temperature series. In figure 6, the influence of monomer
concentration on the kinetic parameter kpC0Cm is shown. Here, the monomer
concentration Cm is based on the monomer concentration in the amorphous part of the
polymer. For a first order reaction, a linear relation is expected with an intercept equal to
zero. As can be seen from figure 6, a linear relation is obtained for pressures between 5.1
and 19.5 bar, while deviations occur at higher pressures (22.6 and 24.6 bar). Moreover,
the intercept is not equal to zero indicating a higher reaction order at low monomer
concentrations. This is in agreement with work published before2,10.
300
250
kpC0Cm [kg PP/gmet.hr]
200
150
100
50
0
0 20 40 60 80 100 120
3
Cm [kg/m ]
Figure 6: Influence of monomer concentration on kpC0Cm.
The deviations observed at high pressures, can be explained in a similar way as was done
for the temperature series. At high polymerization rates, i.e. high monomer
concentrations or bulk temperatures, the particle temperature may be substantial higher
than the bulk temperature, which may lead to chemical deactivation reactions. The
maximum polymerization activity observed for the case of particle excess temperature
behavior, should be in the same order of magnitude for the pressure and temperature
series as in those cases the actual particle temperature can be expected to be similar. The
behavior described above is confirmed by the determined Rp,max values presented in table
2.
50
CHAPTER 3
The deviations observed at high pressures, have not been found in the work published
before2, where the same catalyst was used but on a different silica support. The average
particle size of the support used in this work is about a factor of two (108 vs. 51 µm)
larger than used in this previous work. Therefore, the volume to surface area ratio of the
catalyst used in this work is about a factor of two higher, while the activity per gram of
catalyst is about the same. This makes heat removal from the larger particle more
difficult.
In figure 7 and 8, the influence of the monomer concentration on the deactivation and
activation constant is given. As can be seen, the two constants are hardly affected by the
monomer concentration, except for the two experiments at 22.6 and 24.6 bar. The values
for kd and ki for these two experiments are higher, compared to the values at low
concentration. This is in contradiction to the behavior observed in the temperature series.
0.16
0.12
kd [min ]
-1
0.08
0.04
0.00
0 20 40 60 80 100 120
3
Cm [kg/m ]
Figure 7: Influence of monomer concentration on kd.
51
CHAPTER 3
1.4
1.2
1
ki [min ]
-1
0.8
0.6
0.4
0.2
0
0 20 40 60 80 100 120
3
Cm [kg/m ]
Figure 8: Influence of monomer concentration on ki.
Influence of hydrogen
The influence of hydrogen has been investigated at 15 bar and 70°C between 0 and 0.068
kg/m3 (0 – 5.5 mol%). The hydrogen concentration is calculated as the concentration in
the gas phase, because sorption data of hydrogen in a polymer swollen with monomer is
not available. In figure 9 the influence of hydrogen on the kinetic constant kpC0 is given,
showing a strong increase at low hydrogen concentration. At high hydrogen
concentrations the slope decreases. Samson et al.11 also found a decreasing slope with
increasing hydrogen concentration. Several possible explanations can be given for
increasing polymerization rate at higher hydrogen concentrations12. Firstly, hydrogen
may react with the surface of the heterogeneous catalyst to increase the number of active
sites. Secondly, hydrogen may reactivate deactivated sites, which have been deactivated
by components like metalallylics. Thirdly, hydrogen may prevent the forming of
unsaturated chain-end groups, which may act as a poison. However, the most plausible
explanation is that hydrogen prevents the formation of dormant sites, which occur after a
secondary insertion11.
The explanation for the decreasing slope at higher hydrogen concentration can also be
explained by several theories. Firstly, at higher hydrogen concentration the concentration
of dormant sites will decrease causing a reduced reactivation effect of hydrogen.
Secondly, the temperature and pressure series presented above support the theory of a
runaway on particle scale above a critical polymerization rate. In table 3 values for the
52
CHAPTER 3
maximum polymerization activity are presented. These values are in the same order of
magnitude, in case of high hydrogen concentrations, compared to the values obtained in
the temperature and pressure series.
The given possible explanations do not exclude each other, they might occur
simultaneously.
3.5
2.5
kpC0 [m3/gmet.hr]
1.5
0.5
0
0.0000 0.0100 0.0200 0.0300 0.0400 0.0500 0.0600 0.0700 0.0800
3
[H2] [kg/m ]
Figure 9: Influence of hydrogen on kpC0.
In figure 10 and 11 the influence of hydrogen on the deactivation and activation constant
is given. The deactivation rate in the absence of hydrogen is substantially lower
compared to higher hydrogen concentrations. The activation constant seems to be linearly
dependent on the hydrogen concentration.
53
CHAPTER 3
0.100
0.080
0.060
kd [min ]
-1
0.040
0.020
0.000
0.0000 0.0100 0.0200 0.0300 0.0400 0.0500 0.0600 0.0700 0.0800
3
[H2] [kg/m ]
Figure 10: Influence of hydrogen on kd.

2.00
1.60
1.20
ki [min ]
-1
0.80
0.40
0.00
0.0000 0.0100 0.0200 0.0300 0.0400 0.0500 0.0600 0.0700 0.0800
3
[H2] [kg/m ]
Figure 11: Influence of hydrogen on ki.
54
CHAPTER 3
Interpretation of the acceleration period

As discussed before, several explanations for the initial acceleration period have been
proposed in literature. The particle growth model proposed by Bonini et al.3, assuming a
shell by shell fragmentation from outside, is based on a diffusion limitation process.
According to this theory, the yield obtained at the point of maximum polymerization
activity should be the same for every experiment, assuming little chemical deactivation
processes in the acceleration period. Following our model, the yield at the moment of
maximum polymerization activity can be determined from the surface below the rate-
time curves, see equation 11.
( )
t
ki
Yield = ∫ k p C0Cm e − k i t − e − k d t dt = (11)
0
k d − ki
 1
k p C0 C m
ki
kd − ki
(
 1 − e i −
−k t 1
) (
1 − e−k d t )
 i
k k d 
In figure 12 the calculated yield at the moment of maximum polymerization activity is

given for the pressure series. As can be seen, the yield at maximum polymerization
activity is certainly not the same for every experiment. Therefore, we interpret the
increasing polymerization rate during the initial period as a physical and chemical
process where several components, e.g. metallocene, MAO, TIBA, react to form the
active species. The physical process is highly related to the particle morphology, which in
turn is predefined in the early (fragmentation) stage of polymerization. Catalyst
8
7
Yield at Rp,max [kg PP/gmet]
0
0 20 40 60 80 100 120
3
Cm [kg/m ]
Figure 12: Influence of the relative hydrogen concentration on the chain
termination probability; samples from the hydrogen series.
55
CHAPTER 3
fragmentation depends mainly on two factors: hydraulic pressure generated by the

polymer produced and rigidity of the support, see Weickert et al.13. A fast increase of the
hydraulic pressure, i.e. high initial polymerization rates, leads to a large number of
fragments, whereas low initial rates corresponds to a small number of fragments. We
have chosen to describe the initial acceleration period with an empirical model because
the mechanism seems to be very complex.
Molecular weight and molecular weight distribution

The results from the GPC measurements (Mw, Mn and Mw/Mn) are presented in table 6
for some of the samples produced during the kinetic studies at different process
conditions. The low molecular weight of the polymer is in agreement with results from
literature3,12,14. In general, a narrow molecular weight distribution is obtained during
polymerization with homogeneous metallocene catalysts at constant temperature and gas
composition (Mw/Mn ≈ 2). Higher polydispersities are observed after polymerization with
the heterogeneous analogues3,15. The samples produced during the kinetic measurements
described before show polydispersities of around 2.5. One can calculate the chain
termination probability q in two different ways, either based on Mn or based on Mw
resulting in the same value if Mw/Mn = 2, see equation 10. In figure 13, the chain
termination probabilities based on Mn and Mw of the hydrogen series have been plotted
against the relative hydrogen concentration ( C H 2 /Cm), theoretically giving a straight line
(see equation 9). Because Mw/Mn > 2, the two lines in figure 13 do not coincide.
Moreover, at high relative hydrogen concentrations both kinds of chain termination
probabilities are smaller than expected. Several possible explanations can be given for
this behavior. Firstly, the error made during the GPC analyses may increase with
decreasing molecular weight. Secondly, a possible runaway on particle scale, as argued
before, results in overheating of particles during the start of the reaction. However, a
relative low amount of lower molecular weight polymer will be produced in this period.
Degradation reactions of MAO or other cocatalyst compounds at higher temperatures
may also lead to the forming of chain termination agents.
56
CHAPTER 3
Table 6: GPC data.

T p C H 2 /Cm Mn Mw Mw/Mn q(Mn) q(Mw)
[°C] [bar] [-] [kg/mol] [kg/mol] [-] [-] [-]
50 15 1.19⋅10-4 11 25 2.3 3.82⋅10-3 3.36⋅10-3

60 15 1.64⋅10-4 8.6 23 2.7 4.88⋅10-3 3.65⋅10-3
70 15 2.21⋅10-4 8.1 19 2.3 5.19⋅10-3 4.42⋅10-3
75 15 2.50⋅10-4 6.9 17 2.5 6.09⋅10-3 4.94⋅10-3
80 15 2.88⋅10-4 7 17 2.4 6.00⋅10-3 4.94⋅10-3
50 15 0 13 34 2.6 3.23⋅10-3 2.47⋅10-3
60 15 0 14 31 2.2 3.00⋅10-3 2.71⋅10-3
80 15 0 9.8 24 2.4 4.29⋅10-3 3.50⋅10-3
70 5.1 7.75⋅10-4 3.4 7.3 2.2 1.24⋅10-2 1.15⋅10-2
70 14.8 2.21⋅10-4 8.7 17 2.0 4.83⋅10-3 4.94⋅10-3
70 17.9 1.69⋅10-4 10 20 2.0 4.20⋅10-3 4.20⋅10-3
70 19.5 1.49⋅10-4 10 21 2.1 4.20⋅10-3 4.00⋅10-3
70 22.6 1.15⋅10-4 11 24 2.2 3.82⋅10-3 3.50⋅10-3
70 15 0 12 27 2.3 3.50⋅10-3 3.11⋅10-3
70 15 7.34⋅10-5 9.6 22 2.3 4.38⋅10-3 3.82⋅10-3
70 15 1.05⋅10-4 8.3 20 2.4 5.06⋅10-3 4.20⋅10-3
70 15 2.18⋅10-4 7.3 17 2.3 5.75⋅10-3 4.94⋅10-3
70 15 4.34⋅10-4 5.4 13 2.4 7.78⋅10-3 6.46⋅10-3
70 15 9.05⋅10-4 3.9 10 2.6 1.08⋅10-2 8.40⋅10-3
70 15 1.48⋅10-3 3.3 8.1 2.5 1.27⋅10-2 1.04⋅10-2
Variation of the reaction temperature and pressure will also lead to a variation of the
relative hydrogen concentration, because of the changing monomer concentration in the
polymer. In figure 14 the chain termination probability based on Mw of all kinetic series
(temperature, pressure and hydrogen) are given as function of the relative hydrogen
concentration. It can be seen that the dependency on temperature is not as strong as on
the relative hydrogen concentration. This phenomenon is characteristic for the used
57
CHAPTER 3
catalyst and not generally valid. Phillips catalysts, CrO/SiO2, are for instance hardly
affected by hydrogen but are strongly dependent on temperature15.
0.02
q based on Mn
0.018
q based on Mw
0.016
0.014
0.012
q [-]
0.01
0.008
0.006
0.004
0.002
0
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012 0.0014 0.0016 0.0018
[H2]/Cm

termination probability; hydrogen series.
0.014
0.012
0.01
q(Mw) [-]
0.008
0.006
Hydrogen series
0.004 Pressure series
Temperature series
0.002
Temperature series wihout hydrogen
0
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012 0.0014 0.0016
[H2]/Cm
termination probability; samples from all series.
58
CHAPTER 3
In figure 15 an example is given of the result from a GPC measurement together with two
curves based on a Schulz-Flory distribution from q’s determined from Mn and Mw. The
GPC curve is broader, which was expected because of the higher polydispersity. Fait et
al.10 postulated a kinetic model for a single-center, two-state catalyst. The two states
differ in either their monomer insertion or coordination rate, thus having two different
propagation rate constants. Different chemical possibilities for the nature of the two
stated were discussed. The ratio between the two states depends, among others, on the
monomer concentration. We observed first order reaction kinetics at pressures above 15
bar, but nevertheless observed non-single site behavior. This may be related to the fact
that our catalyst is supported allowing for interaction of active sites and the support.
1.4
1.2 b c
1
a
0.8
Y
0.6
0.4
0.2
0
2 2.5 3 3.5 4 4.5 5 5.5 6
Log Mw
Figure 15: Simulation of the molecular weight distribution with Schulz-Flory
distributions. a) Result from GPC analyses. b) Based on chain termination probability
calculated with Mn. c) Based on chain termination probability calculated with Mw.
59
CHAPTER 3
1.2
GPC result
1 Two-site model
0.8
Y
0.6
0.4
0.2
0
2 2.5 3 3.5 4 4.5 5 5.5 6
Log Mw
Figure 16: Simulation of the molecular weight distribution with the two-site model.
Table 7: Chain transfer probabilities for site 1 and 2 assuming an equal productivity for
both sites (50/50).
C H 2 /Cm q1 q2 1 N
∑ (YGPC − Ymod el )i2
N i =1
[-] [-] [-]
0 2.05⋅10-3 4.95⋅10-3 0.28⋅10-3

7.34⋅10-5 2.49⋅10-3 5.91⋅10-3 0.38⋅10-3
1.05⋅10-4 2.64⋅10-3 6.90⋅10-3 0.49⋅10-3
2.18⋅10-4 3.28⋅10-3 8.07⋅10-3 0.82⋅10-3
4.34⋅10-4 4.02⋅10-3 1.18⋅10-2 1.00⋅10-3
9.05⋅10-4 4.86⋅10-3 1.79⋅10-2 1.90⋅10-3
1.48⋅10-3 7.12⋅10-3 2.61⋅10-2 2.42⋅10-3
60
CHAPTER 3
Table 8: Chain transfer probabilities for site 1 and 2 assuming a relative productivity for
site 1 and 2 of 10 and 90%.
C H 2 /Cm q1 q2 1 N
[-] [-] N i =1
[-]
0 1.18⋅10-3 3.77⋅10-3 4.18⋅10-3

7.34⋅10-5 1.40⋅10-3 4.71⋅10-3 6.55⋅10-3
1.05⋅10-4 1.32⋅10-3 5.50⋅10-3 10.0⋅10-3
2.18⋅10-4 1.73⋅10-3 6.22⋅10-3 7.10⋅10-3
4.34⋅10-4 2.07⋅10-3 8.45⋅10-2 8.35⋅10-3
9.05⋅10-4 2.36⋅10-3 1.18⋅10-2 12.8⋅10-3
1.48⋅10-3 3.20⋅10-3 1.56⋅10-2 11.3⋅10-3
Table 9: Chain transfer probabilities for site 1 and 2 assuming a relative productivity for
site 1 and 2 of 90 and 10%.
C H 2 /Cm q1 q2 1 N
N i =1
[-] [-] [-]
0 2.90⋅10-3 9.00⋅10-3 2.52⋅10-3

