Production of Polyethylene Using Gas Fluidized Bed Reactor

Tham Chee Mun (HT022626U)

Dept. of Chemical & Biomolecular Engineering,
National University of Singapore,
10, Kent Ridge Crescent, Singapore 119260
Email: [email protected]


ABSTRACT

Polyethylene is the most common thermoplastic and used in a wide range of applications. There are
various commercial technologies available to produce polyethylene. Gas fluidized bed polymerization is
one of the later technology developed and is commonly employed in the production of linear-low density
polyethylene (LLDPE) and high density polyethylene (HDPE). This paper reviews the historical
development of fluidized bed polymerization technology as well as the development of catalyst from
Ziegler-Natta catalyst to metallocene-based catalyst. A critical review of the challenges and opportunities
from an operations view-point is presented.

Keywords: Fluidized bed reactor, metallocene, polyethylene, polymerization, Ziegler-Natta.

1 INTRODUCTION

Polyethylene is the most common thermoplastic and used in a wide range of applications. Polyethylene
can be processed into various consumer products using processing techniques such as profile extrusion,
film extrusion, injection molding, blow molding, rotomolding and etc. The wide application has
continuously driven the demand for this thermoplastic. Scientists and engineers also continuously
improved the polymerization techniques to improve polymer properties, increase production capacity and
reduce the cost of material.

Polyethylene is produced using ethylene as a monomer. Ethylene is generally produced via steam
cracking of crude oil derivatives. It is common to find a petrochemical complex where the refinery,
cracker and polymer plant are located on a single site. This illustrates the high capital investment required
to produce polyethylene although the final consumer product may be something very cheap and
disposable. Hence, improving polymer production techniques with the objective to reduce manufacturing
cost continues to be an area of research, development and process improvement.
2 GAS FLUIDIZED BED POLYMERIZATION PROCESSES

2.1 Earlier Technologies

The first commercial polyethylene was produced under very high pressure (~ 3,000 atm). This is a free
radical reaction process which produces low-density polyethylene (LDPE) with narrow molecular weight
distribution. The high operating pressure necessitates high capital investment (equipment to withstand the
high pressure) and operating costs (power to compress reactants to the high operating pressure). Variants
of this technology licensed by ExxonMobil Chemical Co. and Basell Polyolefins continue to be used
today with a worldwide capacity of over 6 MMtpy. This technology is also used to produce ethylene
vinyl acetate (EVA) which is generally used in high clarity shrink-wrap sheets.




1



Figure 1: LDPE/EVA process, ExxonMobil Chemical Co.
(Hydrocarbon Processing, March 2003)
Figure 2: LDPE/EVA process, Basell Polyolefins
(Hydrocarbon Processing, March 2003)

The subsequent technologies developed focused on achieving lower operating pressure. With the
development of catalyst to allow coordination polymerization, slurry and solution phase reactors were
invented. These reactors operate at a lower pressure compared to the earlier high-pressure free radical
process. The slurry-phase loop reactor by Chevron Phillips Chemical Co. operates at 40 atm.
Development for low pressure polymerization processes also started the use of comonomers such as 1-
butene and 1-hexene to produce linear-low density polyethylene (LLDPE) and high density polyethylene
(HDPE). The Chevron Phillips technology is used in eighty-six commercial LLDPE plants and account
for 34% of worldwide capacity. Another variant of this technology by Mitsui Chemicals Inc., named CX
process is used for production of HDPE and has a worldwide capacity of 4 MMtpy.




Figure 3: LPE process, Chevron Phillips Chemical Co., LP
(Hydrocarbon Processing, March 2003)
Figure 4: CX HDPE process, Mitsui Chemical Inc.
(Hydrocarbon Processing, March 2003)

The following table summarizes polyethylene into 5 categories based on polymerization mechanism and
reactor operating conditions.

Table 1: Polymerization Processes and Reactor Operating Conditions
conventional high
press. process
high-press. bulk
process
solution polymn. slurry polymn gas phase polymn.
reactor type tubular or
autoclave
autoclave CSTR loop or CSTR fluidized or stirred
bed
reactor press., atm 1200 3000 600 800 ~ 100 30 -35 30 - 35
temp,
o
C 130 350 200 300 140 200 85 110 80 100
polymn. mech. free radical coordination coordination coordination Coordination
loci of polymn. monomer phase monomer phase solvent solid solid
density, g/cm
3
0.910 0.930 0.910 0.955 0.910 0.970 0.930 0.970 0.910 0.970
melt index, g/10 min 0.10 - 100 0.80 - 100 0.50 - 105 < 0.01 80 < 0.01 200

2

2.2 Process Development

Gas fluidized bed polymerization reactors were invented in the 1950s. The major driving forces to this
invention were to eliminate the need to remove the catalyst after reaction and to make the product in a
form suitable for handling and storage. Distinguishing characteristic of gas phase polymerization is the
system does not involve any liquid phase in the polymerization zone. Polymerization occurs at the
interface between the solid catalyst and the polymer matrix, which is swollen with monomers during
polymerization. The gas phase plays a role in the supply of monomers, mixing of polymer particles, and
removal of reaction heat.

Dye (1962) [4] described one of the earlier reactors as three concentric superimposed vertical sections.
Polymer particles were discharged through an extruder, which was connected to the bottom section of the
reactor. The reactor was operated at 30 atm and 100
o
C. Goins (1960) [5] carried out ethylene
copolymerization in a countercurrent fluidized bed reactor in presence of inert diluent gas. In this process,
polymer particles are passed downward in the reactor and monomer mixed with diluent gas is passed
counter-currently upward in the reactor and monomer mixed with diluent gas is passed counter currently
upward through a series of vertical fluidized bed reaction zones. The reaction zones can be controlled
independently by taking off-gas from the last reaction zone, cooling it, and recycling portions of such off-
gas to each of the reaction zones. Both patents (Dye, 1962; Goins, 1960) were assigned to Phillips
Petroleum Company but were never applied commercially. Nevertheless, they formed the foundation idea
of how a fluidized bed reaction process will be and subsequent commercialized processes are very similar
to these earlier inventions.



Figure 5: Fluidized bed reactor (Dye, 1962) Figure 6: Fluidized bed reactor (Goins, 1960)

The first commercial gas phase polymerization plant using a fluidized bed reactor was constructed by
Union Carbide in 1968 at Seadrift, Texas (Xie, 1994) [22]. This process was developed initially for
HDPE production. The success of this novel technology led to the extension of the process to LLDPE and
polypropylene (PP). The Union Carbide gas process is commonly known as the UNIPOL process and
was described in several US Patents (Miller, 1977 [14]; Levine and Karol, 1977 [11]; Karol and Wu [10],
1978; Wagner et al., 1981 [20]; Jorgensen et al., 1982 [9]). The technology was later transferred to Dow
Chemical Co. and finally to Univation Technologies, a joint-venture between Dow and ExxonMobil.
Collectively, they have 96 reaction lines worldwide.

