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Recent developments in modeling gasphase catalyzed olefin polymerization

fluidized-bed reactors: The effect of bubble
size variation on the reactor's performance
ARTICLE in CHEMICAL ENGINEERING SCIENCE AUGUST 2000
Impact Factor: 2.61 DOI: 10.1016/S0009-2509(99)00565-5

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Chemical Engineering Science 55 (2000) 3237}3259

Recent developments in modeling gas-phase catalyzed ole"n

polymerization #uidized-bed reactors: The e!ect of bubble size
variation on the reactor's performance
H. Hatzantonis, H. Yiannoulakis, A. Yiagopoulos, C. Kiparissides*
Department of Chemical Engineering and Chemical Process Engineering Research Institute, Aristotle University of Thessaloniki, P.O. Box 472,
Thessaloniki, Greece 540 06
Received 8 April 1999; received in revised form 20 September 1999; accepted 9 November 1999

Abstract
In the present study recent developments in modeling gas-phase catalyzed ole"n polymerization #uidized-bed reactors (FBR) are
critically reviewed. A new FBR model is developed to account for the e!ect of varying bubble size with the bed height on the reactor
dynamics and the molecular properties of the polymer product. A comprehensive kinetic model for ethylene copolymerization in
the presence of a multisite Ziegler}Natta catalyst is considered to describe the molecular weight developments in the FBR. The
bubble-growth model developed in the present study is subsequently compared with two well-known FBR models, namely, the
well-mixed and the constant bubble size model. The e!ect of important reactor parameters such as super"cial gas velocity, maximum
stable bubble size, mean particle size, catalyst injection rate, monomer/comonomer feed ratio and temperature of the feed stream, on
the dynamic and steady-state behavior of the FBR is investigated. It is shown that the maximum stable bubble size, a critical
parameter in the constant bubble size model, turns out to be less important when the bubble size is allowed to vary with the bed
height. For typical industrial operating conditions, the constant bubble size model consistently overpredicts the emulsion phase
temperature and monomer conversion, while the well-mixed model underestimates them. On the other hand, the bubble-growth
model shows an intermediate behavior since it represents a more realistic description of the gas phase in the bed.  2000 Elsevier
Science Ltd. All rights reserved.
Keywords: Fluidized bed reactor; Ole"n polymerization; Bubble-growth model; Polymerization modeling; Two-phase #uidization

1. Introduction
Fluidized-bed solid catalyzed ole"n polymerization
has long been recognized as one of the main roads for
producing polyole"ns. In such a process, small catalyst
particles (e.g., 20}80 lm in diameter) are continuously fed
into the #uidized-bed reactor, at a point above the gas
distributor, and react with the incoming #uidizing gaseous monomers to produce a broad distribution of polymer particles in the size range of 100}5000 lm. The
particulate polyole"n product is continuously withdrawn
from the reactor at a point between the distributor plate
and the bed surface, preferably close to the bottom of the
bed. Polymerization heat is removed by means of the

* Corresponding author. Tel.: #3031-99-6211; fax: #31-99-6198.

E-mail address: cypress@alexandros.cperi.forth.gr (C. Kiparissides)

unreacted gas exiting the bed which is subsequently

cooled and recycled to the reactor. Industrial #uidizedbed reactors typically operate at temperatures of
75}1103C and pressures of 20}40 bar (Xie, McAuley, Hsu
& Bacon, 1994). The super"cial gas velocity can vary
from 3 to 8 times the minimum #uidization velocity.
Catalyst injection rates are in the range of 0.001}0.05 g/s,
depending on catalyst activity and reactor capacity.
Single-pass monomer conversion can vary from 2 to 5%,
whereas the overall monomer conversion can be as high
as 98% (McAuley, Talbot & Harris, 1994).
A great number of publications have appeared in the
open literature dealing with the mathematical modeling
of the complex and interrelated physical and chemical
phenomena taking place in conventional #uidized-bed
reactors. Early modeling developments on FBRs include
the fundamental two-phase model of Toomey and
Johnstone (1952), the bubbling-bed model of Kunii and
Levenspiel (1969), and the bubble-assemblage model of

0009-2509/00/$ - see front matter  2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 9 ) 0 0 5 6 5 - 5

3238

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Nomenclature
A
[A]
Ar
AI
QD

cross-sectional area of the bed, cm

cocatalyst concentration, mol/cm
Archimedes number ["do (o !o )g/k]
N E Q
E
fraction of metal that can form `ka catalyst
active sites, mol/mol Me
C
mass fraction of catalyst in the solid phase

