Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
1994,33, 449-479
449
REVIEWS
Gas Phase Ethylene Polymerization: Production Processes, Polymer
Properties, and Reactor Modeling
Tuyu Xie, Kim B. McAuley,' James C. C. HSU,and David W. Bacon
Department of Chemical Engineering, Queen's University, Kingston, Ontario, Canada K 7 L 3N6
A review of relevant macroscopic and microscopic processes of gas phase ethylene polymerization,
both chemical and physical, is given. The commercial technology development of gas-phase ethylene
polymerization processes is illustrated through a selective survey of the patent literature. Both
advantages and disadvantages of gas phase polymerization processes are addressed, and the challenges
of laboratory studies of gas phase polymerization are also outlined. Physicochemical phenomena
of ethylene polymerization using heterogeneous catalysts are discussed, including examination of
catalyst preparation, polymer morphological development, and elementary chemical reactions.
Metallocene-based catalysts and their kinetic performance for olefin polymerizations are also
discussed. The current state of the art for reactor modeling of polymerization rate, molecular
weight development, reactor dynamics, and resin grade transition strategies is illustrated on the
basis of the most recent academic studies. Finally, relationships between resin properties and
polymer microstructures as well as characterization methods are described briefly. In particular,
temperature-rising elution fractionation technology is emphasized for characterization of ethylene
copolymers. The fundamental issues involved in gas phase ethylene polymerization and the&
interrelationships are also discussed in some detail.
Contents
1. Introduction
2. Gas Phase Polymerization Processes
2.1. Commercial Gas Phase
Polymerization Processes
2.2. Experimental Methods
3. Physicochemical Phenomena
3.1. Catalysts for Gas Phase
Polymerization
3.2. Polymer Particle Morphology
Developments
3.3. Chemical Reactions
4. Reactor Modeling
4.1. Kinetic Modeling
4.2. Dynamic Process Modeling and
Control
5. Polymer Properties and
Characterization
5.1. Physical and Mechanical
Properties
5.2. Polyethylene Characterization
6. Summary
7. References
449
450
450
455
456
456
460
461
463
463
467
469
469
470
474
474
1. Introduction
eI-z
6000 -
f
HDPE
vj
2ooo
.""" 80
82
86
84
88
90
TIME, year
92
94
96
0.97 0.96 -
- 0.95 rn
0.94
v)
z
W
0 0.93 -
SHEET
0.92 -
0.91 0.90 1
0.01
1.oo
10.0
MELT INDEX, 9/10 min
0.10
100
The distinguishing characteristic of gas phase polymerization is that the system does not involve any liquid
phase in the polymerization zone. Polymerization does
occur 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. Hence, gas phase polymerization is also
called dry polymerization in some patents (Dormenval et
al., 1975; Havas and Mangin, 1976). In this section,
commercial gas phase polymerization processes and experimental studies of gas phase polymerization are discussed.
2.1. Commercial Gas Phase Polymerization Processes. The invention of gas phase ethylene polymeri-
reactor type
conventional
high-press. process
tubular or autoclave
high-press.
bulk process
autoclave
solution
Polymn
CSTR
1200-3000
130-350
free radical
monomer phase
0.910-0.930
0.10-100
Doak (1986)
600-800
200-300
coordination
monomer phase
0.910-0.955
0.80-100
Grunig and Luft (1986);
Villermaux et al. (1989)
100
140-200
coordination
solvent
0.910.970
0.50-105
James (1986)
GAS RECYCLE
CATALYST
FEEDER
GAS FEED
7
EXCHANGER
slurry polymn
loop or CSTR
30-35
85-110
coordination
solid
0.930.970
<0.01-80
Choi and Ray (1985a);
Short (1981)
gas phase
polymn
fluidized or
stirred bed
30-35
80-100
coordination
solid
0.910-0.970
<0.01-200
James (1986)
CATALYST
FEEDER
INERT GAS
GAS FEED
COMPRESSOR
l h
ACTIVATOR
FEEDER
RECYCLE
CATALYG
SPYY NOZZLES
-h
I!