Another commercialized gas fluidized bed technology was developed by Naphtachimie in the 1970s. This
technology was described in two US Patents (Dormenval, et al., 1975 [3]; Havas and Magin, 1976 [6]).
The technology was transferred to BP Chemicals Ltd. after the Naphtachimie was amalgamated into the
3
latter. The original Naphtachimie design was very similar to the Union Carbide design with exception of
a pre-polymerization step. Monomers, catalysts and hydrogen were first activated in an n-heptane phase
using a mechanically stirred vessel. The catalytically active solids or pre-polymers were decanted and
subsequently fed to the fluidized bed reactor instead of solid catalyst as in the case of UNIPOL process.
This major distinction was incorporated in the latter BP designs until the development of metallocene
catalyst.


Figure 7: Union Carbide fluidized bed reactor (Miller 1977;
Levine and Karol, 1977; Karol and Wu, 1978; Wagner et al.,
1981; Jorgensen et al., 1982 )
Figure 8 BP Chemicals fluidized bed reactor process
(Dormenval et al, 1975; Havas and Magin, 1976; Havas and
Lalanne-Magne, 1992)

Table 2 summarizes the similarities and differences between the Union Carbide and BP Chemicals
fluidized bed reactor technologies. [Note that the later development of metallocene catalysts is not
discussed here.]

Table 2: Fluidized Bed Reactors Processes and Operating Conditions
Union Carbide BP Chemicals
Reactor type Fluidized bed Stirred reactor and fluidized bed
Catalyst Supported Ti, V and CrCO
3
catalyst Supported Ti and CrCO
3
catalyst
Catalyst size, m 30 - 250 ~ 50 for prepolymn
Pressure, atm 20 - 30 15 25
Temperature,
o
C 75 110 70 115
Comonomer 1-butene or 1-hexene 1-butene or 1-hexene
MW control H
2
H
2

MWD, / w n M M
4 - 30 6 20
Density, g/cm
3
0.91 0.97 0.91 0.96
Polymer particle size, m 500 - 1300 300 - 1200

Since the successes of both Union Carbide and BP Chemicals processes, the fluidized bed reactor
technology has been applied and improved in other proprietary polymerization processes. Notable
examples are combination of slurry loop reactor and fluidized bed reactor in series for production of
polyethylene and fluidized beds in series for production of polypropylene. These hybrid systems will be
discussed in a later part of this paper.

2.3 Process Description

Both the Union Carbide and BP Chemicals technologies contain a reactor loop which consists of an
expanded dome reactor vessel, a compressor and a cooler. The earlier designs adopted the cooler before
the compressor configuration. This is to cool down the reacting gas mixture and hence, lowering the
compression power required. The newer plants however adopted the cooler after compressor sequence.
4
Fouling of the cooler (polymer fines buildup in the exchanger tubes) often becomes the criteria of a
shutdown; hence the reconfiguration allows longer service time between cooler cleaning. Putting the
cooler downstream of the compressor also allows the comonomers (more notably 1-hexene) to condense
partially in the cooler. This condensation phenomenon removes a lot of heat from the system and enables
higher production rate. The cyclone shown in both the simplified flow diagrams has the function of
removing polymer fines and reduces the fouling of the cooler or compressor blades. This equipment
however is optional and is omitted in some newer plants built in the last decade. The following
paragraphs are detailed description of the earlier configurations by Union Carbide and BP Chemicals.


Figure 9: Industrial scale UNIPOL reactor (Univation Technologies, 2004)

The fluidized bed reactor in a UNIPOL process consists of a reaction zone and a disengagement zone.
The reaction zone has a height to diameter ratio of about 6-7.5. The disengagement zone has a diameter
to height ratio of about 1-2. To maintain a viable fluidized bed, superficial flow through the bed is about
2-6 times the minimum flow required for fluidization. It is essential that the bed always contain polymer
particles to prevent the formation of localized "hot spots" and to entrap and distribute the powdery
catalyst. On startup, the reaction zone is charged with a base of polymer particles before gas flow is
initiated. Monomer (ethylene gas) is fed to the compressor inlet, whereas the -olefin comonomer (1-
butene or 1-hexene) is added to the reactor inlet. The catalyst is stored in a catalyst feeder under a
nitrogen blanket. Catalyst is injected into the bed at a rate equal to its consumption rate at 114 to 314 of
the height of the bed. If co-catalyst (e.g., trialkyl aluminum) is required, it is fed separately to the reactor
inlet. Catalyst concentration in the fluidized bed is essentially equal to the catalyst concentration in the
product, namely on the order of about 0.005-0.50% of bed volume. Fluidization is achieved by a high rate
of gas recycle to and through the bed, typically on the order of about 50 times the rate of feed of make-up
gas. The pressure drop through the bed is typically on the order of 0.07 atm (1 psi). Make-up gas is fed to
the bed at a rate equal to the rate at which polymer particles are withdrawn. A gas analyzer, positioned
above the bed, determines the composition of the gas being recycled, and the make-up gas composition is
adjusted accordingly to maintain an essentially steady-state gaseous composition within the reaction
zone.

The gas which has not been consumed in the bed passes through the enlarged disengagement zone where
entrained particles drop back into the bed. Particle entrainment is further reduced by a cyclone and a filter
to avoid deposition of polymer on heat-transfer surfaces and compressor blades. Polymerization heat is
removed by a heat exchanger before the recycle gas is compressed and returned to the reactor. The
fluidized bed can maintain itself at an essentially constant temperature under steady-state conditions. To
5
increase heat removal capacity and productivity, UNIPOL reactors can be operated with an inlet gas
temperature at the bottom of the fluidized bed which is below the dew point temperature of that gas.
Recycle gas condenses in the external cooler, and the liquid droplets revaporize upon entry into the bed.
It has been observed that droplets pass through the distributor as a mist and quickly wet the surface and
pores of the polymer particles. The liquid vaporizes very quickly above the distributor. There is a
dramatic change in the gas flow pattern in the gas feed region below the distributor. However, there is no
apparent effect on bulk circulation patterns of bubbles and resin particles above the gas distributor.