CI
concentration of deactivated `ka catalyst active
B
sites, mol/cm
C
speci"c heat capacity of gaseous stream,
NE
cal/g/K
C G speci"c heat of `i a monomer, cal/mol/K
N+
C
speci"c heat capacity of polymer product,
N
cal/g/K
d
bubble diameter, cm
@
d
maximum stable bubble size, cm
@ 
d
particle diameter, cm
N
D
gas self-di!usion coe$cient, cm/s
E
D
bed diameter, cm


DI
concentration of `deada copolymer chains of
L
length n produced at `ka catalyst active site,
mol/cm
E
activation energy, cal/mol
f
mole fraction of monomer i
G
F
catalyst feed rate, g/s

g
acceleration of gravity, cm/s
[H ] hydrogen concentration, mol/cm

h
random bed height, cm
H
total bed height, cm
H
bed height at minimum #uidization conditions,
KD
cm
H
bubble to cloud heat transfer coe$cient,
@A
cal/cm/s/K
H
cloud to emulsion heat transfer coe$cient,
AC
cal/cm/s/K
H
bubble to emulsion heat transfer coe$cient,
@C
cal/cm/s/K
kI
rate constant of initiation by `i a monomer for
G
`ka catalyst active site, cm/mol/s
kI
rate constant of activation by cocatalyst for `ka
?
catalyst active site, cm/mol/s
kI
rate constant spontaneous deactivation for `ka
B 
catalyst active site, 1/s
kI
rate constant of propagation of `j a monomer
NGH
for `ka catalyst active site with `i a terminal
monomer, cm/mol/s
kI
rate constant of transfer to hydrogen for `ka
R&G
catalyst active site with `i a terminal monomer,
cm/mol/s
kI
rate constant of transfer to `j a monomer for
R+GH
`ka catalyst active site with `i a terminal monomer, cm/mol/s

kI
R  G

rate constant of spontaneous transfer for `ka

catalyst active site with `i a terminal monomer,
1/s
k
gas thermal conductivity, cal/cm/s/K
E
K
bubble to cloud mass transfer coe$cient, 1/s
@A
K
cloud to emulsion mass transfer coe$cient, 1/s
AC
K
bubble to emulsion mass transfer coe$cient,
@C
1/s
[M ] active metal concentration, mol Me/cm
C
[M ] `i a monomer concentration, mol/cm
G
[M ] total monomer concentration, mol/cm
2
M
number average molecular weight of `bulka
L
copolymer
M
weight average molecular weight of `bulka
U
copolymer
MW
molecular weight of `i a monomer
G
N
total number of compartments
N
total number of monomers
K
N
total number of catalyst active sites
Q
PI
concentration of vacant `ka catalyst active

sites, mol/cm
PI
concentration of `ka active sites (vacant and
H
occupied by polymer chain), mol/cm
PI
concentration of `livea copolymer chains of
L
length n, with terminal monomer `i a, at `ka
catalyst active site, mol/cm
PD
polydispersity of `bulka copolymer
Q
volumetric product removal rate, cm/s

Re
Reynolds number ("d u o /k)
.KD
N KD E
RI
reaction rate of species X at `ka catalyst active
6
sites, mol/cm/s
SI
concentration of potential `ka catalyst active
N
sites, mol/cm

temperature, K
u
super"cial gas velocity, cm/s

u
bubble rise velocity, cm/s
@
u
emulsion gas velocity, cm/s
C
u
minimum #uidization velocity, cm/s
KD
u
bubble gas velocity, cm/s
@
u
particle terminal velocity, cm/s
2
<
volume, cm
x
number average chain length of `bulka
L
copolymer
x
weight average chain length of `bulka copolymer
U
Greek letters
c
DH
P"L
d
@
e
j
k

reaction order
heat of reaction, cal/g
bubble phase volume fraction
void fraction
`livea copolymer moment, mol/cm
`bulka copolymer moment, mol/cm

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

k
E
l
m
o
u
G
U
G

viscosity of gas, g/cm/s

moment order
`deada copolymer moment, mol/cm
density, g/cm
instantaneous `i a comonomer copolymer composition
cumulative `i a comonomer copolymer composition