POLYMER
DISCHARGE
MONOMER
RECYCLE
Q
9
-4'
COMPRESSOR
Table 2. Ethylene Gas Phaw Polymerization Prowsws and Reactor Operating Conditions
Union Carbide
BASF
AMOCO
nvletortype
fluidized bed
stirred bsd
horizontal stirred bsd
catdlyst
caialyat size,pm
press., atm
temp. O C
comonomer
MWcontrol
MWD. Mw/Mm
density, g/cmJ
supported CrCOS
~ ~ p p o r t Ti
s d and
crcos catalyst
catalyat
-35
100-110
1-butene
1-buteneor 1-hexene
Ha
Ha
4-30
narrow tu broad
0.91-0.87
500-1300
Rasmuassn (1972):
Trieaehmann et al. (1977):
N i d e t t i et al. (1988)
Choi and Ray (1985a)
BP Chemic&
stirred reactor and
f l u i d d bed
supported Ti and
crco2 catalyat
20-40
15-25
70-110
70-115
5-17
0.95-0.98
620
propylene or 1-butene
H,and temperature
I-butene or I-hexene
Ha
0.91-0.96
300-1200
0.970
0.980
0.950
a
-In 0 . 0
5 0.93
0
0.920
0.910
0.01
0.10
1.00
10.0
100
0910
"
"1
"
A
I"
U"
I""
high-pressure process
tubular or autoclave reactor
low-pressure process
fluidized bed or stirred
bed reactor
low operating pressure,
-20 atm
low reaction temperature,
80-110 OC
low energy requirement
low capital cost
can produce both high- and
low-density PE
up to l0-15% comonomer
required (copolymer)
catalyst is very sensitive
to impurities
high raw material cost
currently a limited range
of comonomers
mostly linear polymer
chains with short-chain
branching
rt TO WATER BATH
/1
3
Figure 10. Laboratory reactors for gas phase ethylene polymerization. (1) Choi et al. (1983, 1985b); (2) Lynch et al. (1991); (3)
Dusseault (1991).
456
polymerization process
requirements
high productivity
proper kinetic behavior
catalyst morphology
control of polymer morphology
good comonomer incorporation
easy feed to reactor
low cost and reproducible
catalyst preparation
silica
particle size, pm
surface area, m2/g
pore size, A
concn of catalyst metal,
mmol/g of support
range
10-250
at least 3
at least 80
0.054.5
preferable range
30-100
50
100
0.2-0.3
Mg/Ti/EDa
activator
productivity
Hz response
MWD
a-olefin incorporation
activity decay rate
polymer chain unsaturation
long-chain branching
R3A1
high
moderate
narrow, 3-6
moderate
moderate
low
no
VC13(THF)3
R&l + halocarbon promoter
high
high
intermediate-broad
high
low-moderate
very low
no
CrOs
thermal, 300-1000 OC
high
low
intermediate-broad, 6-30
high
very low
one C=C per polymer molecule
low concn of long-chain branching
ED is an electron donor.
Table 8. Approximate Dimensions of MgCll Supported
Table 7. Operational Methods to Produce High-Activity
Catalyst (Chien et al.. 1983: Chien. 1987: 1988)
Catalysts (Karol, 1984)
1.chemical anchoring to surface of support
pore
surface
(a) TiCWMg(0H)Cl
volume,
area,
(b) CrOa/SiOz
composition
diameter,A
cm3/g
m2/g
(c)
. . (CKHdoCr/SiO,
.