The distribution plate at the bottom of a reactor plays an important role in the operation of the reactor. As
the polymer particles are hot and possibly active, they must be prevented from settling to avoid
agglomeration. Maintaining sufficient recycle and make-up gas flow rate through the distributor to
achieve fluidization at the base of the bed is very important in fluidized bed polymerization reactor
operation. The polymer particles are withdrawn close to the distributor through sequential operation of a
pair of timed valves, defining a segregation zone. The reactor is operated at a temperature below the
melting point of the polymer particles. For HDPE production, the operating temperature is 90-110
o
C. An
operating temperature of about 90
o
C or lower is preferred for production of LLDPE, which contains
about 15 mol % of one or more of the C
3
to C
6
-olefins (Levine and Karol, 1977). The reaction zone and
disengagement zone of the reactor are connected by a transition section having sloped walls. During
polymerization, some fine particles from the disengagement zone fall onto the sloped walls of the
transition section. These fine particles build up during reactor operation. Since the fine particles contain
active catalyst, they further polymerize and form solid sheets which can grow until they block recycle gas
flow or slide off the sloped walls into the polymerization zone. In the polymerization zone, the solid
sheets block the flow of gas and cause fusion of the polymerization particles. Thus, large chunks of
polymer can be formed which can block the entire polymerization zone unless the reactor is shut down
and the sheets are removed.

The BP Chemicals gas phase process is a continuous two-stage polymerization process (Dormenval et al,
1975; Havas and Magin, 1976; Havas and Lalanne-Magne, 1992). This process uses a combination of a
stirred tank reactor and a fluidized bed reactor in series. During conventional gas phase reactor operation,
the catalyst and the cocatalyst may be brought into contact either prior to their introduction into the
fluidized bed, or in the interior of the reactor. Whichever method is employed, the polymerization
reaction always starts up very abruptly and attains a maximum rate soon after the catalyst system is
introduced into the fluidized bed.

The initial phase of polymerization is where the risks of hot spots forming and grains bursting into fine
particles are greatest. Hot spots may lead to formation of agglomerates and to settling of polymer inside
the fluidized bed. Furthermore, during polymerization small variations in the feed rates of catalyst,
monomer, and comonomer or in the withdrawal rate of polymer will also cause an unexpected increase in
the quantity of heat evolved by the polymerization. If the heat cannot be removed efficiently, these small
variations can cause hot spots in the reaction bed and formation of agglomerates by melting polymer.
Such variations can therefore make it difficult to obtain a polymer of consistent quality, in particular, of
constant molecular weight and particle size. These problems can be eliminated by adopting a
prepolymerization stage.

Prepolymerization gives advantages in polymer particle size control and control of the catalyst activity in
the fluidized bed reactor. Prepolymerization can be carried out in a liquid hydrocarbon medium or in a
gas phase stirred reactor at temperatures from 40 to 115
o
C. Catalyst is introduced into the prereactor in
the form of dry powder or in suspension in a liquid hydrocarbon. Prepolymerization is carried out to a
conversion wherein the prepolymer contains 0.002-10 millimol of transition metal/g of polymer. The
diameter of the prepolymer is in the range from 200 to 250 pm. Prepolymer is fed into the fluidized bed
reactor through a metering feed device.

The fluidized bed reactor operates at a superficial velocity of approximately 0.5 m/s, 2-8 times the
minimum fluidization velocity. To avoid induction time at startup, the prepolymer is treated with
6
triethylaluminum for polymerization with chromium oxide as catalyst. To create more porosity, the
prepolymer is also treated with n-hexane to remove low molecular weight polymer (wax). Monomer,
comonomer, hydrogen, and inert gas are fed through the bottom of the fluidized bed. Some comonomer
and inert volatile hydrocarbon, such as isopentane, are introduced into the inlet line of the heat exchanger
to avoid fine particles depositing on heat exchanger surfaces and compressor blades. The ratio of
comonomer to monomer partial pressure is kept constant (normally 0.1-0.2) in the reactor. To avoid
pressure fluctuations during polymer discharge, BP Chemicals developed a continuous discharge device
consisting of two continuously rotating plug valves. These valves are connected with each other in such a
way that the two valves do not open at the same time, rotating at a speed of about 0.5-1.0 rpm. The
volume of the vessel between the valves is between 0.2% and 1% of the volume of the fluidized solid
contained in the reactor.

2.4 Catalyst Development

Development of polymerization catalyst has attracted the participation of both academic and industrial
laboratories. The wide application of polyethylene would not be possible without the thoughtful
development of catalyst at the microstructure level. Catalysts were first developed with the objective to
produce polymers at a low operating pressure. This objective is now shifted to engineer the desired
properties of the final plastic product. Every polymer manufactured by coordination polymerization is
essentially an engineered plastic which was developed meticulously to have the desired physical,
chemical and mechanical properties.

Catalysts for ethylene polymerization are mostly heterogeneous, but some processes also use soluble
catalysts. There are now four types of catalysts for ethylene polymerization: Ziegler-Natta, Phillips,
metallocenes and late transition metal catalysts. Only the first three types are in use commercially,
whereas the last is still in research and development stage.

Ziegler-Natta catalysts have many variations but are generally TiCl
4
supported on MgCl
2
, combined with
a variety of electron donors and cocatalysts. Ziegler-Natta catalysts account for most of the polyethylene
produced industrially. In operations, a trialkyl aluminum co-catalyst (typically triethyl aluminum) is
added separately to the reactor feed. Figure 10 gives an illustration of how polyethylene is made using
Ziegler-Natta catalysts in a fluidized bed reactor.


Figure 10: Ethylene polymerization using Ziegler-Natta catalyst
7

Phillips catalysts are mostly composed of chromium oxide supported on silica or silica/alumina. It is
responsible for a considerable fraction of the HDPE produced. In operations, Phillips catalysts do not
require separate addition of co-catalyst. It is however more exothermic and heat removal needs to be
efficient.




Figure 11: Inorganic oxide supported bis(cyclopentadienyl)
chromium [II] (Karol et al., 1978)
Figure 12: A metallocene structure (Winter et al., 2002)
[21].

Metallocene catalysts are sandwich compounds of the type B(L
1
L
2
)MX
2
, where a transition metal, M
(most commonly zirconium or titanium), is sandwiched between two ligands, L
1
and L
2

(cyclopentadienyl, indenyl, Euorenyl, etc.), and bonded to two substituents, X (very commonly Cl
atoms). The ligands can be connected by a bridge, B (ethyl, silyl, etc.). In some formulations (for
instance, Dow Chemicals constrained geometry catalysts), one of the bulky ligands is absent (half-
sandwich compounds). The industrial use of metallocene catalysts is increasing rapidly due to their high
activities, excellent polymer microstructural control, and easy implementation in existing Ziegler-Natta
and Phillips processes.