Subscripts and superscripts

1
2

b
bed
cat
e
g
in
k
mf
n
pol
ref

3239

bubble phase property

bed property
catalyst property
emulsion phase property
gas mixture property
feed property
type of catalyst active site
minimum #uidization conditions
compartment number
polymer property
reference value

ethylene property
butene-1 property

Kato and Wen (1969). More recently, the multicompartment three-phase model (El-Halwagi & El-Rifay, 1988),
the improved bubble assemblage model (Shiau & Lin,
1993), and the three-phase multicompartment model
(Tabis & Essekkat, 1992), were proposed to account for
the complex mass and heat transfer phenomena occurring in the emulsion, bubble and cloud-wake phases.
Bukur, Wittman and Amundson (1974) and Sheplev and
Luss (1979) considered a particulate solid phase in addition to the bubble and emulsion phases, while Bukur and
Amundson (1975) proposed an axial dispersion model to
describe the nonideal #ow behavior in an FBR. Finally,
"rst principles models based on the fundamental conservation equations of mass, momentum and thermal
energy were developed to describe the hydrodynamic
behavior of industrial #uidized-bed reactors (Kuipers,
van Duin, van Beckum & van Swaaij, 1992; van
Wachem, Schouten, Krishna & van den Bleek, 1998).
However, despite the plethora of modeling studies on
conventional FBRs, only a limited number of publications have appeared in the open literature dealing with
the modeling of catalytic gas-phase ole"n polymerization
#uidized-bed reactors. Choi and Ray (1985) developed an
FBR model, based on the concepts of two-phase #uidization. Recently, McAuley et al. (1994) compared the
predictions of the constant bubble size model of Choi and
Ray with those obtained from the solution of a simpler
well-mixed, single-phase model. McAuley et al. (1994)
argued that the di!erences in the predictions of temperature and monomer concentration, obtained by the two
models, were not signi"cant in the operating regime of
industrial #uidized-bed reactors.
One of the most striking features of bubbling #uidized
beds is that portion of the #uidizing gas travels along the
bed in the form of bubbles which grow in size (Bukur,
Nasif & Daly, 1987). Earlier modeling studies on

catalyzed gas-phase ole"n polymerization FBRs (Choi

& Ray, 1985; Talbot, 1990; McAuley et al., 1994) did not
account for the e!ect of varying bubble size in their
models. Choi and Ray (1985) employed a constant mean
bubble size along the reactor bed. On the other hand,
McAuley et al. (1994) suggested the use of Grace (1986)
and Davidson and Harrison (1963) correlations for the
calculation of a maximum stable bubble size in connection with the constant bubble size model of Choi and
Ray. They concluded that the maximum stable bubble
size was a critical reactor parameter for the constant
bubble size FBR model, a!ecting both the steady-state
emulsion temperature and concentration.
In the present study, previous work on the modeling of
gas-phase ole"n polymerization #uidized-bed reactors is
reviewed and extended to account for the e!ect of varying bubble size on the dynamic and steady-state behavior
of FBRs. To predict the bubble size with respect to the
bed height in bubbling #uidized beds of type B solids,
three well-known correlations, namely, the Kato and
Wen (1969), the Rowe (1976) and the Mori and Wen
(1975), are employed. A comparative study of the wellmixed, constant bubble size and bubble-growth models is
carried out to assess the e!ect of the bubble size on the
reactor's dynamic and steady-state operation. To describe the copolymerization of ethylene with 1-butene
over a heterogeneous Ziegler}Natta catalyst, a two-site
copolymerization kinetic scheme is employed. Assuming
that intraparticle and interparticle heat and mass transfer
resistances are negligible, extensive simulations are
carried out to investigate the e!ect of critical reactor
operating parameters (e.g., catalyst feed rate,
monomer/comonomer feed ratio and feed temperature),
on the dynamic and steady-state reactor temperature,
monomer concentration(s), and the molecular weight of
the polyole"n.

3240

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

2. Reaction kinetics
Heterogeneous Ziegler}Natta catalysts usually comprise multiple active sites which lead to the production of
polymers having broad and, often bimodal, molecular
weight and copolymer composition distributions.
Although the role of multiple catalyst active sites in
controlling the molecular weight and compositional developments has long being recognized, it is not yet clear
whether or not the polymerization at di!erent catalyst
active sites follows the same kinetic mechanism (Xie et al.,
1995; McAuley, McGergor & Hamielec, 1990). To account for the observed product heterogeneity, one usually assumes (Chen, 1993) that the values of the kinetic
rate constants (e.g., propagation and termination) can
vary from one site to another.