MgC12 (HCl treated)
-4000
0.41
2. formation of bimetallic complexes
700-1500
0.41
2.0-7.0
(a) MgClz + 2TiC4 + 8Poc13 [TiCl~~lZ[Mg(POC13)sl~+~2POC13MgCldEB
MgClz/EB/PC/AlEts
300-500
1.2
50-70
(b)2MgC1~+ Tic4 + 7THF [TiCls(THF)l-[Mg2Cl~(THF)61+
MgC12/EB/PC/AlEt3/TiC&
25-170
1.3
100-150
(c) MgC12 + Tic4 + 4CH3COzCzHs TiMgCl&H&OzCzHs)4
3. insertion into defects of support
(a) MgClz + Tic14 + ethyl p-toluate ball-milling
MgClz with an electron donor (internal Lewis base), such
(b) MgClz + TiQedioxane
ball-milling
as ethyl benzoate, can produce a disordered crystal
4. formation of high surface area sponge
structure and reduce crystalline size to 20-40 A. The
~~
I,_
-- - - +- +
bwmyl ether
~~
_I_I
lo
200
150
600
600
700
800 900 lo00
ACTIVATION TEMPERATURE ('C)
460
supported heterogeneous Ziegler-Natta catalysts (Kaminsky and Luker, 1984; Chien and Wang, 1990). Hydrogen also reduces polymerization rate (Kaminsky and
Luker, 1984; Kioka et al., 1992).
Uniform incorporation of comonomers. Composition of copolymer is almost the same as the monomer feed
composition, and comonomer is uniformly distributed in
copolymer chains regardless of chain length (Chien and
He, 1991a,d; Uozumi and Soga, 1992). The effect of
comonomer on ethylene polymerization rate depends on
polymerization temperature. 1-Hexene or propylene
enhances ethylene consumption rate at 30 and 50 "C
(Tsutsui and Kashiwa, 1988; Koivumaki and Seppala,
1993). However, 1-hexene reduces ethylene polymerization rate at 70 and 95 "C (Chien and Nozaki, 1993;
Koivumaki and Seppala, 1993).
Stereochemical control i n microstructures of olefin
polymers. Metallocene catalysts by manipulating the
structures of organocompoundscan polymerize olefins with
very high stereoregularity to give either isotactic or
syndiotatic polymers (Ewen, 1984;Kaminsky et al., 1985,
1986; Kaminsky, 1986; Ewen et al., 1988; Antberg et al.,
1990; Chien and Sugimoto, 1991; Antberg et al., 1991;
Uozumi and Soga, 1992).
Very high cocatalyst ratio. To obtain high polymerization rate and high active center concentration, the
Al/Zr ratio needs to be 1OL1O4orhigher (Chien and Razavi,
1988; Sinn et al., 1988; Chien and Wang, 1989). If the
AVZr ratio is small, the polymerization rate increasesslowly
and has an induction period (Chien and Sugimoto, 1991).
The reason for high cocatalyst ratio is still unclear. The
cost of cocatalyst could be more than 200-300 times the
cost of the catalyst in commercial production (SRI, 1993).
Hence, high cocatalyst ratio is one of the major barriers
to commercialization of metallocene technologies.
Metallocene catalysts must be supported on a carrier
for use in gas phase processes. Chien and He (1991~)
found
that Et[Ind12ZrClz supported on Si02 does not change
polymerization behavior. Interestingly, a smaller amount
of MA0 is required in the case of the supported catalyst
than for the homogeneous system to achieve the same
catalytic activity. Et[IndHrlzZrClz supported on A1203
or MgC12 can be activated by common trialkylaluminums;
however, the catalyst cannot be activated by common
alkylaluminums if it is supported on Si02 (Soga and
Kaminaka, 1992;Soga et al., 1993). The MgClz supported
metallocene catalysts produced a broader MWD (Soga et
al., 1993). CpzZrClz supported on A1203 or MgClz produces
atactic polypropylene, but is inactive to propylene using
Si02 as a carrier (Kaminaka and Soga, 1992). The effect
of a carrier on the performance of metallocene catalysts
is unclear at present.
For six decades, the polyolefin industry has experienced
several great revolutions. Despite the fact that there are
some technological difficulties, commercialization of metallocene-based catalyst technologies may be the greatest
revolution of all. The impact of metallocene-based
catalysts on polyolefin industry is perhaps beyond the
current imagination.