The last class of ethylene polymerization catalysts is based on late transition metals. These catalysts are
capable of producing polyethylene containing short-chain branches from the polymerization of ethylene
alone [17].

2.5 Properties and Characteristics of Polyethylene

Two important properties in polymer production are density and melt flow index (MI). It is a commercial
practice to classify polymer resin grades based on the two properties instead of implicit properties such as
molecular weight and composition.

Polyethylene is generally divided into LDPE (0.91 0.93 g/ml) and HDPE (0.93 0.97 g/ml). LLDPE
shares the same density range of LDPE but display many characteristics of HDPE. Density measurement
is described by ASTM D-1505. Sample of polymer granules discharged from the reactor is converted into
a plaque by conditioning for one hour at 120
o
C to approach equilibrium crystallinity. Density of the
plaque is then measured using a density column. Sales specification of polymer resins are typically
quoted to the third decimal value (in g/ml), hence a very tight control is required.

In general, the density of polyethylene decreases with an increase in branch numbers; the more
branching, the lower the density. The crystallinity of PE decreases significantly with an increase in
branch frequency and size. Hence, any physical properties related to crystallinity, such as stiffness and
yield stress, will be affected by branching or chemical composition. Density decreases with an increase in
molecular weight. This is because of the inhibition of crystallization by longer molecular chains. The
basic relationships between polymer properties and density can be summarized in Figure 13.

8
MI is an interesting property that gives a clue on the chain length of the polymer and hence the molecular
weight. Measurement of MI is described by ASTM D-1238. The apparatus and method is employed is
very similar to viscosity measurement using a viscometer. MI can be translated into the units of viscosity.
A polymer that exhibits a higher MI has a shorter polymer chain length.

Melt flow ratio (MFR) is the ratio of MI under different weight load as described by ASTM D-1238
(ratio of 440 psi melt index to 44 psi melt index). The MFR is a relative measure of the molecular weight
distribution of a resin. This relationship between the MFR and molecular distribution is based on the
phenomenon that polymers having a narrower molecular weight distribution are more Newtonian in melt
flow behavior and thus, have flows which are less sensitive to shear. A polymer having a narrower
molecular weight distribution have a lower MFR. Figure 14 summarizes general relationships between
polymer properties and molecular weight.




Figure 13: Relationship between polymer properties and
resin density
Figure 14: Relationship between polymer properties and
resin molecular weight.

Table 3 illustrates how mechanical properties and processability of the polymer are affected by the
polymer molecular structure we discussed earlier. Molecular weight and molecular weight distribution
affects almost the mechanical properties and directly affects the processability of the polymer. The degree
of branching and its distribution change the mechanical and chemical properties of a polymer.

Table 3: Relationship between molecular structure and properties of polyethylene [15]

Molecular
weight (M
w
)
Molecular
weight
distribution
Branching
chemicals
Degree of
branching
Degree of
branching
distribution
Long chain
branching
(LCB)
Transparency o o o o o
Tensile strength o o o o o o
Impact strength o o o o o o
Rigidity o o
Heat resistance o o
Cold resistance o o o o o
Chemical resistance o o o o o o
Mechanical
and chemical
property
Heat seal o o o o o
Bubble stability o o o
Draw-down o o o
Processability
Extrusion torque o o o
9
3 REACTOR MODELING

3.1 Reaction Mechanisms

Ethylene polymerization can be envisioned as occurring at the interface between the solid catalyst and the
polymer matrix, where the active centers are located. From gas-state monomer to solid-state polymer,
ethylene experiences a dramatic physicochemical transition within a very short time. The polymerization
environment changes with the composition of catalyst, polymerization process, reactant composition,
reactor operating conditions, and extent of polymerization. Although intensive research activity has been
focused on Ziegler-Natta catalyst systems since their discovery in the early 1950s, no definitive chemical
reaction mechanisms have been developed to fully describe the kinetic behavior of ethylene
homo/copolymerization, due to the complexity of the systems employed. Nevertheless, the key
elementary reactions have been established, which include formation of active centers, insertion of
monomer into the growing polymer chains, chain-transfer reactions, and catalyst deactivation. Most of
the proposed mechanisms are based on information about polymerization rate, molecular weight and its
distribution, polymer chain microstructure, and active center concentrations.

Since commercial production of LLDPE and HDPE consists of a copolymerization process,
copolymerization mechanisms are required to understand kinetic behavior and polymer properties. If one
assumes that all of the active centers perform the same reaction mechanisms, but with different reaction
rates for each elementary reaction, then elementary reactions which are commonly adopted in modeling
studies can be summarized as in Table 4, where C, is the catalyst potential active center; P
*
0
is the active
center without polymer chain; P
*
m,n,i
is the active center with m units of monomer 1 and n units of
monomer 2, with the third subscript i denoting the chain terminal monomer type bonded to the active
center; q

m,n
is a dead polymer chain with a terminal double bond; and q
m,n
is a dead polymer chain
without terminal double bond. For simplification of notation, no subscript is shown corresponding to the
type of active center. The reactions shown in Table 3 should be considered to occur at each type of active
center. The mechanisms in Table 4 are summarized based on Ti-based catalysts. Reaction mechanisms
for chromium oxide based catalysts are a subset of those in Table 4.

Table 4: Summary of elementary reactions for ethylene and -olefins co-polymerization [22]
Reaction Description
Activation
*
0
aS
K
p
C P

Spontaneous activation
| |
*
0
aA
K
p
C A P +

Activation by aluminum alkyl (A)
| |
*
0
aE
K
p
C E P +

Activation by electron donor (E)
| |
*
2 0
aH
K
p
C H P +

Activation by hydrogen (H
2
)
| | | |
1
*
1 0
aM
K
p
C M P M + +
1


Activation by monomer 1 (M
1
)
| | | |
2
*
2 0
aM
p
C M P M + +
2
K


Activation by monomer 2 (M
2
)
Initiation
| |
1
* *
0 1 1
i
K
P M P +
,0,1


Initiation of M
1
by normal active center
| |
2
0 2 0
i
P M P +
* * K
,1,2


Initiation of M
2
by normal active center
| |
1
,0 1 1,0,1
iH
H
P M P +
* * K


Initiation of M
1
by active center with H
| |
2
,0 2 0,1,2
iH
H
P M P +
* * K


Initiation of M
2
by active center with H
| |
1
,0 1 1,0,1
iA
A
P M P +
* K *


Initiation of M
1
by active center with A
| |
2
,0 2 0,1,2
iA
A
P M P +
* * K


Initiation of M
2
by active center with A
10
| |
1
* *
,0 1 1,0,1
iE
K
E
P M P +

Initiation of M
1
by active center with E
| |
2
* *
,0 2 0,1,2
iE
K
E
P M P +

Initiation of M
2
by active center with E
Propagation
| |
11 * *
, ,1 1 1, ,1
p
K
m n m n
P M P
+
+