Table 1
Simpli"ed kinetic mechanism of ole"n copolymerization over Ziegler}Natta catalysts
Description

Reaction

Reaction's
order

Activation
I

By Aluminum
Alkyl (A)

I? PI
SI #[A]P
N


cI
?

IIG PI
PI #[M ]P

G
G
IINGH PI
PI #[M ]P
LG
H
L>H

cI
G
cI
NGH

Propagation
Initiation
Additional units
Deactivation
I

IB  CI #DI
PI P
H
B
L

Spontaneous

cI
B 

Chain transfer

2.1. Molecular species and moment rate equations

Spontaneous

Hutchinson, Chen and Ray (1992) proposed a comprehensive multisite kinetic model for the copolymerization
of ole"ns over heterogeneous Ziegler}Natta catalysts. In
the present study, a simpler two-site, kinetic model is
proposed to describe the molecular and compositional
developments in a catalytic gas-phase ole"n polymerization reactor (Table 1). As can be seen, the polymerization scheme comprises a series of elementary reactions
including site activation, propagation, site deactivation
and chain transfer. To further simplify the kinetic model
developments, lumped rate functions and pseudokinetic
rate constants are introduced (Hutchinson et al., 1992;
Carvalho de, Gloor & Hamielec, 1989; McAuley et al.,
1990).
Following the kinetic developments of Hutchinson
et al. (1992), the rate functions for site activation, deactivation and chain transfer reactions are expressed as
follows:
Site activation:
rI "kI [A]AI? .
?
?
Site deactivation:

(1)

rI "kI (PI )AIB  \.

B
B  H
Chain transfer:

(2)

rI "kI #kI [H]AIR&G #kI [M ].

(3)
RG
R  G
R&G
R+G2
2
All symbols appearing in the above equations are
explained in the nomenclature section.
For multicomponent polymerizations, the use of
pseudokinetic rate constants can considerably simplify
the kinetic rate expressions (Carvalho de et al., 1989;
McAuley et al., 1990). The pseudokinetic rate constants
employed in the present study are summarized in Table 2.
Based on the proposed kinetic mechanism (see Table 1),

By Hydrogen (H )

By Monomer (M )
G

R  G
PI IP
PI #DI
LG

L
IIR&G PI #DI
PI #[H ]P

L
LG

IIR+GH PI #DI
PI #[M ]P
LG
H

L

cI
R  G
cI
R&G
cI
R+GH

one can de"ne the corresponding net rates of production

of `livea and `deada copolymer chains:
Net formation rate of **live++ copolymer chains of length
n with terminal monomer i at the **k++ active site:
RI LG "!rI PI !rI PI
.
B LG
RG LG
K
,
#d(n) kI jI [M ]#kI PI [M ]
R+HG H
G
G 
G
H
,K
#(1!d(n)) kI PI
[M ]
GH L\H
G
H
,K
! kI PI [M ]
(4)
GH LH
H
H
where d(n) is the Kronecker's delta function (e.g., d(n)"1
for n"1 and d(n)"0 for nO1), and PI is the concenLG
tration of `livea copolymer chains of total length n ending with monomer `i a, formed at the `ka catalyst active
site.
Net formation rate of **dead++ copolymer chains of length
n at the **k++ active site:

,K
RI L " (rI PI #rI PI )
(5)
"
B LG
RG LG
G
where DI is the concentration of `deada copolymer
L
chains of total length n, formed at the `ka catalyst active
site.
Similarly, the respective reaction rates of potential,
RI , and vacant, RI  , active sites of type k, will be given

.
by Eqs. (6) and (7).
RI "!SI rI ,

N ?

(6)

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

3241

Table 2
De"nition of the pseudokinetic rate constants
Reaction step

Pseudokinetic rate constant

Propagation

,K ,K
kI " kI
I f
N22
NGH G H
G H
K
,
kI " kI
I
N2H
NGH G
G
,K
kI " kI f
NG2
NGH H
H

Transfer to monomer

,K ,K
kI
" KI
I f
R+22
R+GH G H
G H
K
,
kI " kI
I
R+2H
R+GH G
G
,K
kI " kI f
R+G2
R+GH H
H

Reaction step

Pseudokinetic rate constant

Chain initiation

,K
kI " kI f
2
G G
G

Monomer i mole fraction

[M ]
G
f"
G ,K [M ]
G
G

Live polymer chain fraction at active site type-k

 PI
L LG

I"
G ,  PI
G L LG

,K
,

RI  "rI SI !PI kI [M ]! rI PI .
(7)
.
? N

G
G
RG
LG
G
G L
Based on the kinetic scheme shown in Table 1, the
monomer incorporation rate into the polymer chains
formed at the `ka active site can be expressed as
RI G "[M ][kI PI #(kI #kI )jI ],
+
G G 
R+2G
N2G 
i"1, 2, 2, N .
(8)
K
Accordingly, the total consumption rate of the `i a
monomer will be given by