7.34⋅10-5 3.54⋅10-3 1.20⋅10-2 2.86⋅10-3
1.05⋅10-4 3.87⋅10-3 1.47⋅10-2 4.11⋅10-3
2.18⋅10-4 4.58⋅10-3 1.65⋅10-2 4.45⋅10-3
4.34⋅10-4 5.97⋅10-3 2.45⋅10-2 8.00⋅10-3
9.05⋅10-4 7.73⋅10-3 3.91⋅10-2 13.5⋅10-3
1.48⋅10-3 9.57⋅10-3 5.23⋅10-2 18.1⋅10-3
In order to obtain a better description of the molecular weight distribution, a “two-site

model” has been used. The distributions obtained from the hydrogen series have been
used to fit each distribution with two Schulz-Flory distributions, assuming an equal
61
CHAPTER 3
polymerization rate of each site (50/50). In figure 16 an example of such a fit is given
presenting a much better fit as was obtained by using a single site model. The determined
values for the chain termination probability of both sites together with the errors of the
model predictions are given in table 7. To check the assumption of equal productivity of
each site, fitting has been repeated assuming a productivity ratio of site 1 and 2 of 10/90
and 90/10, respectively. The obtained values for the chain termination probability of site
1 and 2 for these cases are given in table 8 and 9, respectively. It can be seen that the
errors found for these cases are larger compared to the errors found for the case in which
equal site productivity was assumed. However, the productivity ratio between the two
sites has not been optimized. The obtained values for the chain termination probability of
site 1 and 2 for all 3 cases are plotted versus the relative hydrogen concentration, see
figure 17. It appears that both sites show a linear relation in all 3 cases, although the
errors for the 10/90 and 90/10 model are much larger. Obviously, the linearity found is
not a sufficient criterion to select the correct productivity ratio of the two-site model. The
relations for the 50/50 model are given in equations 12 and 13.
CH (12)
q 1 = 3.195 2 + 0.0023
Cm
C H2 (13)
q 2 = 14.20 + 0.0051
Cm
0.06
q1 based on 50/50 productivity
0.05 q1 based on 10/90 productivity
0.04 q1 based on 90/10 productivity

q [-]
0.03
0.02
0.01
0
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012 0.0014 0.0016
[H2]/Cm
Figure 17: Determined chain termination probabilities for site 1 and 2 versus
the relative hydrogen concentration.
62
CHAPTER 3
Conclusions
Gas phase polymerizations of propylene with a heterogeneous metallocene catalyst have
been executed at different temperatures, pressures and hydrogen concentrations. The
experimentally measured reaction rate curves have been simulated with a model, which
considers both the activation as well as the deactivation of the catalyst. It is argued that
the clearly observed initial acceleration stage is due to chemical activation processes
rather than a diffusion limitation process.
At relative high polymerization rates deviations have been found from the model, which
is attributed to a thermal runaway on particle scale. At these reaction conditions, the
particle temperature may well be over the bulk temperature resulting in decomposition of
vital catalyst components. Prepolymerization at low pressure and temperature increased
the reaction rates. However, at higher temperatures large deviations with the Arrhenius
plot still exist even for prepolymerization time of 7 minutes. Obviously, there are more
effects than only particle overheating to be taken into account.
For temperatures between 50 and 70°C, an activation energy for propagation was found
to be 43.9 kJ/mol. This value is close to the value found by Meier et al.2, 48.0 kJ/mol
where the same metallocene was used on a similar support with a smaller average particle
size for gas phase polymerizations at 10 bar pressure. Important to mention is that also
the same monomer sorption data has been used in the present paper to allow comparison
of these kinetic data. A higher activation energy has been found for polymerizations in
the absence of hydrogen at 15 bar pressure; 58.9 kJ/mol.
The influence of monomer concentration has been investigated at pressures up to 25 bar.

Again, deviations at high polymerization rates have been found, supporting the theory of
a runaway at particle scale. The deactivation and activation constant are hardly affected
by the monomer concentration for the range in which experiments have been done.
The influence of hydrogen on the polymerization kinetics has been investigated at

concentrations between 0 and 5.5 mol%. At low concentrations, the reaction rate strongly
increases whereas at high concentrations this behavior flattens off. The most plausible
explanation for the increased activity with increasing hydrogen concentration is the
reactivation of dormant sites by hydrogen.
The molecular weight and molecular weight distribution of the polymer samples
produced during the kinetic study have been analyzed by GPC. The low molecular weight
of the polymer is characteristic for the applied catalyst system. The molecular weight
distribution is broader than expected for a single site catalyst, but in agreement with
results reported for heterogeneous metallocene catalysts. The results from the
63
CHAPTER 3
temperature series are reasonably consistent with the results from the hydrogen and
pressure series when the chain termination probability is plotted versus the relative
hydrogen concentration. An empirical “two-site model” has been used in order to give a
better description of the molecular weight distribution. Two Schulz-Flory distributions
have been used to fit the observed distribution assuming an equal productivity of each
site. Variation of the productivity ratio leads to larger errors between the model and GPC
curves. The determined chain termination probabilities for each site are found to be
linearly dependent on the relative hydrogen concentration, independently of the
productivity ratio. The linearity itself is obviously not a sufficient criterion to select the
correct productivity ratio of the two-site model.
technical assistance. G.H. Banis is acknowledged for his technical support and W.R. Smit, O. Slotboom,
M.F. Bergstra and M.J.M. Hattink for their contribution in the experimental part. The authors further
wishes to thank DSM Research for the GPC measurements.
Notation
C Number of potential active sites mol/gmet
C* Number of active sites mol/gmet
Cm Monomer concentration kg/m3
CH2 Hydrogen concentration kg/m3
Eact Activation energy J/mol
j Chain length -
kd Deactivation rate constant min-1
k H2 Chain transfer constant for hydrogen m3/mol.hr
ki Activation rate constant min-1
km Chain transfer constant for monomer m3/mol.hr
kp Propagation rate constant m3/mol.hr
kx Chain transfer constant (other than H2 and m) m3/mol.hr
Mm Molecular weight of the monomer kg/mol
Mn Number averaged molecular weight kg/mol
Mw Weight averaged molecular weight kg/mol
p Pressure bar
q Chain termination probability -
Rp Reaction rate kg/gmet.hr
t Time min
64
CHAPTER 3
T Temperature K
y dj Density function of the instantaneous MWD -
Y Standard format for GPC curve; y dj M m j kg/mol
Greek
χ Flory-Huggins interaction parameter -
Subscripts
0 Initial value
1 Site 1
2 Site 2
d deactivation
i activation
p propagation
Abbreviations
GPC Gel Permeation Chromatography
Literature
1. Resconi, L., Fait, A., Piemontesi, F., Colonnesi, M., Rychlicki, H., Zeigler, R.,
Macromolecules, 28, 6667-6676, (1995)
2. Meier, G.B., Weickert, G., van Swaaij, W.P.M., submitted to J. Appl. Pol. Sci.,
(2000)
3. Bonini, F., Fraaije, V., Fink, G., J. Polym. Sci. Polym. Chem. Ed., 33, 2393-2402,
(1995)
4. Kim, I., Choi, H.K., Kim, J.H., Woo, S.I., J. Pol. Sci. Pol. Chem. Ed., 32, 971-977,
(1994)
5. Weickert, G., Modellierung von polymerisationsreaktoren; Springer-Verlag Berlin
Heidelberg, Chapter 3, p 37, (1997)
6. Floyd, S., Choi, K.Y., Taylor, T.W., Ray, W.H., J. Appl. Polym. Sci., 31, 2231-2265,
(1986)
7 Floyd, S., Choi, K.Y., Taylor, T.W., Ray, W.H., J. Appl. Polym. Sci., 32, 2935-2960,
(1986)
8 McKenna, T.F., Spitz, R., Cokljat, D., AIChE J., 45(11), 2392-2410, (1999)
9. Samson, J.J.C., van Middelkoop, B., Weickert, G., Westerterp, K.R., AIChE J.,
45(7), 1548-1558, (1999)
65
CHAPTER 3
10. Fait, A., Resconi, L., Guerra, G., Corradini, P., Macromolecules, 32, 2104-2109,
(1999)
11. Samson, J.J.C., Bosman, P.J., Weickert, G., Westerterp, K.R., J. Pol. Sci. Polym.
Chem. Ed., 37(2), 219-232, (1999)
12. Carvill, A., Tritto, I., Locatelli, P., Sacchi, M.C., Macromolecules, 30, 7056-7062,
(1997)
13. Weickert, G., Meier, G.B., Pater, J.T.M., Westerterp, K.R., Chem. Eng. Sci., 54,
3291-3296, (1999)
14. Spaleck, W., Aulbach, M., Bachmann, B., Küber, F., Winter, A., Macromol. Symp.,
89, 237-247, (1995)
15. Blom, R., Dahl, I.M., Macromol. Chem. Phys., 200, 442-449, (1999)
66
CHAPTER 4
Chapter 4
FBR mini-plant for catalytic olefin polymerization:

Particle mixing and propylene polymerization.
Abstract
Particle mixing and segregation have been studied in a small-scale fluidized bed reactor
under pressure. It appeared that the solids mixing is relatively fast compared to the
residence time of catalyst particles in case of a polymerization process. However, the
smaller particles accumulate in the upper zone. Moreover, electrostatic charging causes
the forming of a layer of small particles at the reactor wall with increasing thickness in
time. The particles are redispersed after injection of an anti-static agent. Semi-batch
propylene polymerization experiments at different fluidization velocities showed that
vertical temperature gradients are caused by catalyst segregation as the principle factor.
Specially at low gas velocities both segregation and mixing can be different under
reacting conditions compared to non-reacting conditions due to different particle-
particle interactions. Catalyst concentration gradients caused by incomplete mixing are
expressed remarkably by the exothermic reaction even at low polymerization rates.
Despite the fact that fluidized beds can hardly be scaled-up from experiments in reactors
with diameters below 30 cm, small-scale fluidized bed reactor experiments can contribute
to address and quantify incomplete mixing and electrostatic charging effects.
67
CHAPTER 4
68
CHAPTER 4
Introduction
Nowadays, gas phase polymerization of olefins is one of the most important
polymerization processes. Compared to other processes like the slurry and solution
polymerization, gas phase processes have many distinct advantages. Gas phase processes
can reduce capital and operating costs over conventional processes. Moreover, gas phase
polymerizations offer a large variety of products, which could not be produced by other
processes.
The fluidized bed reactor is one of the main types of reactors for producing polyolefins in
the gas phase. In the open literature on polyolefin polymerization there are no
experimental data available obtained with this type of reactor because of the high
investment costs for creating a pressurized experimental facility of this type, the high
activity of the catalyst and its sensitivity to small traces of impurities. Moreover,
phenomena like sheeting, electrostatic charging and entrainment of small particles may
occur.
Industrial fluidized bed reactors for propylene polymerization operate in a pressure range
of 20 to 30 bar. Gas phase conversion per pass is kept low, 1-3%, to facilitate cooling of
the reactor and to diminish concentration and temperature gradients in the reactor. At the
typical residence time of 1 to 3 hours, polymer particles with a broad size distribution are
obtained. Segregation phenomena can play an important role as the bigger particles,
referred as the jetsam, tend to accumulate at the bottom of the bed. The smaller particles,
referred as flotsam, show the tendency to accumulate at the top section. Mixing and
segregation are competitive processes, both affected by the fluidization velocity.
Specially at gas velocities much higher than the minimum fluidization velocity of the big
particles, mixing is strongly enhanced. Because the catalyst/polymer particles grow in
size during polymerization, it is possible that the upper section is rich in small and very
active particles due to segregation. This may even introduce a vertical temperature
gradient, which will affect the subsequent polymer properties. As the product in such a
reactor is removed from the bottom section of the reactor, the bigger particles are
preferentially extracted. This segregation effect results in a narrowing of the particle size
distribution of the product.
Sheeting, elutriation and agglomeration

Sheeting and agglomeration of polymer particles are two serious problems, which can
appear in modern gas phase polymerization processes. Sheeting of the reactor wall
influences the performance of a fluidized bed reactor negatively and can plug the reactor
in a later stadium. Moreover, blow out of highly active small particles elutriated from the
bed can cause sheeting and plugging in other parts of the system. Agglomeration of
particles affects the particle size distribution, fluidization behavior and polymer
69
CHAPTER 4
properties. Moreover, agglomeration of polymer particles reduces the internal heat and
mass transfer thereby limiting the overall yield per gram of catalyst.
Sheeting of the reactor wall of a fluidized bed occurs when the shear forces near the
reactor wall are smaller than the adhesion forces between the particles and the reactor
wall. There are in general three main causes for sheeting of the reactor wall. First,
overheating of particles may occur due to very high reaction rates. The temperature of a
particle can rise in this way above the softening temperature. Secondly, sticking may be
due to polymer properties itself. Some (co-)polymers with low glass temperatures can
easily form agglomerates. Thirdly, sheeting may develop due to the presence of excess
negative or positive static charges pressing charged particles against the wall. The critical
static voltage level for sheet formation is a complex function of polymer sintering
temperature, operating temperature, pressure, gas composition, particle size distribution,
slip velocity between gas and polymer particle, catalyst activity, etc. When the static
charge reaches the level where the particles begin to stick to the wall, a layer of catalyst-
containing polymerizing particles forms a non-fluidized layer at the reactor wall. The
temperature in this layer can rise due to limited heat removal until the particles melt and
fuse. At this point other particles will stick to the layer and it will grow in size. In some
cases the layer will plug the system otherwise it will disturb operation by becoming loose
from the wall.
The phenomena mentioned above are rarely described in the open literature. Some
authors have mentioned the effects but in most cases these are only studied qualitatively.
The fluidization hydrodynamics have a dominant influence on agglomeration and
sheeting since they both directly influence the physical parameters of the fluidizing bed.
In US patent 5,283,2781 the use of an anti-static agent is described. The anti-static agent
can be introduced into the reactor in the form of a solution, but dispersing a liquid
uniformly is difficult. Another way to introduce the anti-static agent is to provide it in a
prepolymerization step. It is known that prepolymerization itself can also prevent
agglomeration of particles as described in US patent 5,241,0232. When the catalyst is
injected without prepolymerization, reaction commences very intensively, creating a
local speeding up of the reaction in the fluidized bed which can give rise to runaway
reactions and also breaking up of solid particles of catalyst and loss of control of particle
size may occur.
Present work
This paper reports on an experimental set up for the polymerization of propylene in a
small-scale fluidized bed reactor under pressure. The set up is used to quantify the effects
of particle mixing and segregation on the temperature profile in the reactor. It is obvious
that the small-scale chosen, 10 cm in diameter and 1 m in height, is not representative for
70
CHAPTER 4
an industrial system. Fluidization in reactors with a small diameter may result in a

slugging type of fluidization because the bubble size may approach the reactor diameter.
This type of fluidization has a smaller vertical mixing rate, compared to the bubbling
regime generally applied in industrial sized reactors. To compare well-mixed stirred
semi-batch reactors, often used for kinetic measurements, with fluidized bed reactors,
particle mixing and segregation in the particular fluid bed will generally be taken into
account. Specially for small-scale fluid beds these effects may be crucial. Moreover,
because of the high surface to volume ratio of small-scale reactors, electrostatic charging
is enhanced, agglomeration of particles occurs more easily due to the lower vertical
mixing rate. In comparison with industrial reactors, the experiments in such small-scale
reactors may be interpreted as a worst case magnifying the different reactor problems
mentioned. For the present work this was further strengthened by using a catalyst that
produces a low molecular weight sticky polymer. In future work3 the reactor will be
modified to allow also comparison with expected full-scale reactor conditions.
In the current paper mixing and segregation have been studied at pressures up to 26 bar.
Isobaric semi-batch polymerization experiments with a heterogeneous metallocene
catalyst have been executed. Especially the influence of the superficial gas velocity has
been investigated. The heterogeneous metallocene catalyst used, was the subject of an
extensive kinetic study published before4.
Experimental
Fluidized bed reactor set up
The experimental set up is schematically shown in figure 1. The reactor consists of a fluid
bed zone and a disengagement zone. The internal diameter and height of the fluid bed
zone is 10 and 100 cm, respectively. The diameter is limited by the capacity of the
compressor and the height of the reactor results in a gas residence times comparable to
industrial units. The disengagement zone has a diameter of 38.5 cm and a height of 25
cm. Observing glasses are available at four different vertical positions (12.5, 37.5, 62.5
and 87.5 cm above the distributor plate). At a distance of 15 cm above the distributor
plate, tracer particles can be injected. Polymer samples can be withdrawn at 7 heights
from 20 to 80 cm above the distributor at 10 cm interdistance. The catalyst is injected 15
cm above the distributor plate, see below. Product can be removed from the bottom
section of the reactor, 5 cm above the distributor plate, semi-continuously by opening a
valve to a container. The distributor plate consists of sintered stainless steel spheres with
an average pore diameter of 0.3 mm. Steel nuts are packed under the distributor in order
to increase mixing and break-up of the inlet velocity profile. Temperatures in the reactor
are measured 50 mm below the distributor plate and at 6 different vertical positions with
10 cm interdistance, starting at 25 cm above the distributor.
71
CHAPTER 4
Vent
Inlet propylene and
hydrogen
Cyclones
T6
IR
T5
NO
T4
Buffer vessel
H2
T3
Vent
T2 Catalyst
T1
injection
T0
NO
Product removal
NO
Control Valve Check Valve Filter
Valve Relief Valve Heat exchanger
Flow meter Rupture Disk