Propagation of chain type 1 with M
1

| |
12 *
, ,1 2 , 1,1
p
K
m n m n
P M P
+
+
*


Propagation of chain type 1 with M
2

| |
11 *
, ,2 1 1, ,2
p
K
m n m n
P M P
+
+
*


Propagation of chain type 2 with M
1

| |
12 *
, ,2 2 , 1,2
p
K
m n m n
P M P
+
+
*


Propagation of chain type 2 with M
2

Chain transfer
* *
, , 0 ,
fspi
K
m n i m n
P P +
'
q

Spontaneous chain transfer or -elimination
| |
* *
, , 2 ,0 ,
fHi
K
m n i H m n
P H P q + +
'


Chain transfer to hydrogen (H
2
)
| |
*
, , ,0 ,
fAi
K
m n i A m n
P A P q + +
* '


Chain transfer to aluminum alkyl (A)
| |
*
, , ,0 ,
fEi
K
m n i E m n
P E P q + +
* '


Chain transfer to electron donor (E)
| |
1 *
, , 1 1,0,1 ,
fM i
K
m n i m n
P M P q + +
* '


Chain transfer to M
1

| |
2 *
, , 2 0,1,2 ,
fM i
K
m n i m n
P M P q + +
* '


Chain transfer to M
2

Deactivation
*
, , ,
dspi
K
m n i d m n
P C + q

Spontaneous deactivation
| |
*
, , ,
dZi
K
m n i d m n
P Z C q + +

Deactivation by impurities or poison (Z)
| |
*
, , ,
dAi
K
m n i d m n
P A C q + +

Deactivation by aluminum alkyl (A)
| |
*
, , ,
dEi
K
m n i d m n
P E C q + +

Deactivation by electron donor (E)
| |
*
, , 2 ,
dHi
K
m n i d m n
P H C q + +

Deactivation by hydrogen (H
2
)
*
, , ,
dMij
K
m n i j d m n
P M C q ( + +



Deactivation by monomers
Other possible reactions
*
1 * ' *
1,0,1 , 1, ,1
p
K
r s r s
P q P
+
+

Formation of short-chain branches
*
2 * ' *
0,1,2 , , 1,2
p
K
r s r s
P q P
+
+
*


Formation of short-chain branches
1 * ' *
, ,1 , , ,1
p
K
m n r s m r n s
P q P
+ +
+
*


Formation of long-chain branches (rare)
2 * ' *
, ,2 , , ,2
p
K
m n r s m r n s
P q P
+ +
+

Formation of long-chain branches (rare)

3.2 Mathematical Model

The multigrain model [13] gives a detailed description of phenomena taking place during polymerization
with supported ZieglerNatta and Phillips catalysts. The multigrain model takes into account the
heterogeneous nature of the resulting polymer particle. Two levels of mass and heat transfer resistances
were considered. The polymeric particle (called macroparticle or secondary particle) is formed by an
agglomerate of microparticles or primary particles. Each microparticle consists of a fragment of the
original catalyst particle, with all active sites on its external surface, surrounded by dead and living
polymer chains (in fact, the microparticles are described by solid core models on a very small scale).

Monomer diffuses through the pores of the macroparticle, adsorbs on the layer of polymer surrounding
the catalyst fragments in the microparticles, and diffuses through this layer to the active sites on the
surface of the fragments, where polymerization finally takes. It is envisioned that the newly formed
11
polymer chains push the previously formed polymer layer, thus increasing the radius of the
microparticles and consequently the size of the macroparticles. Electron microscopy studies confirm the
formation of primary and secondary structures in polymerizations with ZieglerNatta catalysts.



Figure 15: Schematic showing diffusion phenomenon
in a multigrain model (McKenna and Soares, 2001)
Figure 16: Micrograph of the surface of a prepolymer particle. The
particle is clearly an assembly of smaller, spherical structures as
described by the multigrain model (McKenna and Soares, 2001).


For the multigrain model, the radial profile of monomer concentration in the secondary particle
(macroparticle) is described by the well-known diffusion-reaction equations in spherical co-ordinates:


pv
s
s
s eff
s s
s
R
r
M
r D
r r t
M

|
|
.
|

\
|

2
2
1

(1)

( ) 0 , 0 = =

t r
r
M
s
s
s

(1a)

( ) (
s b s s s
s
s
eff
M M k t R r
r
M
D = =

, )
(1b)

( )
0
0 ,
s s s
M t r M = =
(1c)


where D
eff
is the effective diffusivity of monomer in the macroparticle, k
s
is the mass transfer coefficient
in the external film, M
b
is the bulk monomer concentration in the reactor, M
s
and M
s0
are the evolving
and initial monomer concentrations in the macroparticle, respectively, R
pv
is the volumetric rate of
polymerization in the macroparticle, r
s
is the radial position in the macroparticle, R
s
is the radius of
macroparticle, and t is the polymerization time. Note that R
pv
is the average rate of polymerization at a
given radial position in the macroparticle. In the multigrain model, it is supposed that the polymerization
takes place only on the surface of the catalyst fragments in the primary particles (microparticles). It is this
term that couples the models for the micro- and macroparticle.

The radial profile of monomer concentration in the microparticle is the same as that for the solid core
model:


|
|
.
|

\
|

p
p
p p
p p
p
r
M
r D
r r t
M
2
2
1

(2)
12

( )
pc c c p
p
p
p c
R R t R r
r
M
D R
3 2
3
4
, 4 = =

(2a)

( )
s eq p p p
M M t R r M = = ,
(2b)

( )
0
0 ,
p p p
M t r M = =
(2c)


where D
p
is the effective diffusivity of monomer in the microparticle, M
eq
is the equilibrium
concentration of monomer in the interface between micro- and macroparticles, M
p
is the monomer
concentration in the microparticle, M
p0
is the initial monomer concentration in the microparticle, R
pc
is
the rate of polymerization on the surface of the catalyst fragments, R
c
is the radius of catalyst fragments
in the microparticle, r
p
is the radial position in the microparticle, and R
p
is the radius of the microparticle.
The rate of polymerization on the microparticles is generally given by


( ) ( )| |
SA p pc
M t C t k R
*
=
(3)


where R
pc
is the rate of polymerization, k
p
is the propagation rate constant, C
*
(t) is the time-dependent
concentration of active sites on the surface of the microparticle, and [M]
SA
the concentration of monomer
on the active site.