,Q
,K
(9)
R G "[M ] kI PI # (kI #kI )jI .
G
G 
R+GH
HG H
+
I
H
The overall copolymerization rate will be equal to the
sum of the individual monomer incorporation rates into
the polymer chains, taken over all types of catalyst active
sites:
,K ,Q
R " RI G
N
+
G I
,K
,Q
" [M ] [kI PI #(kI #kI )jI ].
(10)
G
G 
R+2G
N2G 
G
I
For modeling purposes, it is often impractical to formulate an in"nite system of di!erential equations to
describe the conservation of polymer chains of various
lengths. Thus, the method of moments is often used to
reduce the resulting system of macromolecular di!erential balance equations into a lower-order system, which
can easily be solved. The method of moments is based on
the statistical representation of the molecular properties

of the polymer (e.g., M , M ) in terms of the leading

L
U
moments of the molecular weight distribution. Accordingly, one can de"ne the moments of the total number
chain length distributions (TNCLDs) of `livea and
`deada copolymer chains:
,K 
(11)
jI " nJPI ,
LG
J
G L

mI " nJDI
(12)
J
L
L
A `bulka moment which includes the contribution of
the `livea and `deada polymer chains can also be de"ned:
kI "jI #mI .
(13)
J
J
J
Thus, one can obtain the corresponding rate functions
for the moments of the TNCLDs of `livea and `bulka
copolymer chains by multiplying each term of Eqs. (4)
and (5) by nJ and summing up the resulting expressions
over the total variation of n. Following the developments
of Achilias and Kiparissides (1992), the rate equations for
the leading moments of `livea and `bulka TNCLDs are
written as:
**Live++ polymer moments:
]#PI [M ]kI ,
RI  "jI [!rI !rI #[M ]kI
H

B
R2
2 R+22
 2 2
RI  "jI [!rI !rI ]
H

B
R2
#jI [M ](kI
#kI )#kI [M ]PI ,

2 R+22
N22
2
2 
RI  "jI [!rI !rI ]#kI
jI [M ]
H

B
R2
R+22 
2
#[M ]kI [jI #2jI ]#kI [M ]PI ,
2 N22 

2
2 

(14)

(15)

(16)

3242

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

**Bulk++ polymer moments:

RI  "kI
[M ]jI #kI [M ]PI ,
I
R+22 2 
2
2 
RI  "RI  #kI [M ]jI ,
I
I
N22
2 
RI  "RI  #kI [M ][jI #2jI ].
I
I
N22
2 


(17)
(18)
(19)

2.2. Polymer properties

The average polymer properties (e.g., number average
molecular weight, M , weight average molecular weight,
L
M , polydispersity index, PD, and copolymer composiU
tion, U) can be calculated in terms of the polymer mass
fractions, formed at various catalyst active sites, and their
respective `bulka moments.
Thus, the instantaneous copolymer composition,
uI , at the `ka catalyst active site can be calculated by
G 
the ratio of the `i a monomer consumption rate, RI G ,
+
over the sum of the monomer consumption rates at site k.

,K
uI "RI G RI G
(20)
G 
+
+
G
The cumulative copolymer composition, UI, of the
G
polymer chains produced at the `ka catalyst active site
will be given by
UI"kI /kI .
(21)
G
G 
The overall copolymer composition, U , of the polymer
G
chains produced over all catalyst active sites, is accordingly de"ned by

,Q
,Q
U " kI
kI .
(22)
G
G

I
I
The number, xI , and weight average, xI , degrees of
L
U
polymerization of the copolymer chains formed at the
`ka active site, can be calculated in terms of the leading
moments of the respective TNCLD.
xI "kI /kI ,
xI "kI /kI .
(23)
L
 