Compressor
Figure 1: Small-scale fluidized bed reactor for propylene polymerization.
Two cyclones and a filter have been installed to remove fines entrained from the reactor.
Gas leaving the reactor is cooled by a vertically positioned heat exchanger. A Eurotherm
900 EPC PID controller, controls the temperature of the gas entering the compressor. The
control circuit comprises cold and hot water streams and an injection pipe of cold water
directly into the inlet pipe of the heat exchanger. A second heat exchanger is used to
72
CHAPTER 4
control the gas inlet temperature of the reactor within 0.2 °C. The reactor is placed in an
air thermostat in order to decrease heat losses from the reactor wall to the surroundings.
A blower circulates heated air in this cage with a temperature of about 50°C. The heat
losses through the wall are thus reduced to less than 5% of the amount of convective
cooling by the inlet gas.
The compressor consists of two parallel heads each containing a double membrane. A
buffer vessel is installed in order to compensate for pressure fluctuations. The flow
circulating through the reactor system is regulated by two control valves (Orion 9000,
USA) and is measured by a Brooks mass flow meter (5865 Ex). One control valve is
located just before the reactor, a second valve is located in the bypass from the
compressor loop. To measure and control the gas composition in the reactor, a sample
flow from the reactor is lead continuously through a cascaded IR propylene analyzer
(Servomex Xendos 2500) and hydrogen analyzer (Maihak, Thermor 615 thermal
conductivity meter).
Catalytic olefin polymerizations require extremely pure raw materials to avoid poisoning
of the catalyst. Propylene, hydrogen and nitrogen are cleaned in separate purification
systems to remove traces of O2, H2O, CO, etc. The purification system consists of BTS
and molsieves columns, see Samson et al.5. Propylene is fed to the system as a liquid just
before the first heat exchanger. A PID controller controls the partial pressures of
propylene and hydrogen. The system is designed to operate at a maximum pressure of 30
bar.
The installation is placed in a well ventilated concrete bunker and fully computer
controlled. Thermocouples and pressure indicators in various places are used to
determine the temperatures and pressures in the system every 10 seconds. If a measured
value indicates a potentially dangerous situation, catalyst injection is stopped. A relief
valve is placed on top of the reactor, which discharges at 30 bar. A rupture disk protects
the installation for pressures exceeding 32 bar. Combustible gas detectors are installed, to
monitor leakage of combustible gas. If a leak is observed, the experiment is stopped and
the installation is flushed with nitrogen.
Catalyst system
The metallocene catalyst used for the polymerizations is rac-Me2Si[Ind]2ZrCl2, which
produces a low molecular weight polymer. The sticky polymer is useful for studying
agglomeration and sheeting in the fluidized bed reactor. The catalyst system used for this
study, was kindly supplied by Witco Co. Bergkamen (Germany). It is supported on Grace
silica with a metallocene concentration of 1 wt%. The MAO/SiO2 – support used for
immobilization of the metallocene contained 25 wt% of alumina, giving a [Al]/[Zr] ratio
73
CHAPTER 4
of 386. The average particle size of the silica used (SD3216-30, 10 – 110 µm) is 51 µm.
Tri-isobuthylaluminium (TIBA) has been used as a cocatalyst to increase the
polymerization activity. The amount of TIBA and the precontact time has been kept
constant for all experiments. The preparation procedure has been described before4.
Catalyst injection system

Injection of the catalyst is crucial in the N2
procedure and needs special precaution, as

only a few milligrams of these
components have to be injected. A semi-
continuous system has been developed to
Reactor wall
inject a reproducible amount of catalyst,
Catalyst storage
see figure 2. The injection proceeds as
follows. Catalyst is prepared under a
nitrogen atmosphere in a glove box. The N2
catalyst is diluted with polypropylene
powder to prevent the catalyst particles
N2
from sticking to each other and to the
Dosage valve
reactor walls, which would possibly lead
to local hot spots in the reactor. The
catalyst container is connected to the
catalyst injection system and all Plunger
connection sections are thoroughly flushed
with nitrogen. A three-way ball valve,
located under the catalyst storage vessel,
is used as a dosing device by injecting the
contents of the ball valve by flushing with
nitrogen. The valve thus provides a Figure 2: Injection system for catalyst.
reproducible amount of polymer/catalyst
mixture. Shortly before injection a plunger is displaced, which seals the reactor. To
prevent monomer from entering the injection system, a small continuous flow of nitrogen
blows into the reactor when the plunger is pulled back. A small nitrogen overpressure is
always kept in the whole injection system to prevent monomer leakage into the injection
system. The injection procedure itself is automated but the operator can adjust the time
space between the successive injections from outside the box. For the semi-batch
experiments described in this paper, the total amount of catalyst is injected in 12
injections at the beginning of the experiment with 20 seconds time space in between.
74
CHAPTER 4
Electrostatics
To prevent electrostatic charging in the fluidized bed reactor, the whole set up is
connected to the electrical earth. Moreover, in all regular tests Larostat 519
(dimethylethyl ammonium ethosulfate supported on silica, kindly supplied by PPG/Mazer
chemicals) as anti-static agent has been used. The bulk density of the powder is 540
kg/m3 and the mean particle size is 9 µm. No effect of the anti-static agent on the
polymerization rate has been found during separate tests in a 0.5-Liter stirred reactor.
Addition of a small amount (~200 mg) prior to the catalyst injections assures a sufficient
amount of anti-static agent in the reaction zone. This amount of anti-static agent
corresponds to about 0.01 wt% of the total reactor contents. Due to the small average
particle size of the powder, some anti-static agent leaves the fluidized bed reactor zone at
high superficial velocities but the anti-static effect remains.
Experimental procedures for mixing and segregation experiments

For the mixing and segregation experiments a LLDPE powder has been used, kindly
supplied by BASF AG (Germany), with a particle size distribution from 100 to 1400 ìm.
The average particle size is 900 ìm. The powder is of type B, according to the Geldart
classification system. For the mixing experiments, black tracer particles have been
prepared from a sieved fraction (420 - 720 ìm) by coloring with black ink. For a mixing
experiment, 15-18 grams of tracer particles have been injected into the fluidized bed
reactor. At a specified time interval, samples are taken from the reactor at 7 vertical
locations. The concentration of tracer is determined using a picture of the sample and
counting the colored particles with imaging software. The vertical segregation profile has
been determined by analyzing the particle size distribution of samples taken from the bed
by laser diffraction (Sympatec Helos LF). The mixing and segregation experiments have
been executed, with and without anti-static agent, using nitrogen as fluidization medium
at 25 °C. The minimum fluidization velocities of the fluid bed at different conditions
have been determined in a classical way from the pressure drop curve by changing the
gas velocity.
Experimental procedures for semi-batch polymerizations

On start-up, the fluidized bed reactor is charged with 1.9 kg of a polypropylene powder,
kindly supplied by DSM (The Netherlands). This powder consists of almost ideally
spherical particles with a narrow particle size distribution. The average particle size is
570 µm. Before polymerization can take place the system must be freed from
contamination. This can be done by thoroughly flushing the system with nitrogen and
propylene followed by evacuation for 1 hour. Propylene is much more effective in
cleaning the system than nitrogen. The reason for this is probably that propylene absorbs
in the polypropylene under pressure, removing most of the contamination after venting.
75
CHAPTER 4
Before polymerizations are started, 30 grams polypropylene precontacted with 0.5 gram
of TIBA is injected to remove the last traces of impurities.
When the system is at the desired conditions, i.e. constant temperature, pressure,
fluidization velocity and gas composition, the system is ready to start the catalyst
injections. In this paper, the results from semi-batch experiments are reported. During
these experiments, a certain amount of catalyst is injected at the beginning of the
experiment. No product is removed from the reaction zone. The amount of polymer
produced in such a batch experiment is small (less than 300 g compared to 1.9 kg start-up
powder), which implies a limited change in bed height. During the experiments the inlet
temperature, fluidization velocity, the total pressure and partial pressures are kept
constant.
The reaction is followed by monitoring the temperature at 6 vertical positions inside the
reactor.
Results
Mixing of particles
The minimum fluidization velocity has been determined experimentally at 15 and 26 bar
nitrogen pressure and 25°C using the LLDPE powder. The determined minimum
fluidization velocity at 15 bar is 7.5 cm/s, at 26 bar a value of 6.0 cm/s has been found.
At 15 bar, slugs have been observed in the upper part of the bed starting at 14 cm/s. At 26
bar, slugs became visible at a slightly higher velocity: 16 cm/s.
Particle mixing has been studied at 11 cm/s and 26 bar nitrogen pressure corresponding to
1.8*Umf. In figure 3, the concentration of tracer versus the vertical position in the reactor
at different time intervals is presented. The concentration of tracer has been made
dimensionless by division with the mean tracer concentration after complete mixing.
After 15 seconds, the tracer is only detected at the second sampling point, probably due
to upward transport of the tracer during injection with nitrogen. The tracer is mixed-up
completely after 300 seconds, which is fast compared to the average residence time for a
catalyst particle in a continuous polymerizing system.
76
CHAPTER 4
4
t = 15 s
3.5 t = 30 s
t = 45 s
3
t = 75 s
2.5 t = 120 s
C/Cmean [-]
t = 300 s
2
1.5
0.5
0
0 100 200 300 400 500 600 700 800 900
Z [mm]
Figure 3: Tracer concentration at different time intervals and vertical position.

Tracer particles injected at Z = 150 mm. U0 = 11 cm/s, 26 bar N2 and 25°C.
Segregation of particles
Vertical segregation has been studied by measuring the flotsam concentration of the
LLDPE powder at different vertical positions. Initially these experiments were carried out
in absence of the anti-static agent. The flotsam has been defined as particles smaller than
500 ìm. In figure 4 the effect of the fluidization time on segregatio n at 11 cm/s and 26
bar is shown. It can be seen that the concentration of flotsam in the bottom zone of the
bed is much lower compared to the concentration in the upper zone. After 1 hour, a fully
segregated pattern can be distinguished. Moreover, the concentration of flotsam in the
upper zone decreases with fluidization time. However, the particles are not leaving the
reactor because no particles were found in the collectors of the cyclones or filter. A layer
of fines with increasing thickness over time could be observed visually over the length of
the reactor wall obviously caused by electrostatic charging. After addition of the anti-
static agent the wall deposits disappeared after a few minutes. In the absence of
electrostatic charges the particles can move more freely through the bed causing better
mixing. In figure 5, the concentration of particles smaller than 420 ìm are compared of
samples taken before and after the injection of the anti-static agent. The average
concentration of particles smaller than 420 ìm observed before the addition of the anti -
static agent is smaller than the original value, presented by the horizontal line in figure 5.
77
CHAPTER 4
After addition of the anti-static agent, the observed average concentration equals the
average of the original powder indicating that no layer is build-up anymore. The results
of the mixing and segregation experiments, together with additional measurements, will
be the subject of a more detailed paper6.
35
1 hour
30 2 hours
3 hours
25 4 hours
Cflotsam [vol%]
20
15
10
0
0 200 400 600 800 1000
Z [mm]
Figure 4: Segregation profile of flotsam as measured at different time intervals
illustrating the build up of a stagnant layer of fines. U0 = 11 cm/s, 26 bar N2 and 25 °C.
12
With anti-static agent
10 Without anti-static agent
Mixed value of original powder

8
C [vol%]
0
0 100 200 300 400 500 600 700 800 900
Z [mm]
Figure 5: Effect of anti-static agent on the observed concentration profile of
particles < 420 ìm. U 0 = 11 cm/s, 26 bar N2 and 25 °C.
78
CHAPTER 4
Batch polymerization experiments

For the batch polymerization experiments a polypropylene powder with almost no fines
has been used for each experiment, see the experimental section, to minimize the risk of
fines sticking at the reactor wall. At 25 bar and 68.5°C, Umf has been derived by
measuring the pressure drop over the bed at different velocities, see figure 6. Using the
same gas composition as used for the polymerization experiments, see table 1, a value of
4.2 cm/s has been found. Using air at atmospheric pressure and room temperature, a
minimum fluidization velocity has been found of 7.4 cm/s. The bed height at minimum
fluidization conditions could be estimated by visual observation. The results are
presented in table 2 together with some physical constants and parameters of the reactor
model for the batch polymerization experiments.
Table 1: Experimental operating conditions.
Inlet temperature 68.5 °C

Pressure 25 bar
Amount of catalyst 0.5 gram
Fluidization velocity Variable
Gas composition
Propylene 65 %
Nitrogen 33 %
Hydrogen 2 %
Three polymerization experiments were executed at 3 different superficial gas velocities.