Most models have tried to relate the effective diffusivity, D
eff
, to the value of the diffusivity of the
component in question in the bulk phase of the reactor, D
b
, using the expression commonly used for
heterogeneous catalysts,

b
eff
D
D ==
(4)

where and are the porosity and tortuosity of the macroparticle, respectively. Note that due to particle
fragmentation and growth, it is very likely that both and are functions of time and of radial position.
This makes the estimation of these parameters a particularly difficult task. Given that adsorption and
diffusion of monomer and other reactants can take place only in the amorphous fraction of a polymeric
material, D
p
needs to be corrected as a function of the crystallinity of the polymer matrix in the growing
microparticles. If D
a
stands for the diffusion of a given reactant in amorphous polymer, then D
p
can be
estimated according to the equation,

a
p
D
D ==
(5)

where and are correction factors to account for polymer crystallinity and chain immobilization of the
amorphous fraction.

The multigrain model also includes analogous equations to calculate the radial temperature profile in the
macroparticle,


( )
pv p
s
s
s e
s s
s
p p
R H
r
T
r k
r r t
T
C +
|
|
.
|

\
|

2
2
1

(6)

( ) 0 , 0 = =

t r
r
T
s
s
s

(6a)
13

( ) (
s b s s
s
s
e
T T h t R r
r
T
k = =

, )
(6b)

( )
0
0 ,
s s s
T t r T = =
(6c)

where C
p
is the heat capacity of the macroparticle, h is the film heat transfer coefficient, H
p
is the heat
of polymerization, k
e
is the effective heat conductivity in the macroparticle, T
b
is the temperature of the
continuous phase in the reactor, T
s
is the temperature in the macroparticle, T
s0
is the initial temperature in
the macroparticle, and
p
is the density of the macroparticle.

Similarly, for the microparticles, the temperature profile is given by


|
|
.
|

\
|

p
p
p e
p p
p
p p
r
T
r k
r r t
T
C
2
2
1

(7)

( ) ( )
c c p c p
p
p
e c
r R H t R r
r
T
k R
3 2
3
4
, 4 = =

(7a)

( )
s p p p
T t R r T = = ,
(7b)

( )
0
0 ,
p p p
T t r T = =
(7c)

where T
p0
is the initial temperature in the microparticle. Equations for intraparticle monomer
concentration and temperature radial profiles for the polymer flow model are similar to the ones for the
macroparticles of the multigrain model. It is either assumed that the mass transfer resistance at the level
of the microparticles is negligible or that it can be accounted for indirectly in the effective diffusivity D
eff
,
so that one can use Eq. (3) with a monomer concentration in equilibrium with the concentration of the
macroparticle to calculate the radial variation of the polymerization rate. The multigrain model is
certainly the most studied expansion model for polymerization of olefins with supported ZieglerNatta
catalysts. It has been used extensively to predict heat and mass transfer resistances for homo- and
copolymerization of ethylene, propylene, and higher -olefins, in slurry and gas-phase reactors.

3.3 Melt Flow Index and Density Control Model

The models proposed above are used in design of polymerization reactors and developing new polymer
grades. In industrial-scale production, different models are needed for real-time control using properties
measurable explicitly or analytically in a relatively short period of time. For this reason, density and melt
flow index (MI) are controlled at the polymerization reaction stage.

Density is a relative measure on degree of branching. The branching mechanism as discussed earlier is a
chain transfer step which requires the presence of a comonomer molecule. In an industrial reactor, the
ratio of comonomer to ethylene is a manipulated parameter to control density. To achieve a higher
density, the ratio is reduced and less comonomer is added.

The melt flow index (MI) is a relative measure of the polymer chain length. Referring to the reaction
mechanism, this is controlled by the termination step which requires either a monomer or a hydrogen
molecule. In an industrial reactor, the ratio of hydrogen to ethylene is a manipulated parameter to control
the MI. To achieve a higher MI, the ratio is increased and more hydrogen is fed to the reactor.

Some mathematical models have been developed to relate density and MI to the two feed ratios. These
correlations combined reaction kinetics with empirical parameters and serve as good guidelines to startup
a reactor or transition to a different resin grade. The following equation developed by McAuley and
MacGregor (1991) [12] illustrates how the instantaneous MI is estimated and related to the feed ratio as
well as the reactor temperature.
14

( )
| |
| |
| |
| |
| |
| |
| |
| |
2 3 4
0 1 2 3 4 5
2 2 2 2
1 1
ln 3.5ln
i
H C C R
MI k k k k k k
C C C C T
| |

= + + + + +
` |
\ . )
0
T
(8)

where, MI
i
is the instantaneous MI; H
2
, C
2
, C
3
and C
4
are concentration of hydrogen, ethylene, propylene
and 1-butene respectively; R is concentration of higher -olefin comonomer and T is the reactor
temperature.

Typically, during a startup or product grade transition, the comonomer to ethylene ratio is first adjusted to
achieve the desired density before trying control the MI. The primary reason is because polymer density
must be controlled to sustain the fluidization in the reactor. A sharp increase in density can result the
polymer granules becoming too heavy and lose fluidization. The secondary reason is density is also a
function of molecular weight. As MI is adjusted, density may change slightly. Depending on the final
value, the comonomer to ethylene ratio can be fine tuned to achieve the desired density without affecting
the MI.
4 CHALLENGES AND OPPORTUNITIES

Three decades have passed since the Union Carbide and BP built the earlier fluidized bed reactors.
Although many reaction lines have since been built, some inherent features of the process remain as a
challenge for an engineering breakthrough. Some of these challenges have even caused manufacturers to
choose alternative processes despite higher capital investment and/or utilities costs. In this section we
shall discuss some of these challenges and opportunities for process improvement.

4.1 Minimize off-specification product during grade changeover

One of the greater attractions of the fluidized bed reactor technology is the ability to produce polymers
with a wide range of density and melt flow index combination. This attraction is severely undermined by
the production loss involved in transition between resin grades. It will be ideal to switch between grades
seamlessly without any off-specification product while maintaining the production rate. In practice,
grade specifications rarely overlap, hence generating off-specification products during transition. The
production rate is also sacrificed to minimize these off-specification products, which can only be sold for
a small fraction of the prime grade resins. Grade transitions pose quality and capacity utilization
challenges.