3.2. Polymer Particle Morphology Developments.
One of the most important features of ethylene polymerization using heterogeneous catalysts is replication of
polymer particles (Berger and Grieveson, 1965;Mackie et
al., 1967). This suggeststhat the morphologydevelopment
of polymer particles depends on the original morphology
of the catalysts. Polymer growth on titanium crystal
surfaces has been carefully examined using electron
microscopy (Carradine and Rase, 1971;Baker et al., 1973),
8o
70
CATALYST
/
,
0-38
45-75
3845
100-250
500-1000
75-100
250-500
>loo0
LOW
POLYMER
YIELD
MEDIATE
description
Activation
spontaneous activation
activation by aluminum
alkyl (A)
activation by electron
donor (E)
activation by hydrogen
(Hz)
activation by monomer
1 (Mi)
activation by monomer
2 (Mz)
Initiation
initiation of M 1 by normal
active center
initiation of Mz by normal
active center
initiation of MI by active
center with H
initiation of Mz by active
center with H
initiation of MI by active
center with A
initiation of Mz by active
center with A
initiation of M 1 by active
center with E
initiation of Mz by active
center with E
Propagation
KPll
propagation of chain
type 1with M 1
P m , n , l + [MI3
Pm+l,n,I
K~LZ
propagation of chain
type 1with M 2
P*m,n,l + [ M 2 1
p*m,nt1,2
K~PI
propagation of chain
type 2 with MI
P m , n , z + [MI3 -* P m + l , n , *
KPln
propagation of chain
type 2 with Mz
P m , n , z + [Mz] P m , n + l , z
Chain Transfer
Kbpl
spontaneous chain transfer
or &elimination
P*m.n.i
PO+ 4'm.n
KIN
chain transfer to hydrogen
P m n L + [HJ
PH.O
+ Q'm.n
(Hz)
KfAl
chaintransfer to aluminum
P m , n , L + [AI
P*A,O + Q'm,n
alkyl (A)
Kls,
chain transfer to electron
P m , n , i + [El -+ P*E,o
+ P'm,n
donor (E)
KMl3
chain transfer to M 1
P m , n i + [MI]
P*I,o,I+ Q'm,n
K m
chain transfer to Mz
P m , n , i + [Mz]
*o,I,,
+ q'm.n
Deactivation
KW
spontaneous deactivation
Pm,n,i
-*
'
cd
qm,n
Kd7i
Pm,n,i
+ lZ1
plm,n,i
cd
+ qm,n
d'
+ qm,n
- '
-*
KW
KdW
..+
cd
Pm.n.i
4m.n
KdHl
Pm,n,+
+ [H21
d'
+ qm,n
d'
+ 4m,n
KdJ&
Pm,n,L
rMj]
deactivation by impurities or
poison (Z)
deactivation by aluminum
alkyl (A)
deactivation by electron
donor (E)
deactivation by hydrogen (H2)
deactivation by monomers
-+
+ 4,
MICROSCALE
MESOSCALE
1
I
M ACROSCALE
i=l j - 1
MW f ~ ~ , ~ ~ * ~ l , ~ ~ j .-.)
l , ~ ~ (2)
~ l
where binary copolymerization is assumed. With the longchain approximation, polymerization rate is a function of
the propagation rate constants, monomer concentrations,
and active center concentration. Complexity can arise
through the expression for active center concentration.
Molecular weight development is a function of all the
components which affect polymer chain length, as shown
in Table 9. One of the important features of ethylene
polymerization is the broad molecular weight distribution
of the polymer. Two theories have been developed to
explain broad MWD of polyethylene, namely, diffusion
theory and multiple active center theory. The former
emphasizes the effect of monomer concentration on
molecular weight development. The latter is more concerned with the influence of active centers and associated
kinetic parameters. Some of the experimental results in
support of these theories are as follows.
Diffusional limitations:
1. Polymerization rate depends on stirring speed when
agitation speed is below a critical level (Berger and
Grieveson, 1965; Bohm, 1978b).
, ~ ~ l , ~
0
E
"i
8-
*.