0.5 gram of catalyst was used for each experiment. The process conditions are
summarized in table 1. The development of the vertical temperature profile in time, both
experimental result and model prediction, are given in figure 7, 8 and 9. The model
prediction is based on a simple dynamic model using the well-mixed assumption and will
be explained below. The superficial velocities were 8, 10 and 13.5 cm/s, respectively.
During these experiments the thermocouple at the highest position, T6, is located above
the surface of the bed. T0 represents the thermal couple below the distributor plate. T1 till
T6 are positioned at 6 different vertical positions, starting at 25 cm above the distributor.
79
CHAPTER 4
25
20
pressure drop [mbar]
15
10
0
0 5 10 15 20 25
U0 [cm/s]
Figure 6: Pressure drop versus the superficial gas velocity at 25 bar and 68.5 °C.
Table 2: Physical constants and parameters for modeling of the fluidized bed reactor.
Parameter Value Parameter Value
Ar (m2) 7.854⋅10-3 Hmf (m) 0.54*

Cp,g (J/kg⋅K) 1473 **
∆Hr (J/kg) 2.47⋅106
Cp,p (J/kg⋅K) 1926 kd0 (s-1) 1.325⋅102
3
Cp,w (J/kg⋅K) 450 kp0 (m /kg.s) 1.303⋅109
Dr (m) 0.1 Umf (m/s) 0.042*
dw (m) 3⋅10 -3
εmf 0.44*
dp (m) 570⋅10 -6
ρg (kg/m )3
35.04**
Eact,d (J/mol) 31.0⋅10 3
ρp (kg/m )3
910
Eact,p (J/mol) 48.0⋅10 3
ρw (kg/m )3
7860
*
Experimentally determined at 25 bar and 68.5°C, see experimental results.
**
Value based on 65% propylene, 33% nitrogen, 2% hydrogen at 341.5 K and 25 bar.
As a finite amount of catalyst is introduced, which is subject to deactivation, the

responding temperature behavior of the semi-isolated fluid bed will be of the shape of a
broad pulse. Only if the bed would be well mixed all thermocouples would indicate the
same temperature.
The experiment at 8 cm/s, 1.9*Umf, shows a very diffuse and complex temperature
profile, see figure 7. Due to the low value of U0-Umf, mixing in the bed is limited and
80
CHAPTER 4
local hot spots are observed. It is remarkably that even with a low activity catalyst as
used in the present work, high local temperatures can be observed. In the beginning of the
experiment the highest temperature is observed in the bottom section of the reactor. It
seems that a hot front, slowly moves upwards to the top of the bed. This can be explained
in two different ways. Firstly, by a slowly segregating bed where a zone with high
catalyst concentration is moving to the top of the bed. Secondly, by a propagating thermal
wave through a packed bed where all reaction heat is generated in bottom part of the bed
at the beginning of the experiment. The speed of such a propagating wave can be
calculated, see equation 1.
(ρC )p g (1)
U front ≈ U 0
(ρC ) + (ρC )
p g p p
The speed of the front observed during the experiment is about 0.03 cm/s, whereas 0.23
cm/s is expected based on equation 1. Thus, the slowly segregating bed is the most
probable explanation for the experimentally observed behavior.
110
T0
T1
100 T2
T3
T4
90 T5
T [°C]
T6
Model
80
70
60
0 10 20 30 40 50 60 70 80
Time [min]
Figure 7: Temperature profile, experiment and model prediction, at 8 cm/s; 1.9*Umf.
The mixing experiments presented in this paper, carried out by tracer injection at 11 cm/s
(about 1.9*Umf), showed a relative fast mixing behavior. This seems to be in
contradiction with the results of the batch polymerization experiment at 8 cm/s, about
1.8*Umf. There are several reasons for the reduced mixing under reaction conditions.
Firstly, it has to be mentioned that the mixing experiments were carried out with a
different polymer, LLDPE vs. iPP, with a different particle size distribution. Moreover,
81
CHAPTER 4
the mixing experiments were carried using nitrogen as fluidization gas. During the
polymerization experiments, propylene is solved into the amorphous phase of the
polypropylene, which causes swelling of the polymer. The molecular weight of the
polypropylene produced with the applied metallocene catalyst system is very low; about
20 kg/mol. This polymer is somewhat sticky, which is probably the major source of the
limited mobility in the bed.
The experiment at 10 cm/s, 2.4*Umf, shows a more regular temperature pattern with a
lower maximum temperature and some temperature gradients inside the bed. The lowest
temperature was found at the bottom section of the bed, as expected. The two
thermocouples T5 and T6 measure a significant higher temperature than the
thermocouples in the bed indicating a relative high polymerization activity in the top
section of the bed and the lean phase above the bed.
90
T0
T1
85 T2
T3
T4
80 T5
T [°C]
T6
Model
75
70
65
0 20 40 60 80 100
Time [min]
Figure 8: Temperature profile, experiment and model prediction, at 10 cm/s; 2.4*Umf.
The experiment at 13.5 cm/s, 3.2*Umf, shows the lowest maximum temperature and
lowest temperature gradients in the bed. The two thermocouples T5 and T6 measure
again a significant higher temperature than the thermocouples in the bed. It appears that
the upper zone of the bed has a high catalyst concentration due to segregation of the
catalyst. Due to the enlarged disengagement zone the elutriation of fine particles did not
result in entrainment of particles from the reactor because no material, except from some
anti-static agent, was found in the cyclones.
82
CHAPTER 4
75
T0
74 T1
T2
73 T3
T4
72 T5
T [°C]
T6
71
Model
70
69
68
67
0 10 20 30 40 50 60 70
Time [min]
Figure 9: Temperature profile, experiment and model prediction, at13.5 cm/s; 3.2*Umf.
Simplified reactor model

The modeling of fluidized bed reactors for olefin polymerization has been the subject of
several papers. No experimental data were used for verification in these publications.
Choi et al.7 developed a model that takes temperature and concentration gradients within
the bubble phase into account. McAuley et al.8 compared the two-phase model with a
simple well-mixed model and concluded that the well-mixed model is appropriate for
predicting the temperature and concentration in the gas phase of industrial fluidized bed
polyethylene reactors if the bubble size is small as predicted by several maximum stable
bubble size correlations. If the well-mixed assumption is valid, both for concentration as
well as temperature profiles, experimental results and correlations developed from well-
stirred gas phase laboratory reactors could be used immediately to model industrial-scale
fluidized bed reactors.
None of the models mentioned above takes the segregation of particles into account. In
order to compare the measured temperature profiles, a simple dynamic model is given
here assuming the well-mixed assumption.
83
CHAPTER 4
Model assumptions:
1. During the reaction polymer is formed causing an increase in the bed level and
possibly a change in average bed properties since the polymer formed has different
polymer and morphological properties. These aspects are not taken into account. The
model calculates with an average density and heat capacity of the reaction zone.
2. The heat transfer from the bed to the reactor wall combined with the heat transfer
through the wall is relatively fast compared to the heat transfer from the reactor wall
to the reactor surroundings. It is assumed that the temperature of the reactor wall
equals the temperature of the reactor contents. Heat losses from the wall are not taken
into account.
3. The kinetic constants are based on an experimental kinetic study (see Meier et al.4)
with the same catalyst system.
Under these assumptions, the modeling equations are as follows:

The reaction rate is first order with respect to the number of active sites, C*, and the
monomer concentration in the polymer, Cm.
R p = k p C*C m (2)
Here kp=kp,0exp(-Eact,p/RT), where kp is the propagation rate constant and Eact,p the
activation energy for propagation. The monomer concentration in the polymer has been
calculated with the Flory-Huggins equation. The Flory-Huggins interaction parameter, is
based on the experimental data published before4.
The deactivation of the catalyst is described by a first order relation, see equation 3.
dC * (3)
= −k d C*
dt
Here kd=kd,0exp(-Eact,d/RT), where kd is the deactivation rate constant and Eact,d the
activation energy for deactivation.
The mass balance for monomer:
d (Vr ερ g X m )
= U 0 A r ρ g (X m , 0 − X m ) − R p (4)
dt
The energy balance:
d (Vr + w ρ av C p,av T )
= U 0 A r ρ g C p ,g (T0 − T ) + R p ∆H r (5)
dt
84
CHAPTER 4
The initial conditions are as follows:
at t = 0, C* = C0 (6)
Xm = Xm,0
T = T0
Vr+w is based on the volume of the reaction zone plus the volume of the reactor wall:
Vr + w = Vr + π(D 2r + w − D 2r )H r
1 (7)
4
with Dr+w = Dr + 2dw.
The average density and heat capacity of the volume heated-up:
1
ρ av = (8)
mp mgm
+ + w
ρp ρg ρw
C p ,av = m p C p , p + m g C p,g + m w C p , w (9)
Here mp, mg and mw are the mass fractions of the polymer, monomer and wall
respectively. They are defined as:
Mp (10)
mp =
M p + Vr ερ g + Vr + w ρ av
Vr ερ g (11)
mg =
M p + Vr ερ g + Vr + w ρ av
m w = 1 − m p − mg (12)
The mass fractions are influenced by the superficial gas velocity U0 since the volume of
the reaction zone is increasing with increasing U0. Correlations given by Kunii and
Levenspiel9 have been used to calculate the fraction of bubbles in the bed, which is
required to calculate the bed volume.
Many fluidization correlations published in literature are based on experimental work

executed at normal pressure. It is known that the gas density applied for the
polymerization of olefins can cause severe deviation. Properties like bubble size and
regime of fluidization may change with increasing pressure. Moreover, the absorption of
propylene in the amorphous part of the polymer may effect the interaction between
polymer particles due to swelling of the polymer. This will affect hydrodynamic
85
CHAPTER 4
properties like minimum fluidization velocity Umf. Therefore, Umf, Hmf and εmf have been
determined experimentally.
The results of the model prediction are presented together with the experimental results in
figure 7 – 9. The simple model seems to be able to describe the general shape of the
temperature profiles inside the bed if U0 is not too low. Since the model is based on an
ideal mixed system of both the gas and solid phase, i.e. segregation and mixing
phenomena have not been taken into account, the model is not able to predict the
temperature gradients observed. The increase in temperature during the first couple of
minutes seems to be overestimated. This is because the kinetic model does not take the
activation of the catalyst into account. The over prediction of the temperature rise for the
experiment at 13.5 cm/s is due to the elutriation above the highest thermocouple in the
reactor.
It is clear from these results that the mixing and segregation processes of the solids
should be included in the model. Such a model should also consider scaling-up relations
for the actual solids mixing and segregation under reaction conditions if the model is to
be used for industrial applications.
Discussion
It has to be noted that only batch polymerizations have been executed where at the
beginning of the experiment a certain amount of catalyst is injected. In case of a
continuous system, fresh catalyst is added continuously resulting in a particle size
distribution, which is directly related to the residence time distribution of catalyst and
polymerization kinetics. This of course will affect the mixing and segregation behavior of
the system. A more complex model based on CFD and discrete particle description, see
e.g. Hoomans et al.10, should be able to cope with these phenomena.
Vertical solids mixing in a fluidized bed reactor is strongly related to the reactor scale.
The solids mixing rate is in general expressed in engineering models in the form of an
overall diffusion or dispersion coefficient, although this concept does not explain the
complex physical phenomena involved. Matsen11 reported that the dispersion is directly
proportional to bed diameters up to 10 m. In our small-scale fluidized bed reactor the
average bubble size is about half of the reactor diameter. In case of an industrial sized
reactor, this ratio is quite different. Here the reactor diameter and height are about 4 and
12 meters, respectively. Moreover, the mixing of solids is determined by the gross
circulation pattern of solids generally observed in reactors of this scale. The bubbles tend
to accumulate in the center of the reactor causing an upward “gulf stream” of solids in the
center and down flow near the reactor wall. These phenomena are not observed in
reactors at a small-scale as used in the present study. Matsen11 concluded that the limited
86
CHAPTER 4
success of bubbling bed models for the description of large units can be explained by the
fact that bubble velocities and bed densities cannot be calculated from knowledge of
superficial gas velocity and bubble size caused by the “gulf stream” present in the
reactor. In our next paper3 we will report upon the controlled mixing in a small-scale
fluidized bed reactor by installation of a draft tube in the center of the reactor. The small-
scale fluidized bed reactor as described in the present paper cannot be used for scale-up.
However, phenomena like electrostatic charging, sheeting and agglomeration, catalyst
screening, slugging and the elutriation of fines are subjects that can be studied at actual
reaction conditions in the present set up.
Conclusion
Vertical particle mixing and segregation have been studied in a small-scale fluidized bed
under pressure. At higher gas velocities relative fast mixing of tracer particles has been
found compared to the overall residence time of catalyst particles normally encountered
in a polymerizing system. Particle size analysis of samples taken at different vertical
positions showed that the smaller particles accumulate in the upper zone of the bed. The
influence of electrostatic charging is important. A layer of small particles with increasing
thickness in time is formed over the total length of the reaction zone but is redispersed
after injection of an anti-static agent.
The simple back-mixed model is not able to describe the vertical temperature gradients
observed during the batch polymerization experiments, because no segregation and no
mixing phenomena have been taken into account. Mixing and segregation phenomena of
the solid phase (valid for reaction conditions) have to be incorporated.
Three semi-batch polymerization experiments have been executed at different

fluidization velocities. The phenomena observed during the mixing and segregation
experiments were also observed during the polymerization experiments. It turned out that
the catalyst particles accumulate in the upper zone of the bed creating a vertical
temperature gradient. The speed of segregation is directly related to the mixing rate and
therefore to the fluidization velocity. The balance between segregation and mixing cannot
be compared to an industrial sized unit and vertical mixing should be enhanced to be
more representative.
technical assistance. G.H. Banis is acknowledged for his technical support and E. Vellenga, M.J.
Mollenhorst, N.F. Geijsen and A.A. van Klaveren for their contribution in the experimental part. The
author further wishes to thank DSM Research and BASF AG for the materials and help they provided.
87
CHAPTER 4
Notation
Ar Cross-sectional area of fluidized bed m2
C* Amount of active sites kg
Cm Monomer concentration in polymer kg/m3
Cp Heat capacity J/kg⋅K
dp Mean particle size of polymer m
dw Wall thickness of reactor m
Dr Diameter of fluidized bed reactor m
Eact,p Activation energy for propagation J/mol
Eact,d Activation energy for deactivation J/mol
Hr Bed height m
Hmf Bed height at Umf m
∆Hr Heat of reaction J/kg
kd Reaction rate constant for deactivation sec-1
kp Reaction rate constant for propagation m3/kg.s
m Mass fraction -
Mp Mass of start-up powder kg
Rp Reaction rate kg/s
t Time s
T Temperature K
T0 Temperature of inlet gas K
Umf Minimum fluidization velocity m/s
U0 Inlet gas velocity m/s
V Volume m3
X Mass fraction of monomer in gas phase -
Z Vertical position in reactor m
Greek
ε Void fraction of gas in bed -
ρ Density kg/m3
Subscripts
av Average value
g Gas
m Monomer
p Polymer
r Reactor
w Wall
88
CHAPTER 4
0 Initial value
Abbreviations
Al Aluminium
Zr Zirconium
Literature
1. US 5,283,278: BP Chemicals Ltd., (1994)
2. US 5,241,023: BP Chemicals Ltd., (1993)
3. Meier, G.B., Weickert, G., van Swaaij, W.P.M., submitted to AIChE J., (2000)
(2000)
5. Samson, J.J.C., Weickert, G., Heerze, A.E., Westerterp, K.R., AIChE J., 44, 1424,
(1998)
6. Roos, P., Westerterp, K.R. “Segregation and mixing at elevated pressures in a
fluidized bed polymerization reactor”, in preparation.
7. Choi, K.Y., Ray, W.H., Chem. Eng. Sci., 40(11), 2261 – 2279, (1985)
8. McAuley, K.B., Talbot, J.P., Harris, T.J., Chem. Eng. Sci., 49(13), 2035 – 2045,
(1994)
9. Kunii, D., Levenspiel, O., “Fluidization Engineering”, 2nd edition, Butterworth-
Heinemann, USA, (1991)
10. Hoomans, B.P.B., Kuipers, J.A.M., van Swaaij, W.P.M., in Fluidization IX, L.-S.
Fan, T.M. Knowlton (eds), 485, (1998)
11. Matsen, J.M., Powder Techn., 88, 237-244, (1996)
89
CHAPTER 4
90
CHAPTER 5
Chapter 5
FBR mini-plant for catalytic olefin polymerization:

Controlled particle mixing, propylene polymerization and
reactor modeling.
Abstract
A small-scale fluidized bed reactor has been equipped with a draft tube and cone to
control the vertical solids mixing. The internal solids circulation rate is a non-linear
function of the gas velocities. Strongly reduced elutriation and entrainment have been
observed, compared to experiments without draft tube. Semi-batch propylene
polymerizations have been executed at elevated pressures. The temperature profiles can
be controlled by the solids circulation rate. Hydrogen injections led to an instantaneous
increased polymerization rate, probably due to the reactivation of dormant sites. The
irreversible deactivation rates of dormant and active sites seem to be the same.
Moreover, hydrogen appeared to be very effective to broaden the molecular weight
distribution. A compartment model is developed to describe the temperature profile in the
reactor and related molecular weight distribution of the polymer.
91
CHAPTER 5
92
CHAPTER 5
Introduction
The most widely established industrial gas phase technology for polyolefin production is
the fluidized bed reactor operating at elevated pressures between 20 and 30 bar. In these
large-scale units, bubbles rising from the distributor plate tend to accumulate in the center
of the reactor, causing an upward “gulf stream” of polymer powder. Particles closer to the
wall are generally moving in downward direction thus creating an overall circulation.
Depending on the H/D a single or more mixing cells may occur. Intensive exchange
between up and down flows may create a diffusion type of mixing. This strong
mechanism of solids mixing reduces temperature and concentration gradients in fluid
beds. In polymerization temperature and concentration gradients would affect directly the
molecular weight distribution of the polymer. However, the rate of mixing in fluid beds is
strongly dependent on the scale of operation, see e.g. Matsen et al.1, and on a small scale
the axial mixing is lower and “gulf streaming” less prominent or absent.
In a previous paper2, we have reported upon the solids mixing and propylene
polymerization in a small-scale fluidized bed reactor. Severe particle segregation and
elutriation was found. At polymerization conditions, where the small particles are most
active, high local temperatures were found due to segregation insufficiently counteracted
by vertical mixing.
In the present paper, a modified small-scale fluidized bed reactor is used to study aspects
of the polymerization of olefins at conditions resembling those of industrial fluidized bed
reactors as well as strongly deviating conditions with controlled thermal gradients. The
latter may be of interest for a controlled broadening of the molecular weight distribution
of the polymer. To realize this, the vertical solids mixing, elutriation and entrainment
should be controlled. A vertical draft tube installed in the center of the fluid bed is a well-
known instrument of chemical engineers to control the axial solids mixing but has never
been used for a fluidized bed polymerization reactor before according to the scientific
and patent literature. Using the draft tube, the internal solids circulation rate can be
controlled by the gas velocity in the draft tube and in the annulus space. In this way it is
possible to simulate the solids circulation pattern observed at industrial scale in a small-
scale unit. Because the draft tube and annulus are generally operated at different gas
velocities, both sections have different heat transport properties, temperatures and
temperature gradients. Therefore, for a particle circulating through the reactor an
oscillating particle temperature may occur along the particle trajectory.
The temperature profiles in the reactor will broaden the molecular weight distribution of
the polymer. Moreover, it should be possible to control the molecular weight distribution
of the polymer by controlling the circulation rate of the solids in the reactor.
93
CHAPTER 5
Note that a recently developed new multi-zone process for the polymerization of olefins3
is based on the same principles. However, here the solids circulation is external and based
on a riser-downer combination. Although the draft tube can be used to increase the solids
mixing in the present investigation, the emphasis is placed on the elimination of
segregation and the creation of different zones in one reactor. This was already realized
with one single gas phase reactant injection point although the draft tube would also
allow injection of different gases in different zones. The latter is not part of the present
work.
Experimental
FBR set up
The experimental set up, see figure 1, comprises a fluidized bed reactor, 10 cm inner
diameter and 1 m in height, a special catalyst injection system, two cyclones, a membrane
compressor, two heat exchangers, flow control valves, mass flow meter and has been
described in detail in a previous paper2. For the experiments presented in this paper, a
draft tube and conical bottom section have been installed to force the solids circulation
with a single gas injection point. In this set up particles are forced to move upwards in the
draft tube section and enter the annulus section where they move in a densified form with
no bubbles present under the action of gravity (“moving bed”). Polymer particles leaving
the annulus section are entering the well-mixed cone section and are reintroduced to the
draft tube section. In this way a solids circulation is set up, which can be controlled by
the inlet gas velocity of the unit. The length, inner diameter and wall thickness of the
draft tube are 770, 50 and 5, respectively. The draft tube, made of glass, is placed in the
center of the reactor 130 mm above the distributor plate and is fixed in place with three
horizontal rods at the bottom and the top. The inlet diameter and height of the cone are 50
and 150 mm, respectively. Thermocouples in the annulus section are available at 6
different vertical positions (25, 35, 45, 55, 65 and 90 cm above the distributor plate). 2
thermocouples are installed in the draft tube section (20 and 60 cm above the distributor
plate). The device to measure the pressure over the annulus is connected to the reactor at
15 and 90 cm above the distributor plate. The installation is placed in a concrete bunker
and fully computer controlled.
94
CHAPTER 5
Vent
Inlet propylene and
hydrogen
IR
T a(6) Cyclones
T a(5)
H2 T d(2)
NO
T a(4)
dP Buffer vessel
T a(3)
Vent
T a(2)
T a(1)
T d(1)
Catalyst
injection
Te
NO
Product removal
NO
Control Valve Check Valve Filter
Valve Relief Valve Heat exchanger
Flow meter Rupture Disk

Compressor
Figure 1: Schematic representation of the fluidized bed reactor equipped with draft tube.
Catalyst system
The catalyst used, is the well-known metallocene rac-Me2Si[Ind]2ZrCl2. The catalyst,
kindly supplied by Witco Co. Bergkamen (Germany), is supported on PQ silica with a
concentration of 0.79 wt% of metallocene. The MAO/SiO2 – support used for
immobilization of the metallocene contained 19.1 wt% of alumina. Tri-
isobuthylaluminium (TIBA) has been used as cocatalyst to increase the polymerization
95
CHAPTER 5
activity. The amount of TIBA and the precontact time has been kept constant for all
experiments. The exact preparation procedure has been described in a previous paper4.
Experimental procedure for solids circulation measurements

The solids circulation rate as function of the inlet gas velocity has been determined by
measuring the residence time of tracer particles in the annulus section. On start-up, the
reactor is charged with 2 kg of polypropylene powder. This powder consists of almost
ideally spherical particles with a narrow particle size distribution and may be regarded as
a type B powder according to the Geldart classification system. The average particle size
is 570 µm. With this amount of polymer in the system, the bed level in the annulus is
about 10 cm below the top of the draft tube. To prevent electrostatic charging, about 200
mg Larostat 519 (dimethylethyl ammonium ethosulfate supported on silica, PPG/Mazer
chemicals) as anti-static agent has been used for every experiment. Before the tracer
injection, the system is brought to the desired temperature, pressure, gas composition and
gas velocity. About 25 grams of colored tracer particles are injected from above at the top
of the annulus bed. Because the particles are moving under nearly plug flow conditions in
the annulus, the tracer particles can be followed through the observing glasses located at
4 different vertical positions (12.5, 37.5, 62.5 and 87.5 cm above the distributor plate).
The time required to flow through the annulus section has been measured in this way and
is used to calculate the circulation rate.
Experimental procedure for semi-batch polymerizations

On start-up, the reactor is charged with 1.9 kg of a polypropylene powder, the same as
was used for the circulation rate measurements. Before polymerization can take place the
system must be freed from contamination. The exact cleaning procedure has been
described in a previous paper2. When the system is at the desired conditions, i.e. constant
temperature, pressure, anti-static agent concentration, gas velocity and gas composition,
the system is ready to start the catalyst injections. In this paper, the results of semi-batch
experiments are reported. During these experiments, a small amount of catalyst is
injected at the beginning of the experiment. No product is removed from the reaction
zone. The amount of polymer produced in such a batch experiment is relatively small
(less than 300 g) compared to the amount of start-up powder, which implies a limited
change in bed height and circulation rate. However, the bed level in the annulus never
exceeds the height of the draft tube during the experiment. During the semi-batch
experiments the inlet temperature, gas velocity, the total pressure and partial pressures are
kept constant. As the reactor is to a large degree isolated from the environment, the
reaction rate in semi-batch operation can be followed by the temperature response,
interpreted by the in-stationary heat balance. The temperature is therefore monitored
continuously at the several vertical positions in the annulus and draft tube section. The
polypropylene samples obtained at the end of the experiment were characterized with
96
CHAPTER 5
respect to their molecular weight and molecular weight distribution by Gel Permeation
Chromatography (GPC). These GPC measurements were carried out on a Waters M150C
apparatus with TSK columns at 140°C using 1,2,4-trichlorobenzene as solvent.
Results
Solids circulation
Experiments at different pressures and gas compositions have been executed, see table 1,
to study the influence on the circulation rate. The residence time of solids in the annulus
section has been measured as function of the gas velocity, see figure 2. Note that the gas
velocity is based on the velocity at the cone inlet, i.e. 50 mm in diameter. This velocity
does not represent the fluidization velocity in the draft tube or annulus section, as the gas
is divided over these two sections. As can be seen from figure 2, the residence time of
solids in the annulus decreases with increasing gas velocity. The gas density hardly
influences the circulation rate, although some differences have been observed between
the experiments at 15 and 25 bar with 65% propylene. The measured solids velocity in
the annulus stays for all experiments (between 1.7 and 3.5 cm/s) below the minimum
fluidization velocity, i.e. 4.2 cm/s.
Table 1: Process conditions for circulation rate measurements.

T [°C] p [bar] Propylene [%] Nitrogen [%] ρg [kg/m3]
338 25 65 35 35.5
338 25 0 100 25.0
338 15 65 35 20.4
293 1 Air 1.0
A certain minimum gas velocity (Ue,min) is required to start the circulation of solids in the
system. This minimum gas velocity decreases with increasing density of the gas phase.
The minimum gas velocity required at atmospheric pressure is about 42 cm/s, whereas
this velocity is about 24 cm/s at 25 bar with 65% propylene.
Further visual observation of the solids circulation experiments showed that the tracer
particles were mixed through the reactor contents after 3 to 4 circulations. Most of the
mixing is achieved in the cone section. The flow behavior of solids in the draft tube is of
the slugging type. At very high velocities, 45 cm/s, a transition towards turbulent
fluidization is observed. Only minor dispersion of solids in the annulus is observed. No
bubbles in the annulus section have been detected.
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CHAPTER 5
90
Ue,min
25 bar, 100% Nitrogen
80
25 bar, 65% Propylene
70 15 bar, 65% Propylene
1 bar, air
Residence time [s]
60
50
40
30
20
10
0
0 20 40 60 80 100
Ue [cm/s]
Figure 2: Solids residence time in the annulus with a length of 77 cm as function of
gas velocity. Ue,min represents the minimum gas velocity to start solids circulation.
The pressure drop over the annulus has been measured at different gas velocities and bed
weights using nitrogen at 25 bar and 60 °C as fluidization medium, see figure 3. As
expected, larger pressure drops have been observed with increasing bed weight.
Increasing the gas velocity results in a decreasing pressure drop over the annulus,
indicating a lower solids hold up in the draft tube with increasing gas velocity because of
the coupled pressure balance for the annulus and draft tube. The bed height in the annulus
is almost constant with increasing gas velocity. The decreasing pressure drop over the
system with increasing gas velocity also indicates a decreasing upward gas velocity in the
annulus section with increasing gas velocity. The lower gas bypassing to the annulus
section with increasing gas velocity is in agreement with the results reported by Ji et al.5.
The Ergun equation have been used to calculate the minimum upward gas velocity in the
annulus, i.e. at the highest solids circulation rate. Assuming a bed porosity of 0.42 and a
shape factor of 1, a slip velocity of 4.6 cm/s have been found. The downward solids
velocity at these conditions is 3.5 cm/s. The minimum upward gas velocity in the annulus
is therefore 1.1 cm/s.
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CHAPTER 5
20
1.8 kg
19 1.9 kg
2.0 kg
2.1 kg
pressure drop [mbar]
18
2.2 kg
2.3 kg
17
2.4 kg
16
15
14
13
18 22 26 30 34 38 42 46 50 54
Ue [cm/s]
Figure 3: Influence of total polymer hold up on the pressure drop over the
annulus as function of the gas velocity using 25 bar N2 at 60°C.
Semi-batch polymerizations
Semi-batch propylene polymerizations have been executed at 25 bar and different gas
velocities, i.e. different solids circulation rates. The first experiment has been executed
with a gas inlet temperature of 68°C. Before the catalyst is injected the system is
stabilized, i.e. constant temperature, pressure, gas velocity, etc. Then the total amount of
catalyst, 1 gram, is injected in about 4 minutes. The responding temperature behavior of
the semi-isolated fluid bed will be of the shape of a broad pulse, because the catalyst is
subject to deactivation. Only at a very high solids circulation rate all thermocouples, both
in the draft tube and annulus, would indicate the same temperature. At lower circulation
rates temperature gradients will appear in both sections as follows. Particles coming from
the annulus will be cooled down in the cone by the relative cold gas thereby absorbing
monomer. On the way up in the draft tube, the temperature will increase a little due to the
polymerization reaction although this remains a small effect due to the short residence
time in this section. Along the way down in the annulus much more polymerization takes
place at these longer residence times and less convective cooling capacity is available
resulting in a relative large temperature gradient.
The temperature profile of the annulus section of the first experiment is presented in
figure 4. The initial decrease in temperature is due to the catalyst injections with cold
nitrogen. After the catalyst injections, the temperature starts rising rapidly and reaches a
99
CHAPTER 5
maximum after about 15 minutes. At this point, the largest temperature gradients inside
the reactor have been observed, about 5°C. Then the catalyst starts to deactivate and the
temperature inside the reactor returns to its initial value after about 1.5 hours. The
maximum temperature observed in this experiment was about 83°C. This would be above
the critical temperature for which a thermal runaway on particle scale may occur4.
86
Ta(1)
83
Ta(2)
80 Ta(3)
Ta(4)
77 Ta(5)
T [°C]
Ta(6)
74
71
68
65 Catalyst injections
62
0 10 20 30 40 50 60 70 80 90 100
t [min]
Figure 4: Temperature profile of the annulus as a function of time during a semi-
batch polymerization. Ta(1) and Ta(6) indicate the temperature in the bottom and top
of the annulus, respectively.
Table 2: Process conditions for batch polymerization experiments with Te = 58°C.