U
 
The average chain lengths of composite (over all sites)
`bulka polymer are similarly given by
x "k /k ,
x "k /k
(24)
L
 
U
 
where k , k , k are the composite `bulka moments
  
de"ned by
,Q
k " kI .
(25)
J
J
I
Accordingly, one can calculate the corresponding
cumulative number and weight average molecular
weights (MI , MI ) using the following expressions:
L
U
MI "MWI xI
(26)
MI "MWI xI ,
U
L
L
U

where MWI is the average molecular weight of the

repeating monomer units in the copolymer chains
de"ned by
,K
MWI" UI MW
(27)
G
G
G
where MW is the molecular weight of the `i a monomer.
G
Similarly, one can de"ne the overall number average, M ,
L
and weight average molecular weight, M :
U
,Q
,Q
M "x MWI,
M "x MWI.
(28)
L
L
U
U
I
I
Finally, the polydispersity index, PDI, of polymer
chains produced at the `ka active site, and the composite
polydispersity index, PD, will be given by
PDI"MI /MI ,
U L

PD"M /M .
U L

(29)

3. Fluidized-bed reactor modeling

In general, the operation of a catalytic gas-phase ole"n
polymerization #uidized-bed reactor can be approximated with that of a bubbling FBR, shown schematically
in Fig. 1. Bubbling #uidized beds have extensively been
studied over the past forty years and a variety of models
have been proposed to describe their steady-state and
dynamic behavior. In a bubbling FBR, bubbles formed at
or near the gas distributor rise towards the bed's surface.
As they travel upwards, they coalesce forming larger
bubbles, which may then split and recombine. The bubbles contain few particles, but their wakes and induced
drift result in vigorous vertical mixing and some lateral
displacement of the solid particles in the bed (Grace,
1986). Although the inclusion of a cloud-wake phase in
modeling #uidized-bed reactors has been suggested by
many investigators (Kunii & Levenspiel, 1969; El-Halwagi & El-Rifay, 1988; Tabis & Essekkat, 1992; Shiau
& Lin, 1993), the practical importance of such a consideration has not clearly been demonstrated. Thus, in many
cases, a separate cloud-wake phase is not included in the
model (Kato & Wen, 1969; El-Nashaie & Yates, 1973;
Sheplev & Luss, 1979; Werther, 1980; Choi & Ray, 1985;
Talbot, 1990).
Thus, a catalytic gas-phase ole"n polymerization
FBR can be considered to consist of two distinct phases,
namely, the `bubblea and the `emulsiona phase. The
mixing and contacting patterns of the bubble and emulsion phases are very complex and di$cult to characterize, thus, various mixing models have been proposed to
describe the hydrodynamic behavior of two-phase
#uidized-bed reactors. Concerning the #ow characteristics of the bubble phase, assumptions ranging from plug
#ow to perfect mixing have been made, although the
application of the former has more often been cited
(Kunii & Levenspiel, 1969; Bukur et al., 1974; Werther,

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

3243

a two-phase constant bubble size model consisting of

a perfectly mixed emulsion phase and a plug-#ow bubble
phase, to describe the dynamic behavior of the FBR.
More recently, McAuley et al. (1994) developed, as a limited case of the constant bubble size model of Choi and
Ray, a simpli"ed well-mixed model by assuming unrestricted mass and heat transfer between the bubble and
emulsion phases.
In what follows, a uni"ed modeling approach is developed to describe the dynamic behavior of catalytic
gas-phase ole"n polymerization FBRs. Three FBR models (e.g., the well-mixed, the constant bubble size and the
bubble growth) are derived based on the kinetic developments described in the previous section. In addition to
the basic overall dynamic mass and energy conservation
equations, detailed balance equations are derived to describe the molecular and compositional developments in
the FBR.
3.1. The well-mixed model

Fig. 1. Schematic representation of a catalytic gas-phase ole"n polymerization FBR.