Figure 17: Grade changeover scheme for ethylene polymerization

The root cause of this problem is the fluidization nature of the reactor. Unlike certain slurry and solution
reactor configurations, the reaction in a fluidized bed reactor cannot be terminated during transition.
There must always be polymer granules fluidized in the reactor, which necessitates catalysts to be fed
continuously. An easy way to overcome this problem is to develop polymer grades that have overlapping
15
specifications. Having too many product grades make it difficult to market the products and hence is
seldom practiced.

4.2 Heat removal control

The greatest challenge to the operators is the heat removal control. Polymerization is a very exothermic
reaction and it is essential to keep the reactor temperature constant. The challenge is greater if the cooler
is fouled and heat transfer is poor. If localized hot spot occurs, the fluidization pattern is modified. The
hot spot becomes a nucleus for polymerization at a much rapid rate. The granules can fuse into a sheet or
chunk. This sheet or chunk is too heavy to be suspended and will fall down to the gas distributor. It can
block the gas feed causing the reactor to lose fluidization and cease heat removal. Worst case scenario is
losing fluidization totally and all gases in the reactor convert into a single polymer chunk. This has
occurred in practice and the unit needs to be shut down. The polymer chunk was slowly cut into smaller
pieces before removing from the reactor.

One of the protection system employed is to reduce the polymerization rate by injecting some poison into
the reactor when temperature rises above the control limit. Usually carbon monoxide is injected in small
doses to prevent temperature excursion. If a chunk is detected, carbon monoxide is injected in a large
dose to terminate the reaction totally.

Heat removal capability also limits the production capacity. This means an existing production line
cannot be debottlenecked easily without large capital investment. One method to overcome this challenge
led to the development of the condensed mode operation. This mode of operation as discussed earlier
involves using large amount of 1-hexene comonomer which will condense in the cooler and vaporizes at
the gas feed distributor. This action removes a large amount of heat and enables higher production rate.
The scarcity of 1-hexene supply in some regions however limits the usefulness of this novel method.

4.3 Removal of reaction poisons

The gas fluidized bed process is very sensitive to poisons. Acetylene, carbon monoxide and carbon
dioxide are by-products of the pyrolysis process to make ethylene. These by-products in minute levels are
able to reduce the polymerization rate significantly. It is surprising that the high pressure and slurry
processes are not affected by these poisons.

To ensure the ethylene feed is free of the poisons, the supply has to be purified using a series of
adsorption beds. A typical purification train will have a palladium bed to remove acetylene, a copper
oxide bed to remove carbon monoxide, a copper bed to remove oxygen and molecular sieves to remove
moisture. For the same reason, comonomers also require a purification step. Comonomers are usually
degassed using a stripper column and dried using molecular sieve. The purification train poses a capital
investment cost and operating costs that is not incurred in other processes.


Figure 18: Ethylene purification train


16


4.4 Static Control

When polyethylene granules are fluidized within the reactor, they also rub with each other during their
random collision. This rubbing action generates static electricity. When two granules with dissimilar
electrical charges meet, they are attractive to each other and fuse into a larger granule. Left uncontrolled,
this can also form a nucleus for rapid polymerization similar to the hot spot phenomenon. This problem is
also unique to fluidized bed process.

In an industrial reactor, probes are added at different locations of the reactor to measure electrical
potential. Under normal situation, the static voltage reading will vary close to neutral state. For some
catalyst grade, the potential may swing towards positive or negative voltage. To control the static voltage,
a small dose of water or methanol (simple polar molecules) is injected into the reactor. This helps to
neutralize the static voltage.

4.5 Gel formation

Gels are polyethylene granules that are very hard and dense. They are after effects of localized hot spots
or temperature excursions but did not grow big enough to form a chunk. Gel can either remain as part of
the fluidized phase or stick to the walls of the reactor. Either way, they will finally come out as part of
product. The problem with these gels is that they do not melt under the normal extrusion temperature
either during pelletizing or extruded into the final product. They pose a major problem to film blowing
grade resins. The gels are visible on the blown film and may burst the film bubble.

When gels are detected in the product, the reactor needs to be shut down for mechanical cleaning. Gel
formation is a common operations phenomenon, causes unplanned production outage and further reduces
the capacity utilization.

4.6 Film clarity

All grades of polyethylene produced using the fluidized bed reactor processes are co-polymers of
ethylene with -olefins (usually 1-butene or 1-hexene). Films made from these co-polymers lose out in
film clarity compared to the homopolymers LDPE made using the free radical high pressure process.
There is a continuous demand for high clarity LDPE film especially for food packaging (e.g. bread
packaging) and films made from co-polymers loses out in this market.

This is one of the areas of improvement in the last few years. Special metallocene catalysts are
formulated to improve the clarity of the film. Some of these metallocenes are already commercialized
[19]. The successful development of late transition metal catalysts will enable manufacturers to produce
homopolymers using the fluidized bed reactor process. The commercialization of such catalyst however
is projected to be only in 2010 as development is still restricted to laboratory-scale experiments.
5 HYBRID TECHNOLOGIES

Hybrid technologies development is another area of active research and development. Utilizing the
principles of fluidized bed reactor, the process has been expanded to production of a wider range of
polyethylene and extended to production of polypropylene. Two commercial processes of such nature are
reviewed here.

5.1 Combination of Loop Reactor and Fluidized Bed Reactor [8]

The Spherilene gas-phase technology was developed by Basell Polyolefins to produce very low density
polyethylene (VLDPE), LLDPE as well as HDPE. The process uses a single Ziegler-Natta titanium-based
17
catalyst family. The process has a loop reactor and two fluidized bed reactors in series. Catalyst
components are mixed and fed directly to the loop reactor for pre-polymerization. This step exploits the
catalyst system potential in terms of morphology and mileage.

Product density is controlled from less than 0.9 g/ml (VLDPE) to more than 0.96 g/ml (HDPE). MI
capability ranges from 0.01 to > 100 g/ 10 min. Because of the two fluidized bed reactors setup, this
technology is able to produce bimodal grades (MI, density) and specialty polymers based on new
molecular models. For example, terpolymer grades which have better properties compared to
conventional 1-butene LLDPE/VLDPE and hexene quattropolymer to replace hexene based LLDPE.
LDPE replacement grades for clarity and shrink film applications have also been developed. There are 8
plants using this technology and a combined capacity of 1.8 MMtpy.