Ue [cm/s] ua,s [cm/s] [C3H6] [%] [N2] [%] [H2] [%]
25.1 1.7 69.6 29.4 1.0

30.4 2.3 69.0 30.0 1.0
36.2 3.0 66.6 32.4 1.0
42.7 3.5 67.1 31.9 1.0
There are several ways to prevent the thermal runaway, for instance by prepolymerization
or by lowering the gas inlet temperature. The next series of experiments were executed
with a gas inlet temperature of 58°C to minimize the risk of a thermal runaway, see table
2. The temperature profiles of the annulus section of these experiments are given in
100
CHAPTER 5
figure 5 – 8. The experiment at the lowest gas velocity, 25.1 cm/s, shows the highest
internal temperature gradient and absolute temperature. The experiment at 42.7 cm/s
shows only minor internal temperature gradients, about 1°C, and may be interpreted as an
experiment in a CSTR. The scattering during the initial phase of the experiment at 30.4
cm/s and twice during the experiment at 36.2 cm/s is due to some solids circulation
disturbances, probably because of some temporary sticking of particles at thermocouples.
The temperature gradients measured inside the draft tube section are much less due to the
high gas velocity. The gas velocity in the draft tube is for the experiments at 25.1 and
42.7 cm/s about 3.3 and 7.6 times Umf, respectively. The temperature gradients in the
draft tube observed for the experiment at the highest and lowest circulation rate were 0.2
and 1°C, respectively.
76
Ta(1)
73 Ta(2)
Ta(3)
70 Ta(4)
Ta(5)
67
T [°C]
Ta(6)
64
61
58
55
0 10 20 30 40 50 60 70 80
t [min]

batch polymerization. Ue = 25.1 cm/s, ua,s = 1.7 cm/s.
101
CHAPTER 5
76
Ta(1)
73 Ta(2)
Ta(3)
70 Ta(4)
Ta(5)
67
T [°C]
Ta(6)
64
61
58
55
0 10 20 30 40 50 60 70 80
t [min]
69
Ta(1)
67 Ta(2)
Ta(3)
65 Ta(4)
Ta(5)
63
T [°C]
Ta(6)
61
59
57
55
0 10 20 30 40 50 60 70 80 90
t [min]
102
CHAPTER 5
65
Ta(1)
Ta(2)
63
Ta(3)
Ta(4)
61 Ta(5)
T [°C]
Ta(6)
59
57
55
0 10 20 30 40 50 60 70 80 90 100 110
t [min]
Injection of hydrogen
From kinetic experiments published before4, it was concluded that the current catalyst
system is sensitive towards hydrogen. The molecular weight of the produced polymer is
decreasing with increasing hydrogen concentration, whereas the polymerization activity
is increasing with increasing hydrogen concentration. The main reason for the increased
polymerization rate is that hydrogen prevents the formation of dormant sites, which occur
after a secondary insertion of propylene.
In a next series of experiments, see figure 9, hydrogen has been injected in the gas
recycle at different moments during semi-batch experiments. Thus a certain fraction of
the end product is produced at a low hydrogen concentration giving a high molecular
weight polymer, the other part of the product is produced at a high hydrogen
concentration giving a low molecular weight polymer. During the experiment the
propylene concentration is kept at its initial value, 60 vol%, i.e. the pressure increases
about 1 bar after the injection of hydrogen. The hydrogen concentration before injection
is 0.0217 kg/m3 (∼1 vol%) , after the injection of hydrogen the concentration is raised to
0.123 kg/m3 (7 vol%). All experiments have been executed with a gas inlet temperature
of 59.5 °C and a gas velocity of 36 cm/s, i.e. about 3 cm/s solids velocity in the annulus.
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CHAPTER 5
Due to some problems with the catalyst injection system, the experiments showed lower
polymerization activities. The results will be interpreted in a qualitative way, based on
the temperature measurements of the annulus, by normalizing the curves. In figure 9, the
results are given of the hydrogen pulse experiments showing the difference between the
gas inlet temperature and the temperature at the bottom of the annulus, Ta(1), during the
experiments. The negative value of Ta(1)-Te during the first couple of minutes is the
result of the catalyst injections with cold nitrogen. As can be seen from figure 9, the
temperature immediately increases after injection of hydrogen, indicating an almost
instantaneous increase in polymerization rate. The reaction rate to reactivate the dormant
sites is probably fast.
7
Injection after 12.5 min
6
Injection after 16 min
5
4
3
∆T [°C]
0
0 10 20 30 40 50 60 70
-1
-2
t [min]
Figure 9: Normalized temperature profiles in the bottom of the annulus during
different semi-batch polymerizations with hydrogen injections at different moments.
Ue = 36 cm/s, ua,s = 3 cm/s.
A second feature observed from figure 9 is that the different temperature curves follow
more or less the same master curve before and after the injection of hydrogen. The active
sites probably deactivate with about the same rate at the applied process conditions.
Moreover, the relative increase in temperature after the injection is more or less constant.
Because the increase is probably caused by the reactivation of dormant sites, one may
conclude that the relative concentration of dormant sites, relative towards the amount of
active sites, is constant during the experiment. Dormant sites deactivate probably with the
same rate as the active sites.
104
CHAPTER 5
Reactor model
A reactor model has been developed, which should be able to describe the temperature
and concentration gradients inside the reactor and the related molecular weight
distribution of the polymer product. The reactor model uses the measured solids
circulation rate measurements as input. The results of the circulation rate measurements
are highly related to the geometry of the set up, e.g. diameter and length of the draft tube,
the distance between draft tube and cone
and the angle of the cone. Several Gas out
authors have reported that the geometry
of the reactor has a large influence on the
solids circulation rate6-9. No data are
available on pressurized systems. In the Solids
present paper at the given geometry, just
the influence of the gas velocity on the Nd Na
solids circulation rate has been
investigated and is used as input for the
model.
The assumptions for the reactor model

Draft tube
Annulus
are summarized below. 3 3
1. The reactor is divided in three
sections; the annulus, draft tube
and cone section. The draft tube
and annulus sections are divided 2 2
in N CSTR’s in series to simulate
plug flow in both sections. The
cone is considered as one CSTR.
The reactor model is 1 1
schematically presented in figure
10.
2. The resistance towards mass and
heat transfer between the gas and Cone
solids in each compartment is
negligible, which is acceptable10
in case the catalyst activity is not Gas
extremely high and the particles
are relatively small. Particles Figure 10: Schematic presentation
circulating in the system are of the reactor model.
continuously absorbing and
105
CHAPTER 5
desorbing propylene due to the temperature gradients in the system. Equilibrium

is assumed in each compartment.
3. The energy effects due to absorption and desorption of propylene have been
neglected.
4. The gas and solids velocities in the reactor are assumed to be constant, because
the monomer conversion per pass through the reactor is low.
5. Minimum fluidization conditions for the annulus have been assumed. The voidage
of the cone and draft tube section are equal to the experimentally determined
value.
6. No heat transfer from the annulus to the draft tube section takes place.
7. The heat transfer from the annulus bed to the reactor wall combined with the heat
transfer through the wall is relatively fast compared to the heat transfer from the
reactor wall to the reactor surroundings. This, because the reactor is placed in an
air thermostat at 50 °C, which reduces the heat losses to a large extend. It is
assumed that the wall temperature of the adjacent annulus compartment equals the
temperature of the reactor contents. Heat losses are described using a Nusselt
correlation for heat transfer from a flat plate to laminar flowing air.
The kinetic model and kinetic constants are based on an experimental study4 with the
same catalyst system. The model does respect the initiation and deactivation of the
catalyst, see scheme 1. The reaction rate is described by first order kinetics with respect
to the number of active sites, C*, and the monomer concentration in the polymer, Cm. The
monomer concentration is calculated using the Flory-Huggins equation. The Flory-
Huggins interaction parameter, is based on the experimental data published before11. The
density and heat capacity of the gas phase are functions of the local temperature and gas
composition and have been described according to Peng-Robinson and Daubert et al.
(1985), respectively.
ki kp
C C* C*-Pj
kd kd
Deactivated catalyst
Scheme 1: Activation, propagation and deactivation of the catalyst.

To obtain a clear understanding of the reactor model, the material and energy balances
will be described separately for the cone compartment, an arbitrary draft tube
compartment and an arbitrary annulus compartment.
106
CHAPTER 5
Cone compartment
Mass balance for non-activated catalyst in the cone:
= φm , s (X Ca ,1 − X Cc ) − k i Cc
dCc (1)
dt
Here X Cc is the mass fraction of non-activated catalyst in the cone, defined as:
Cc (2)
X Cc =
Cc + Vc (1 − ε c )ρs
The first term in the right side of equation 1 concerns the convective flow of non-
activated catalyst. The second term concerns the initiation of non-activated catalyst with
initiation rate constant ki.
Mass balance for activated catalyst in the cone:
dC*c
dt
( )
= φm,s X Ca,1 − X Cc + k i Cc − k d C*c
* * (3)
*
Here X Cc is the mass fraction of activated catalyst in the cone, defined as:
C*c (4)
X Cc =
*
C + Vc (1 − ε c )ρs
*
c
The first term in the right side of equation 3 concerns the flow of activated catalyst, the
second term the initiation towards active catalyst and the third term the deactivation of
the catalyst.
Mass balance for monomer in the cone:
(
d Vc ε c ρ g m cm ) = U A ρ (m m
)
− m cm − R p ,c
(5)
e e g e
dt
The first term in the right side of equation 5 concerns the flow of monomer through the
cone. The second term represents the consumption of monomer in the cone due to
polymerization.
The reaction rate in the cone compartment is described with:
R p , c = k p C*cC m , c (6)
Here C*c stands for the amount of activated catalyst in the cone compartment.
Energy balance for the cone:
107
CHAPTER 5
d (Vc ρ av ,c C p,av ,c Tc ) (7)

= U e A e ρ g C p,g (Te − Tc ) + φ m,s C p ,s (Ta ,1 − Tc ) + R p,c ∆H r
dt
The first two terms in the right side of equation 7 concern the enthalpy associated with
the gas and solid flow through the cone. The third term stands for the amount of heat
produced due to polymerization.
Starting conditions for the cone at t = 0:
C c (0) = C c , 0 (8)
C*c (0) = 0
Tc (0) = T0
m cm (0) = m 0m
Draft tube compartment i

The mass and energy balances for a draft tube compartment are analogous:
Mass balance for non-activated catalyst:
= φm , s (X Cd ,i −1 − X Cd , i ) − k i Cd ,i
dCd , i (9)
dt
Here X Cd , i is the mass fraction of non-activated catalyst, defined as:
Cd ,i (10)
X Cd ,i =
Cd , i + Vd , i (1 − εd )ρs
Mass balance for activated catalyst:
dC*d , i
dt
( )
= φm, s X Cd ,i −1 − X Cd ,i + k i Cd ,i − k d C*d ,i
* *
(11)
*
Here X dC, i is the mass fraction of activated catalyst, defined as:
C*d , i (12)
X Cd ,i =
*
C + Vd , i (1 − εd )ρs
*
d,i
Mass balance for monomer:
108
CHAPTER 5
(
d Vd ,i ε d ρ g m dm,i )=u ( )
A d ρ g m dm,i−1 − m dm,i − R p ,d ,i
(13)
d ,g
dt
The equation for the polymerization rate:
R p ,di = k p C*d ,i C m ,d ,i (14)
Energy balance:
d (Vd ,i ρ av
d ,i C p ,d ,i Td ,i )
av (15)
= u d ,g A d ρ g C p ,g (Td ,i−1 − Td ,i ) + φ m ,s C p,s (Td ,i−1 − Td ,i )
dt
+ R p,d ,i ∆H r
Starting conditions for t = 0:
C d ,i (0) = C d , 0 (16)
C*d ,i (0) = 0
Td,i (0) = T0
m dm,i (0) = m 0m
Coupling between cone and draft tube:
Td , 0 = Tc (17)
X dC, 0 = X Cc
X dC, 0 = X Cc
* *
m dm, 0 = m mc
Annulus compartment i
Mass balance for non-activated catalyst:
dCa , i
dt
( )
= φm, s X Ca , i +1 − X Ca , i − k i Ca , i
(18)
Here X aC, i is the mass fraction of non-activated catalyst, defined as:
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CHAPTER 5
Ca , i (19)
X Ca , i =
Ca , i + Va , i (1 − εa )ρs
Mass balance for activated catalyst:
dC*a , i
dt
( )
= φm, s X Ca , i +1 − X Ca , i + k i Ca , i − k d C*a , i
* *
(20)
*
Here X Ca ,i is the mass fraction of activated catalyst, defined as:
C*a ,i (21)
X Ca , i =
*
C + Va ,i (1 − ε a )ρs
*
a ,i
Mass balance for monomer:
(
d Va ,i ε a ρ g m am,i )=u ( )
A a ρ g m am,i−1 − m am,i − R p ,a ,i
(22)
a ,g
dt
The equation for the polymerization rate:
R p,ai = k pC*a ,i Cm,a ,i (23)
Energy balance:
d (Va , w ,i ρ av
a ,i C p ,a ,i Ta ,i )
av (24)
= u a ,g A a ρ g C p,g (Ta ,i−1 − Ta ,i ) + φ m ,s C p ,s (Ta ,i+1 − Ta ,i )
dt
πD 2r (Ta ,i − T∞ )
1
+ R p,a ,i ∆H r − α a ,i
4
Because the heating and cooling of the reactor wall is respected in the accumulation term,
the density and heat capacity of the annulus compartment is based on the weight-
averaged value of the gas, solids and the stainless steel wall. The last term in equation 24
concerns the heat transfer from the reactor wall to the air flowing through the isolated
metal cage.
Starting conditions for t = 0:
C a ,i ( 0) = C a , 0 (25)
C*a ,i (0) = 0
Ta,i (0) = T0
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CHAPTER 5
m am,i (0) = m 0m
Coupling between cone and draft tube and annulus:
Ta , 0 = Tc (26)
Ta , N a +1 = Td , N d
X Ca , N a +1 = X dC, N d
X Ca , N a +1 = X dC, N d
* *
m am, 0 = m cm
Sensitivity towards hydrogen

Both the propagation rate constant as well as the initiation rate constant depend on the
concentration of hydrogen in the gas phase, see Meier et al.4. The deactivation rate
constant was found to be not sensitive towards hydrogen above hydrogen concentrations
of 0.01 kg/m3. The sensitivity towards hydrogen of both kp and ki are described as
empirical relations4, see equations 28 and 29.
Eact , p (27)
(
k p = a p [ H 2 ] c + bp e ) −
RT
−
Eact ,i (28)
k i = (a i [ H 2 ] + bi )e RT
−
Eact ,d (29)
k d = k d ,o e RT
Molecular weight distribution

The molecular weight distribution of the product from a single site catalyst can in general
be described with a Schulz-Flory distribution. It has been shown in a previous paper4 that
the molecular weight distribution of the polymer produced with the current
heterogeneous metallocene catalyst can best be described with a “two-site model”. The
chain transfer probability of site 1 and 2 depends only on the hydrogen concentration
divided by the monomer concentration (in the polymer).
At constant temperature, pressure and gas composition, the instantaneous molecular
weight distribution of a polymer synthesized with a single-site catalyst can be described
with a Schulz-Flory distribution, see equation 30.
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CHAPTER 5
ydj = jq 2e − jq (30)
Here, y dj is the density function of the instantaneously formed molecular weight

distribution. The “two-site model” presented in a previous paper4 uses two Schulz-Flory
distributions, equal polymerization rate of each site but with a different chain termination
probability q. The chain transfer probability of site 1 and 2 depends only on the relative
hydrogen concentration4, see equations 31 and 32. Cm, the monomer concentration in the
polymer, depends on the temperature.
C H2 (31)
q 1 = 3.027 + 0.0023
Cm
C H2 (32)
q 2 = 14.31 + 0.0051
Cm
The molecular weight distribution of the polymer product obtained after a polymerization
experiment in the internally circulating fluidized bed reactor can be calculated by
integration over time and place in the reactor. For our reactor model, we can summarize
the molecular weight distributions produced during an integration interval for every
compartment, based on the amount of polymer produced in that time interval.
The related weight and number averaged molecular weight of the polymer can be
calculated by the moments of the distribution:
∞ (33)
N n = ∑ M nw−,1j y dj
j=1
N2 N1 (34)
Mw = , Mn =
N1 N0
Modeling results
The number of mixing cells in the annulus and draft tube (Na and Nd) remain to be
determined or fixed. It was found from preliminary calculations that 20 compartments in
the annulus and draft tube were sufficient (Na=Nd=20) to simulate the plug flow behavior
in these two sections. Increasing the number of compartments in these two sections does
not affect the predicted results. Other input data are summarized in table 3.
112
CHAPTER 5
Table 3: Input data for reactor model.