1992). On the other hand, the #ow behaviour of the

emulsion phase has been the subject of serious debate
among the various investigators. Bukur et al. (1974) reported that, under perfectly well-mixed conditions of
solids and gas, the #ow pattern of the emulsion phase
(e.g., plug-#ow versus well-mixed) did not a!ect the
model predictions on temperature and concentration for
a non-isothermal gas #uidized-bed catalytic reactor with
continuous circulation of catalyst particles, in agreement
with the results of Kato and Wen (1969).
Fluidized-bed reactor models rely heavily on the use of
semi-empirical and empirical correlations for the calculation of key model parameters, including the minimum
#uidization velocity, the bubble volume fraction, the
bubble size, interphase mass and heat transfer coe$cients, etc. The evaluation of these parameters is crucial
for the accurate simulation of the operation of an industrial FBR. A brief survey of some known correlations
employed for the calculation of important bed properties
is presented in a subsequent section of the present study.
The "rst attempt at modeling the operation of a catalytic gas-phase ole"n polymerization #uidized-bed reactor was made by Choi and Ray (1985). They proposed

In the well-mixed model, the #uidized bed is approximated by a single phase continuous stirred tank reactor
(McAuley et al., 1994). This assumption is valid for small
size bubbles or/and very high interphase mass and heat
transfer rates. Since no bubble phase is included in the
model, the bed voidage, e , accounts for the overall gas


volume fraction in the bed. Assuming uniform temperature and monomer concentration throughout the bed,
the unsteady-state material and energy conservation
equations can be derived. Thus, for the `i a monomer, the
following dynamic molar balance is written:
d[M ]
u
Q [M ]
G "  ( [M ] ![M ] )! 
G
G 
G
dt
He
AHe




(1!e )R G

 +
!
(30)
e


where Q , u , and R G denote the polymer product
 
+
removal rate, the super"cial gas velocity, and the consumption rate of the `i a monomer, respectively. The
dynamic mass balance for the catalyst will be given by
F
Q C

 
!
(31)
(1!e )o
< (1!e )



  




where C , and F denote the catalyst concentration in


the bed and the fresh catalyst feed rate, respectively.
Similarly, the mass balance for the potential active catalyst sites of type k, will be
dC
 "
dt
<

dSI
F SI
Q SI
N"
  N  !RI !
 N
(32)
 < (1!e )
dt
< (1!e )








where RI is the consumption rate of potential active

catalyst sites of type k, given by Eq. (6), and
SI "[Me]AI .
N 
QD

3244

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

The dynamic molar balances for all other species XI,

(e.g., jI , jI , jI , kI , kI , kI , PI ) can be expressed as
      
dXI/dt"RI !Q XI/(< (1!e )).
(33)
V





In order to maintain a constant level in the bed, the
volumetric product removal rate is set equal to the rate of
polymer production. Thus, the steady-state mass balance
of the polymer in the bed will satisfy the following equation:

,K
Q (1!e )o #e MW [M ]


 


G
G
G
,K
"< (1!e ) MW R G .
(34)




G +
G
Finally, the dynamic energy balance equation will be
given by

,K
(1!e )
d

 o C
[M ]C G #
G N+
 N dt
e


G
u
,K
"  [M ] C G ( ! )
G  N+ 

He

 G
Q
,K

!
[M ]C G #o C
(! )
G N+
 N

AHe

 G
,K
u
!  [M ]C G (! )
G N+

He

 G
(1!e ) ,K

 DH
#
R .
(35)
P"LG +G
e

 G
Notice that, in the derivation of the energy equation,
the enthalpy associated with the catalyst feed stream is
considered to be negligible. For the solution of model
Eqs. (30)}(35), one should specify the initial conditions
for all model variables:

[M ] "[M ] ;
G R
G 
C (t"0)"SI (t"0)"XI(t"0)"0 ;

N
T(t"0)" .


(36)

3.2. The constant bubble size model

In the constant bubble size model it is assumed that
the #uidized bed consists of two phases: the emulsion or
dense phase where polymerization takes place, and the
bubble or dilute phase. In the model of Choi and Ray
(1985) the bubbles are assumed to have a constant uniform spherical size, traveling through the bed in plug
#ow at constant velocity. On the other hand, the emulsion phase is considered to be perfectly mixed, interchanging heat and mass with the bubble phase. The
corresponding heat and mass transfer coe$cients are

Fig. 2. The constant bubble size model.

constant throughout the bed. A schematic representation

of the constant bubble size model of Choi and Ray is
illustrated in Fig. 2. Furthermore, mass and heat transfer
resistances between the gas and the solid polymer particles in the emulsion phase are assumed to be negligible.
The last assumption will be valid for su$ciently small
catalyst particles, exhibiting low to moderate polymerization rates (Floyd, 1986).
Due to the low value of the bubble mean residence
time (e.g., less than 5 s), steady-state mass and energy
balances can be written to describe the spatial variation
of the monomer concentration and temperature in the
bubble phase. Assuming that no reaction takes place in
the bubble phase, the molar balance for the `i a monomer
can be written as follows:
d[M ] /dz"K ([M ] ![M ] )/u
G @
@C
G C
G @ @