Figure 19: Spherilene gas-phase technology (Hydrocarbon Processing, 2003)

5.2 Fluidized Bed Reactors in Series [8]

The UNIPOL PP process was developed by Dow Chemical to produce homopolymers, random
copolymer and impact copolymer polypropylene. A wide range of polypropylene is made in a gas phase
fluidized bed reactor using proprietary catalysts. Melt flow index, isotactic level and molecular weight
distribution are controlled by utilizing the proper catalyst, adjusting operating conditions and adding
molecular weight control agent. Random copolymers are produced by adding ethylene or 1-butene.
Ethylene addition to a second reactor in series is used to produce the rubber phase of impact copolymers.


Figure 20: Dow Chemical Co. UNIPOL PP technology (Hydrocarbon Processing, 2003)

18
Homopolymers can be produced with MI from less than 0.1 to 3,000 g/ 10 mins and isotactic content up
to 99%. Random copolymers can be produced with up to 12% ethylene or up to 21% 1-butene. Impact
copolymers can be polymerized with a good stiffness to impact balance. More than 30 reaction lines are
in operation. Total worldwide production is over 5 MMtpy.
6 CONCLUSIONS

Polyethylene is the most common thermoplastic and used in a wide range of applications. There are
various commercial technologies available to produce polyethylene. Gas fluidized bed polymerization is
one of the later technology developed and is commonly employed in the production of linear-low density
polyethylene (LLDPE) and high density polyethylene (HDPE). The early fluidized bed reactor
technology was developed independently by Phillips Petroleum, Union Carbide and Naphtachimie.
Commercial fluidized bed PE technology is now licensed by Univation Technologies and BP Chemicals.
There are three types of commercial catalysts, namely Ziegler-Natta catalyst, Phillips catalyst and
metallocene catalyst. A fourth type of catalyst based on late transition metal is still in the research and
development phase. Polymerization mechanism is made up of a series of reactions. Multigrain model was
presented to describe the reaction process mathematically. Mechanical properties and processability is
affected by molecular weight distribution and the degree of branching. In production process, this is
measured as melt flow index and density. Some operational challenges were presented to highlight the
limitations of the process. Some new polymerization processes are hybrid processes which borrowed the
principles of fluidized bed reactors for polyethylene production.
7 REFERENCES
[1] Alizadeh, M, Mostoufi, N., Pourmahdian, S., Sotudeh-Gharebagh, R., Modeling of fluidized bed
reactor of ethylene polymerization, Chemical Engineering Journal, 2004, 97, 27 35.
[2] Cerruti, L., Historical and Philopsophical Remarks on Ziegler-Natta Catalyst, A Discourse on
Industrial Catalysis, HYLE-International Journal for Philosophy of Chemistry, 1999, 5, 3 41.
[3] Domenval, R., Havas, L., Mangin, P., Process for dry polymerization of olefins, US Patent
3,922,322, 1975, assigned to Naphtachimie [transferred to BP Chemicals Limited].
[4] Dye, R.F., Polymerization Process, US Patent 3,023,203, 1962, assigned to Phillips Petroleum
Company.
[5] Goins, R.R., Olefin Polymerization, US Patent 2,963,303, 1960, assigned to Phillips Petroleum
Company.
[6] Havas, L., Mangin. P., Method of producing solid polymers, US Patent 3,954,909, 1976,
assigned to Naphtachimie [transferred to BP Chemicals Limited].
[7] Havas, L., Lalanne-Magne, C., Gas phase polymerization process, US Patent 5,306,792, 1994,
assigned to BP Chemicals Limited.
[8] Hydrocarbon Processing, Petrochemical Processes 2003, Hydrocarbon Processing 2003, March,
116 120.
[9] Jorgensen, R.J., Goeke, G.L., Karol, F.J., Catalyst composition for copolymerizing ethylene, US
Patent 4,303,771, 1982, assigned to Union Carbide Corporation.
[10] Karol, F.J., Wu, C.S., Ethylene polymerization with silane modified catalyst, US Patent
4,086,408, 1978, assigned to Union Carbide Corporation.
[11] Levine, I.J., Karol, F.J., Preparation of low and medium density ethylene polymer in fluid bed
reactor, US Patent 4,011,382, 1977, assigned to Union Carbide Corporation.
[12] McAuley, K.B., MacGregor, J.F., On-line inference of polymer properties in an industrial
polyethylene reactor, AIChE J., 1991, 37 (6), 825 - 835.
[13] McKenna, T.F., Soares, J.B.P., Single particle modeling for olefin polymerization on supported
catalysts: A review and proposals for future developments, Chemical Engineering Science,
2001, 56, 3931 3949.
[14] Miller, A.R., Fluidized Bed Reactor, US Patent 4,003,712, 1977, assigned to Union Carbide
Corporation.
[15] Ohshima, M., Tanigaki, M., Quality control of polymer production processes, Journal of
Process Control, 2000, 10, 135 148.
19
20
[16] Sishta, P.C., Wasserman, E.P., Karol, F.J., Production of polyethylene using stereoisomeric
metallocenes, US Patent 5,852,143, 1998, assigned to Union Carbide Chemicals & Plastics
Technology Corporation.
[17] Soares, J.B.P., Mathematical modeling of the microstructure of polyolefins made by
coordination polymerization: a review, Chemical Engineering Science, 2001, 56, 4131 4153.
[18] Swindoll, R.D., Story, B.A., Kolthammer, B.W.S., Pell, K.P., Wilson, D.R., Stevens, J.C., Gas
phase polymerization of olefins, US Patent 6,538,080 B1, 2003, assigned to BP Chemicals
Limited.
[19] Univation Technologies, viewed on March 12, 2004. [URL: www.univation.com]
[20] Wagner, B.E., Goeke, G.L., Karol, F.J., Process for preparation of high density ethylene
polymers in fluid bed reactor, US Patent 4,303,771, 1981, assigned to Union Carbide
Corporation.
[21] Winter, A., Kueber, F., Spaleck, W., Riepl, H., Herrmann, W.A., Dolle, V., Rohrmann, J.,
Process for the preparation of an olefin polymer using metallocenes containing specifically
substituted indenyl ligands, US Patent RE37,573 E, 2002, assigned to Basell Polyolefin GmbH.
[22] Xie, T., McAuley, K.B., Hsu, J.C.C., Bacon, J.W., Gas Phase Ethylene Polymerization:
Production Processes, Polymer Properties, and Reactor Modeling, Ind. Eng. Chem. Res. 1994,
33, 449 479.