Constant Value Unit Constant Value Unit
ap 1.8· 107 m3/(kg.s.(kg/m3)c) Eact,p 43.9 kJ/mol

ai 9.72· 104 m3/kg.s ∆Hr 2471 kJ/kg
Ae 1.96· 10-3 m2 kd0 0.36 1/s
Aa 5.03· 10-3 m2 Na 20 -
Ad 1.96· 10-3 m2 Nd 20 -
bp 2.27· 106 m3/kg.s T∞ 50 °C
bi 1.07· 103 1/s εa 0.44 -
c 0.3 - εc 0.75 -
dw 4· 10-2 m εd 0.75 -
Eact,d 17.4 kJ/mol ρs 910 kg/m3
Eact,i 35.6 kJ/mol
The system of differential equations (164 in total) is numerically solved with a Runge-
Kutta method. In figure 11 and 12 the model prediction of the temperature profile in the
annulus together with the results of the experiments at 25.1 and 42.7 cm/s are presented.
The shapes of the temperature curves are comparable with the experimental results. It
seems that the rate of deactivation of the catalyst is overpredicted by the model, leading
to an under prediction of the temperature at the end of the experiment. The temperature
gradient over the length of the annulus is somewhat underpredicted. This may be
explained as follows. The model uses the solids circulation measurements described
earlier in this paper as input data. These measurements were carried out under non-
polymerization conditions with the same polymer powder as has been used as start up
powder for the polymerization experiments. However, during the polymerization
experiments a low molecular weight polymer is formed which behaves somewhat sticky.
This may cause a reduced mobility of the polymer powder inside the reactor leading to
reduced circulation rates and higher internal temperature gradients than expected.
Furthermore, the model assumes minimum fluidization conditions for the annulus. The
solids circulation experiments showed that the annulus is probably below the minimum
fluidization velocity. Therefore, the model calculates with a too large upward gas velocity
in the annulus, which implies an under prediction of the temperature gradient. Model
simulations showed however that the sensitivity of the temperature gradient in the
annulus towards the gas velocity in the annulus is small. The input for the solids
circulation rate is much more important.
113
CHAPTER 5
76
Ta(1)
73
Ta(2)
Ta(3)
70
Ta(4)
67 Ta(5)
T [°C]
Ta(6)
64
Model prediction for Ta(1)

61
Model prediction for Ta(6)

58
55
0 10 20 30 40 50 60 70 80
t [min]
Figure 11: Comparison between experimental result and model prediction for the
experiment at 25.1 cm/s.
In figure 13 Mw, Mn and Mw/Mn of the formed polymer are presented as function of time
for the experiment at 25.1 cm/s. This experiment shows the highest temperature gradients
(both in time and over the annulus), leading to the highest polydispersity of the final
product compared to the experiments at higher gas velocity. As can be seen from figure
13, both Mw and Mn are decreasing in time and Mw/Mn is increasing in time. The
polydispersity at the beginning of the experiment is around 2.56, reflecting the two-site
model. However, the increase of Mw/Mn is very small indicating that the temperature
gradients are too small to see any broadening of the molecular weight distribution.
114
CHAPTER 5
67 Ta(1)
Ta(2)
65
Ta(3)
Ta(4)
63
Ta(5)
T [°C]
61 Ta(6)
59 Model prediction for Ta(1)
57 Model prediction for Ta(6)
55
0 10 20 30 40 50 60 70 80 90 100 110
t [min]
Figure 12: Comparison between experimental result and model prediction for
the experiment at 42.7 cm/s.
20 2.62
Mw
18
2.61
16
14 Mw/Mn 2.60
Mw and Mn [kg/mol]
12
Mw/Mn [-]
2.59
10
2.58
8 Mn
6 2.57
4
2.56
2
0 2.55
0 10 20 30 40 50 60 70 80
t [min]
Figure 13: Model prediction of the weight and number averaged molecular weight
and polydispersity as a function of time during the experiment at 25.1 cm/s.
115
CHAPTER 5
Injection of hydrogen
In figure 14 the normalized temperature profiles obtained from the experiments with
injection of hydrogen and the prediction of the model are presented. The model over
predicts the temperature increase after hydrogen injection considerably. Moreover, the
temperature before hydrogen injection is over predicted. The deactivation observed
during the experiments, both before and after the injection of hydrogen, is higher than
predicted by the model.
7 Injection after 12.5 min
6 Injection after 16 min

∆T [°C]
0
0 10 20 30 40 50 60 70
-1
-2
t [min]
Figure 14: Comparison between experimental results and model predictions for the
experiments with injection of hydrogen.
The calculated polydispersity versus time of the formed polymer is shown for each
experiment in figure 15. Directly after the injection of hydrogen, the polydispersity starts
to increase. The molecular weight distributions of the final polymers are presented in
figure 16. It can be seen that the distribution moves from lower average molecular
weights (hydrogen injection after 12.5 minutes) to higher average molecular weights
(hydrogen injection after 30 minutes).
The polymer obtained from the experiments is a mixture of the start-up powder and the
low molecular weight polymer produced during the experiment. The molecular weight of
the start-up powder is about 300 kg/mol, but with a rather high polydispersity (about 7).
The molecular weight distribution of the start-up powder is given in figure 17. The GPC
measurements of the mixed powders (start-up material and own produced polymer) were
not very reproducible due to the low content of own produced polymer in the samples
obtained from the experiments (less than 10%). For one experiment (hydrogen injection
116
CHAPTER 5
after 24 minutes), a significant broadening at the low molecular tail of the original curve
could be detected, see figure 17. A fit of the molecular weight distribution of the start-up
powder has been subtracted from this curve in order to isolate the molecular weight
distribution of the own produced powder. Figure 18 presents the normalized subtracted
distribution together with the prediction of the model for this experiment. Note that the
errors of the subtracted distribution are quite large. Under these circumstances the
experimental data are quite well represented by the model.
3.6
3.4
3.2
Polydispersity [-] .
2.8
2.6
Injection after 12.5 min
2.4 Injection after 16 min
2.2
2
0 10 20 30 40 50 60 70 80
t [min]
Figure 15: Model prediction of the polydispersity as function of time for the
experiments with injection of hydrogen.
117
CHAPTER 5
0.9 Injection after 12.5 min

0.8
0.7
0.6
Y
0.5
0.4
0.3
0.2
0.1
0
0 1 2 3 4 5 6
log Mw
Figure 16: Model prediction of the MWD of the final polymer for the experiments
with injection of hydrogen.
0.8
0.7 Start-up powder
0.6
Fit of high
molecular part
0.5
Y
0.4
0.3 Mixed powder
0.2
0.1
0
0 1 2 3 4 5 6 7 8
log Mw
Figure 17: MWD of the start-up powder, MWD of polymer obtained from an
experiment with injection of hydrogen (start-up powder and produced polymer), MWD
of start-up powder used for subtraction.
118
CHAPTER 5
0.9
0.8
Subtracted and normalized GPC curve
0.7
0.6
Y
0.5
0.4
0.3
Model prediction
0.2
0.1
0
0 1 2 3 4 5 6
log Mw
Figure 18: Model prediction of the MWD of a polymer from an experiment with
injection of hydrogen and the distribution obtained after subtraction of the
distribution of the start-up powder.
Discussion
The developed reactor system enables us to control the solids mixing required to study
the polymerization of olefins in a small-scale fluidized bed reactor. The temperature
gradients caused by catalyst segregation observed in a previous paper2 have not been
found anymore. Moreover, elutriation of fines has not been observed despite the high gas
velocities applied in the draft tube. The slugs rising through the draft tube (containing the
whole particle size distribution) probably take the smaller particles to the annulus,
thereby preventing serious elutriation.
The 3 zones in the reactor with different heat transport properties may help to
systematically broaden the molecular weight distribution. However, the temperature
gradients observed during a series of experiments in which the gas velocity was varied,
were too small to see a significant broadening.
The presented model uses the measured solids circulation characteristics as input data. If
the model is to be used for scale-up, a model for the solids circulation rate should be
included, which describes the circulation rate as function of the gas velocity, reactor
geometry, etc. Furthermore, the model should be improved by implementing the
119
CHAPTER 5
dynamics of absorption and desorption of monomer in the polymer particles with related
energy effects, thereby respecting the (changing) particle size distribution.
Conclusion
A small-scale fluidized bed reactor has been equipped with a draft-tube and conical
bottom section to control the solids mixing inside the reactor. The solids circulation rate
has been measured at different gas densities and gas velocities. It appeared that the
particles in the draft tube and annulus part of the reactor move in plug flow. Slugging
takes place in the draft tube and a moving bed flow in the annulus. Segregation and
elutriation of the fine particles, which was a dominant effect without the draft tube, could
not be detected anymore during operation with the draft tube.
Semi-batch polymerizations have been executed at different gas velocities, thereby

varying the temperature gradients in the reactor from important to almost absent.
Hydrogen was injected at different moments during the experiment in a special series of
experiments. Directly after the injection of hydrogen, temperatures are increasing due to
reactivation of dormant sites causing a higher polymerization rate. Because the relative
temperature increase after hydrogen injection is independent of the injection time, one
may conclude that the relative concentration of dormant sites is constant during the
experiment.
A compartment model has been developed, which is able to describe the general
instationary temperature profiles in the reactor and related molecular weight distribution
of the polymer. The underprediction of the temperature gradient over the annulus is
probably due to the inaccuracies in the input data for the solids circulation rate. The
solids circulation rates have been measured under non-polymerization conditions while
during polymerization, a sticky polymer is formed which limits the mobility of the
powder.
The prediction of the model for the molecular weight distribution could be checked for a
single experiment. In this case the prediction of the molecular weight distribution is in
reasonable agreement with the experimental result.
Acknowledgement - This work has been funded by BRITE-EURAM Project CATAPOL (BE 96-3022).
The author wishes to thank DSM Research for the GPC measurements and materials they provided. We
greatly acknowledge the technical team of the High Pressure Laboratories. N.F. Geijsen, M. Poortenga,
J.M. Rutten and M.J.M. Hattink are acknowledged for their contribution in the experimental part.
120
CHAPTER 5
Notation
A Cross-sectional area m2
C Amount of non-activated catalyst kg
C* Amount of activated catalyst kg
Cm Monomer concentration in polymer kg/m3
Cp Heat capacity J/kg⋅K
d Thickness m
Eact,d Activation energy for deactivation J/mol
Eact,i Activation energy for initiation J/mol
Eact,p Activation energy for propagation J/mol
∆Hr Heat of reaction J/kg
j Chain length
kd Reaction rate constant for deactivation sec-1
ki Reaction rate constant for initiation sec-1
kp Reaction rate constant for propagation m3/kg.s
Mn Number averaged molecular weight g/mol
Mw Weight averaged molecular weight g/mol
mm Mass fraction of monomer -
N Total number of compartments -
Nn nth moment of the MWD -
p Pressure bar
q Chain transfer probability -
Rp Reaction rate kg/s
t Time s
T Temperature K
T∞ Temperature in air thermostat K
u Velocity m/s
Umf Minimum fluidization velocity m/s
Ue Inlet gas velocity m/s
V Volume m3
X Mass fraction -
y dj Density function of the instantaneous MWD -
Greek
α Heat transfer coefficient W/m2.K
ε Void fraction -
ρ Density kg/m3
φm Mass flow kg/s
121
CHAPTER 5
Sub- or superscripts
a Annulus
av Average value
c Cone
comp Compartment
d Draft tube
e Conditions at reactor entry
g Gas
i Compartment number
m Monomer
p Polymer
r Reactor
s Solids
w Wall
0 Initial value
Abbreviations
MWD Molecular weight distribution
Literature
1. Matsen, J.M., Powder Techn., 88, 237-244, (1996)
2. Meier, G.B., Roos, P., Weickert, G., van Swaaij, W.P.M., submitted to AIChE J.,
(2000)
3. US 5,698,642: Montell technology, (1997)
4. Meier, G.B., Weickert, G., van Swaaij, W.P.M., submitted to J. Pol. Sci., (2000)
5. Ji, H., Tsutsumi, A., Yoshida, K., J. Chem. Eng. Japan, 31(5), 842-845, (1998)
6. Alappat, B., Rane, V.C., Ind. J. Eng. Mat. Sci., 2, 113-117, (1995)
7. Song, B.H., Kim, Y.T., Kim, S.D., Chem. Eng. J., 68, 115-122, (1997)
8. Berruti, F., Muir, J.R., Behie, L.A., Can. J. Chem. Eng., 66, 919-923, (1988)
9. Yang, W.C., Keairns, D., Can. J. Chem. Eng., 61, 349-355, (1983)
10. Floyd, S., Choi, K.Y., Taylor, T.W., Ray, W.H., J. Appl. Polym. Sci., 32, 2935-2960,
(1986)
(2000)
12. Daubert, T.E., Danner, R.P., “Data compilation of pure compounds”, DIPPR Project,
AIChE, New York, (1985)
122
SAMENVATTING
Samenvatting
Dankzij de voortdurende ontwikkeling van katalysatoren en processen zijn polyolefinen

belangrijke plastics geworden. Polyolefinen kunnen tegenwoordig tegen lage
productiekosten en met zeer variërende producteigenschappen geproduceerd worden.
Polypropyleen wordt nu voor het grootse deel in gasvormig en/of vloeibaar propyleen
gemaakt. Het merendeel van het kinetiekonderzoek wordt echter in de slurry-fase
uitgevoerd. Bijzonder schaars is het onderzoek dat bij industrieel relevante
procescondities wordt uitgevoerd, d.w.z. bij hoge druk en relatief hoge temperatuur. De
bekendste industriële technologie voor de gasfase polymerisatie van olefinen is de
gefluïdiseerde bed reactor. Dit proces wordt bedreven bij een dru k van 10 – 30 bar. De
conversies per gang door de reactor worden laag gehouden, 1- 3%, om concentratie en
temperatuur gradiënten, die beide een directe invloed op de polymeereigenschappen
hebben, te voorkomen. De deeltjes die in 1 tot 3 uur verblijftijd worden verkregen hebben
een brede deeltjesgrootteverdeling. Er zijn geen experimentele gegevens beschikbaar in
de open literatuur over dit type reactor m.b.t. olefine polymerisatie.
In dit proefschrift worden de resultaten gepresenteerd die onder andere verkregen zijn
met een gemodificeerde fluïd bed reactor. Hiermee worden verschillende aspecten
bestudeerd van de gasfase polymerisatie van propyleen met een heterogene metalloceen
katalysator bij condities die de industriële condities benaderen of daar sterk vanaf wijken.
Om dit te kunnen bestuderen is een experimenteel gevalideerd kinetisch model een
vereiste. Dit kinetische model, afgeleid van experimenten bij isotherme en isobare
condities, kan dan gebruikt worden om de niet isotherme experimenten in het fluïd bed te
beschrijven met de daarbij behorende beschrijving van de molecuulgewichtsverdeling
van het polymeer. Andere aspecten die in dit proefschrift aan de orde komen zijn de
elektrostatische oplading van deeltjes, de deeltjes menging en de elutriatie van de kleine
deeltjes.
Polymerisatie kinetiek
In zowel gasvormig als vloeibaar propyleen is propyleen gepolymeriseerd in geroerde
semi-batch reactoren met rac-Me2Si[Ind]2ZrCl2 / MAO / SiO2(Grace) als metalloceen
katalysator. Gasfase polymerisaties zijn uitgevoerd bij temperaturen tussen 40 en 80°C en
drukken tussen 5 en 25 bar. Polymerisaties in vloeibaar propyleen zijn uitgevoerd bij
temperaturen tussen 40 en 80°C met waterstofconcentraties tussen 0 en 2.2% in de
gasfase boven de vloeistof. De kinetiek is beschreven met een vereenvoudigd model dat
een eerste orde reactie aanneemt m.b.t. het aantal actieve plaatsen en de concentratie van
het monomeer in het polymeer. De propyleenconcentratie in het amorfe gedeelte van het
123
SAMENVATTING
semi-kristallijne polymeer, d.w.z. bij het actieve centrum van de katalysator, is