Prediction
D,
1 x 10-~ c d i s
+ + Laboratory Data
7ooOo
960000
3
4 s
,%J
'
3oooo
4oooo-
*++L++**+*-'+++++
ib
io io
4b
**+**++,++++++
io ab
7b
io ~b id^ iio
Time in Hours
Figure 15. Comparison of model predictions and industrial laboratory data for gas phase ethylene copolymerization in a fluidized
bed reactor. Reprinted with permission from McAuley et al. (1990).
Copyright 1990 AIChE.
n
2
) . . .
Mb
1
Mn2
0.0
0.2
0.4
4 mOl/f
1
'
30,000
0.8
0.8
1.0
WElaHT FRACTION
Figure 17. Polydispersityresulting from combinationof two polymer
fractions, each with polydispersity of 2. Reprinted with permission
from Floyd et al. (1987). Copyright 1987 John Wiley & Sons.
u * 2 cm/s
fi inslonloneous breakup
00
IO2
3 r
0.5
1.0
1.5
2.0
2.5
3.0
hslonloneous brrohuv
00
05
I.o
1.5
20
25
3.0
TIME (sec)
Figure 18. External film heat- and mass-transfer resistances in gas
phase polymerization of polyethylene under stirred bed conditions
with high activity catalyst. Reprinted with permission from Floyd
et al. (1986~).Copyright 1986 John Wiley & Sons.
R,, P,,
M,,a,, polydispersity
basic assumption
isothermal, spherical
particles, two active sites,
effect of diffusion control
1imitation
multiple active sites,
concentration of reactant
is independent of active
sites, deactivation depends
on site type, steady state
for growing chains
two or three active sites,
steady state for living
chains, first-order
deactivation
multiple active sites,
monomer concentration
in the active sites is
proportional to gas phase
pressure and independent
of sites, steady state for
growing chains, uniform gas
composition and temperature
multiple active sites,
consider effect of diffusion
limitation, steady state
for growing chains, multiple
grain particles
reference
CSTR, high-temperature
and high-pressure
copolymerization
'
30u
SPECIFICATION LIMITS
COMPLETED
O.DOO
n.nn2
0.n08
0.004
0.008
o.010
.in
Dlstrlbutlon
,,,,,,,,, ,,,,,,,,, .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
o. aa
a. as
a.
io
0.
IS
a. 20
2
TIME, hr
0
0
0.4
0.8
1.2
1.6
SCALED MOLE FRACTION OF BUTENE IN POLYMER
2.0
a,(ln MI, - In
Vpdes)'
0.4
0.8
1.2
1.6
2.0
* STIFFNESS
'TENSILE STRENGTH
* HEAT RESISTANCE
* HARDNESS
* PERMEATION RESISTANCE
'SHRINMGE
* DISTORTION RESISTANCE
* OPTICALS 7
;
v)
* FLEXIBILITY
* IMPACT STRENGTH
/
)O
\
I
DENSITY, g/ml
0 97
0.1
MELT INDEX
100
-MOLECULAR WEIGHT
0.93-0.97
HDPE
giml
I,
LLDPE
0.91-0.93 giml
LDPE
0.91-0 93 glml
32
A b
ia
25
16 .
%X 2 O
y
- c
P4:
m
16
$ 13
5 12
10
2 7.8 -
g 6.3
b>5.0
"3;
1
-
"1
Y
a
2
a 10
3
a 6
6
2.5
2.0
4
0 01
01
10
MELT INDEX, 9/10min
10
100
10
12
14
16
MELT FLOW RATIO
ia
20
472
BRANCH FREQUENCY
,r m
40
40
Figure 30. Schematic diagram for an autoanalytical TREF instrument. Reprinted with permission from Hazlitt (1990). Copyright
1990 John Wiley & Sons.
$70
40
V
-.30
0
0
e,,,,,,
E 20
w7
L L
O
-M, 10X I 0
50
100
IO
0
IO1
IO'
IO'
IO'
HOLECULRR WEJCHT
Figure 33. Contour map of distributionof compositionandmolecular
weight for LLDPE. Reprinted with permission from Hosoda (1988).
Copyright 1988 The Society of Polymer Science, Japan.
6. Summary
7. Literature Cited