experimenteel bepaald. Bij lage drukken kan de wet van Henry worden gebruikt om de
concentratie te beschrijven, bij hogere drukken wordt de Flory-Huggins vergelijking
gebruikt. Dalende waarden voor de Flory-Huggins interactie parameter zijn gevonden
met stijgende temperaturen. De sorptie gegevens zijn gebruikt om de relatieve
reactiesnelheden in gasvormig en vloeibaar propyleen te vergelijken. Lagere
reactiesnelheden zijn gevonden voor de gasfase polymerisaties. De gevonden
activeringsenergieën uit experimenten in beide fasen zijn ongeveer gelijk.
In een andere serie van experimenten is propyleen in de gasfase gepolymeriseerd bij

verschillende temperaturen, drukken en waterstofconcentraties met dezelfde katalysator,
echter op een andere silica drager. De reactiesnelheden zijn beschreven met een kinetisch
model dat zowel de activering als de deactivering van de katalysator beschrijft. Bij
hogere temperaturen, drukken en waterstofconcentraties zijn relatief lagere opbrengsten
gevonden die geïnterpreteerd zouden kunnen worden als het gevolg van een thermische
runaway op deeltjes schaal. De polymeer monsters zijn met behulp van een GPC analyse
op de molecuulgewichtsverdeling geanalyseerd. Deze verdeling is beschreven met een
model gebaseerd op twee actieve centra. Bij constante temperatuur blijken de
ketenoverdrachtswaarschijnlijkheden van het eerste en tweede centrum alleen afhankelijk
van de waterstofconcentratie gedeeld door de monomeerconcentratie.
Polymerisatie in de FBR
Op het hogedruk laboratorium van de Universiteit Twente is een fluïd bed reactor op
kleine schaal gebouwd voor de katalytische polymerisatie van olefinen onder druk. De
menging en segregatie van deeltjes zijn bestudeerd. Het bleek dat de menging relatief
snel is vergeleken met de verblijftijd van de katalysator in een polymeriserend systeem.
De kleine deeltjes in de reactor accumuleren echter in het bovenste gedeelte van het bed.
Verder werd een laag van fijne deeltjes met een in de tijd groeiende dikte op de wand
aangetroffen, veroorzaakt door electrostatische oplading. Deze deeltjes werden weer
gemengd na een injectie van een anti-statisch poeder. Semi-batch polymerisaties zijn
uitgevoerd bij verschillende fluïdisatiesnelheden. De gevonden vertic ale
temperatuurgradiënten blijken hoofdzakelijk door de segregatie van de katalysator
veroorzaakt te worden. Vooral bij lage fluïdisatiesnelheden bleken onder reactieve
omstandigheden de menging en segregatie van deeltjes anders te zijn vergeleken met niet
reactieve omstandigheden door het verschil in de interactie tussen de deeltjes. Ondanks
het feit dat gefluïdiseerde bedden nauwelijks opgeschaald kunnen worden met behulp van
experimenten die uitgevoerd zijn in reactoren met een diameter kleiner dan 30 cm,
kunnen kleine fluïd bed reactoren toch nuttig zijn om electrostatische oplading en de
gevolgen van onvolledige menging te bestuderen. De gevonden balans tussen segregatie
en menging mag echter niet vergeleken worden met de situatie op industriële schaal. Het
124
SAMENVATTING
is daarom noodzakelijk om de verticale menging in deze kleine reactor te verbeteren om

representatiever te kunnen zijn.
De laboratoriumopstelling is daartoe uitgerust met een “draft tube” en een conus om de

verticale menging te controleren. In deze aangepaste opstelling worden de deeltjes in de
draft tube met behulp van een relatief hoge gassnelheid omhoog getransporteerd.
Vervolgens bewegen de deeltjes als een “moving bed” in de annulus omlaag, om daarna
weer de conus binnen te treden. De circulatiesnelheid van het poeder neemt versneld toe
met toenemende gassnelheid. Vergeleken met experimenten zonder draft tube, werd een
sterke afname van elutriatie waargenomen. Semi-batch propyleen polymerisaties zijn
uitgevoerd bij verhoogde druk. Bij deze experimenten lag de nadruk op het creëren van
verschillende zones in de reactor met verschillende temperaturen. De
temperatuurgradiënten in de reactor kunnen gevarieerd worden met behulp van de
circulatiesnelheid van het poeder. Een injectie van waterstof tijdens een experiment
veroorzaakte een instantane stijging van de polymerisatiesnelheid, waarschijnlijk door het
activeren van “dormant sites”. De irreversibele deactivatiesnelheid van dormant en
actieve centra lijken identiek te zijn. Verder blijkt waterstof zeer effectief te zijn voor het
verbreden van de molecuulgewichtsverdeling. Een reactormodel is ontwikkeld om de
temperatuur- en concentratieprofielen in de reactor te kunnen beschrijven met de daarbij
behorende molecuulgewichtsverdeling van het ontstane polymeer.
125
SAMENVATTING
126
DANKWOORD
Dankwoord
Met het afronden van dit proefschrift kan ik met veel genoegen terugkijken op een zeer
interessante en leerzame periode. Een ieder die tot de totstandkoming van dit proefschrift
heeft bijgedragen wil ik hartelijk bedanken voor de vaak belangeloze inzet. Een aantal
van hen wil ik echter niet ongenoemd laten.
Tijdens mijn afstudeerproject was mij de enthousiaste werkwijze van de polymerisatie

club van IPP niet ontgaan. Ik ben dan ook professor Westerterp zeer erkentelijk voor de
geboden mogelijkheid een promotieonderzoek uit te voeren in zijn vakgroep. De
dagelijkse begeleiding lag in handen van professor Guenter Weickert. Grote waardering
heb ik voor zijn enthousiasme en passie voor het vak. De talrijke discussies, kritische blik
gecombineerd met zijn vele experimentele en modelmatige ideeën zijn van onschatbare
waarde geweest. Professor van Swaaij ben ik zeer dankbaar voor zijn ondersteuning in de
eindfase van het project. Veel dank ben ik hem dan ook verschuldigd voor de bijdrage
aan mijn proefschrift via discussies en zeer snelle correctierondes.
De twee belangrijkste opstellingen waarvan ik op het Hogedruk Laboratorium gebruik

heb gemaakt waren deels al gedurende de promotieprojecten van Job Jan Samson en
Peter Roos opgebouwd. Karst van Bree ben ik zeer dankbaar voor de vakkundige wijze
waarop de talloze wijzigingen zijn doorgevoerd. Ook de andere leden van het
ondersteunende team op het lab ben ik zeer erkentelijk: Fred, Geert, Gert en Arie
bedankt!
Een groot gedeelte van het werk dat in dit proefschrift beschreven staat is in het kader
van doctoraal opdrachten uitgevoerd door studenten. Bart Wijers, Nathan Kuper, Rik
Uiterwijk, Robert Smit, Jeroen Dunnewijk, Japke ten Have, Oskar Slotboom, Michiel
Bergstra en Wilma Aanstoot ben ik zeer dankbaar voor hun bijdrage aan de kinetiek
gerelateerde onderwerpen. Arjan van Klaveren, Marc Poortenga, Niels Geijsen, Marjorie
Hattink en Jasper Rutten wil ik danken voor hun bijdrage aan de onderwerpen aangaande
de fluid bed reactor en Sander Breeveld voor het modelleren van een enkel groeiend
polymeer deeltje.
Alle partners binnen het Brite Euram project Catapol wil ik bedanken voor de nuttige
bijeenkomsten waar de voortgang van het project werd besproken. Deze bijeenkomsten,
meestal gehouden op zeer aangename locaties, hebben ook zeker mijn blikveld verbreed.
DSM ben ik dank verschuldigd omdat zij dit project mede financieel mogelijk hebben
gemaakt. Ik heb de discussies met Stan Mutsers, Tjaart Molenkamp, Gerwin Wijsman,
127
DANKWOORD
Gerard Krooshof en Denise Bakker zeer gewaardeerd. Ilco de Vries wil ik graag
bedanken voor de GPC analyses en de hulp bij de interpretatie van de resultaten.
Bestellingen en reparaties werden uitgevoerd door het Techno Center CT. Hierbij hebben
met name Wim Platvoet, Jan Jagt, Bert Kamp en Jan Heezen bijgedragen. Alle leden van
de Doctoraal commissies van mijn afstudeerders ben ik erkentelijk voor de tijd die zij
hierin hebben gestoken.
In het bijzonder wil ik Jochem bedanken voor de gezellige tijd in ons koffiehok met de
bijbehorende discussies, die ons enthousiasme voor PP tot grote hoogte heeft doen
stijgen. Mijn (oud) collega’s wil ik graag bedanken voor de gezellige sfeer tijdens het
werk en onze reizen. Yvonne Bruggert en Gery Stratingh zorgden voor een prima
afwikkeling van de administratieve zaken. De paranimfen Jochem “dikke” Pater en
Michiel “Waterreus” Bergsma wil ik hierbij bedanken voor hun inzet en talloze voetbal
discussies.
Een dag die ik niet snel vergeten zal is 2 december 1998. De explosie die op die dag in
bunker 7 van het HDL plaatsvond was een, voor sommigen letterlijke, klap in het gezicht.
Gelukkig hebben zich geen ernstige persoonlijke ongelukken voorgedaan, maar de
impact op allerlei andere vlakken was enorm. Ik heb hier, en met mij waarschijnlijk vele
anderen, enorm veel van geleerd. Ik wil graag iedereen die bij de nasleep van dit ongeval
betrokken was enorm bedanken voor de goede en zorgvuldige afhandeling.
Ik wil bij deze graag mijn ouders, familieleden en vrienden bedanken voor de getoonde
interesse en steun. Tot slot wil ik Dynah bedanken voor haar steun, begrip en vertrouwen
gedurende de afgelopen jaren.
128
LEVENSLOOP
Levensloop
Gerben Meier werd op 22 april 1972 geboren in Stad Delden. Na de lagere school
bezocht hij het Twickel College te Hengelo waar hij in juni 1990 het VWO diploma
behaalde. In augustus van datzelfde jaar begon hij met de studie Chemische Technologie
aan de Universiteit Twente. Tijdens zijn studie liep hij stage bij Akzo Nobel Engineering
Obernburg in Duitsland. In juni 1996 sloot hij de opleiding af binnen de vakgroep
Industriële Processen en Producten met een onderzoek naar de gasfase polymerisatie van
ethyleen met behulp van heterogene metalloceen katalysatoren.
In juli 1996 trad hij vervolgens in dienst als assistent in opleiding en verrichtte onder
leiding van prof. dr. ir. K.R. Westerterp en prof. dr. G. Weickert het onderzoek dat in dit
proefschrift beschreven staat. Na het emeritaat van prof. Westerterp in 1998 werd de
supervisie in 1999 overgenomen door prof. dr. ir. W.P.M. van Swaaij. Sinds augustus
2000 is Gerben Meier werkzaam bij Montell te Ferrara in Italië.
129

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Fluidized Bed Reactor for Catalytic Olefin Polymerization

Kinetics and Fluidization

Fluidized bed reactor for catalytic olefin polymerization

Copyright  2000 by G.B. Meier, Enschede, The Netherlands

Referent: Dr. ir. S.M.P. Mutsers

Cover design: L.H.M. Meier and M.G.J.J. Hartgerink

ter verkrijging van

Gerhardus Bernardus Meier

geboren op 22 april 1972

Chapter 1: General introduction 5

Chapter 2: Comparison of gas and liquid phase polymarization of 9

Chapter 3: Gas phase polymerization of propylene with a 37

Chapter 4: FBR mini-plant for catalytic olefin polymerization: 67

Polymerization in a small-scale FBR

Semi-batch propylene polymerizations have been executed at elevated pressures.

Outline of the thesis

At present heterogeneous metallocene catalysts, which are able to produce polyolefins

History of the project

Comparison of gas and liquid phase polymerization of

Propylene polymerization with a heterogeneous catalyst is a complex process, involving

Pressure Reducer 5 Capillary

Figure 1: Experimental set up for sorption measurements.

Polymer sample characterization

Prior to measurements 0.91 43.5 22

Experimental set up for liquid propylene polymerizations

Experimental set up for gas phase polymerizations

Figure 2: Experimental setup for gas phase polymerizations.

Liquid phase polymerization procedure

Here kH is the Henry coefficient and PH 2 the partial pressure of hydrogen.

40 0.0205 33.96 475.50 2.39 2.61

Gas phase polymerization procedure

At higher monomer concentrations, the interaction between monomer and polymer

Here C Lm is the concentration of liquid monomer for a given temperature9.

In the simple power law equation 8 kp=kp,0exp(-Eact,p/RT), where kp is the propagation

R p = k p C m C *max e − k d t = R p , max e − k d t (11)

Results from sorption measurements

Figure 6: Fitting measurements with the Flory-Huggins equation.

Figure 8: Measured Flory-Huggins parameters vs. the reciprocal temperature.

Table 4: Flory-Huggins interaction parameter as function of temperature; literature vs.

Results of liquid phase experiments

400 Al/Zr = 700

Table 5: Summary of the liquid phase experiments at different temperatures.

40 2.45 0.028 208.8 200.3 125.8 0.0088

Figure 11: Influence of hydrogen on the maximum polymerization rate.

Figure 12: Influence of hydrogen on the deactivation constant kd.

Results of gas phase experiments

In figure 15 the deactivation rate constant kd is given as function of the monomer

Figure 14: Influence of monomer concentration on maximum polymerization rate

Comparison between liquid and gas phase polymerization kinetics

0.6 Gas phase

sorption behavior of hydrogen in polypropylene swollen with propylene is unknown and

Sub- and superscripts

Swelling of the polymer results in an increase of the polymer volume:

Gas phase polymerization of propylene with a heterogeneous

Pore diameter 0.004 0.2 5

Particle size 27 108 170

Scheme 1: Activation, propagation and deactivation of the catalyst.

In equation 2, kd=kd,0exp(-Eact,p/RT) where kd is the deactivation rate constant and Eact,d

Here C0 is the initial amount of non-activated catalyst.

Molecular weight and molecular weight distribution

k p Cm >> k mCm + k H 2 CH 2 + k x (8)

140 Model without activation

Table 2: Summary of the experiments; temperature and pressure series.