(37)

where K , and u denote the mass transfer coe$cient

@C
@
between the bubble and emulsion phase and the bubble
rise velocity, respectively.
By integrating the local monomer concentration
[M ] with respect to the bed height, one can calculate
G @
the mean concentration of the `i a monomer in the
bubble phase:

1 &
[M
M ] "
[M ] dh
G @ H
G @

"[M ] #([M ] ![M ] )
G C
G 
G C

u
K H
; @ 1!exp ! @C
K H
u
@C
@



(38)

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Accordingly, the bubble phase energy balance will be

given by
,K
d
H
[M ] C G @ " @C ( ! )
(39)
G @ N+ dz
@
C
u
@
G
where H is the heat transfer coe$cient between the
@C
emulsion and the bubble phase.
The mean temperature in the bubble phase can be
calculated by integrating Eq. (39) over the total bed
height:

1 &
M "
dh
@ H
@


H H
u CM
" #( ! ) @ N 1!exp ! @C
C

C H H
u CM
@C
@ N



 ] C G is the average heat capacity

where CM " ,K [M
G @ N+
N
of the reactingG
monomers.
The dynamic molar balance for the `i a monomer in
the emulsion phase can be written as follows:
d[M ]
u
G C " C ([M ] ![M ] )
G 
G C
H
dt
d K
@ @C
#
([M ] ![M ] )
G @
G C
e (1!d )
KD
@
Q
(1!e )

KD R
!
[M ] !
(41)
G
C
+G
(1!d )AH
e
@
KD
where u , d , e are the emulsion gas velocity, the volC @ KD
ume fraction of bubbles in the bed and the bed voidage at
minimum #uidization conditions, respectively.
Similarly, one can derive the dynamic mass balance for
the catalyst as follows:
F

)(1!d )AHo
KD
@

Q C
 
!
.
(42)
(1!e )(1!d )AH
KD
@
The mass balance for the potential active sites of type
k can be written as
dC
 "
(1!e
dt

dSI
F SI
N"
  N 
dt
< (1!d )(1!e )o
@
@
KD  
Q SI
 N
!RI !
.
(43)
 < (1!d )(1!e )
@
@
KD
The dynamic molar balances for all other species XI in
the emulsion phase (e.g., PI , jI , jI , jI , kI , kI , kI ) can be
      
expressed as
dXI
"RI !Q XI/((1!e )(1!d )AH).
V

KD
@
dt

As in the case of the well-mixed model, the volumetric

product removal rate is set equal to the rate of polymer
production. Thus, the steady-state polymer mass balance
in the bed will be given by

,K
Q (1!e )o #e [M ] MW

KD 
KD
G C
G
G
,K
"AH(1!e ) MW R G .
(45)
KD
G +
G
Finally, the dynamic emulsion phase energy balance
can be written as


(40)

(44)

3245

,K
1!e
d
KD o C
C
[M ] C G #
G C N+
 N dt
e
KD
G
,K
d[M ]
G C ( ! )
"! C G
N+ dt
C

G
u ,K
# C [M ] C G ( ! )
G  N+ 

H
G
u ,K
! C [M ] C G ( ! )
G C N+ C

H
G
d
H
@
@C ( !M )
!
C
@
(1!d ) e
@ KD
Q

(1!e )o C
#
KD  N
AHe (1!d )
KD
@
,K
#e [M ] C G ( ! )
KD
G C N+
C

G
1!e ,K
KD DH
MW R G .
(46)
#
P"LG
G +
e
KD G
Since the reactor operates in an adiabatic mode, the
heat of polymerization is removed via the polymer product stream and the unreacted gas of the emulsion and
bubble phases. To simulate the dynamic operation of
a catalytic gas-phase ole"n polymerization FBR, the
above model Eqs. (37)}(46) must be solved numerically
with the following boundary and initial conditions:

Boundary conditions:
[M ]
"[M ] ; (z"0)
G @X
G 
@

Initial conditions:
[M ]
"[M ] ; (t"0)" ;
G CR
G 
C

C (t"0)"SI (t"0)"XI(t"0)"0.

N

(47)

(48)

3.3. The bubble-growth model

Based on the two-phase #uidization theory, the original constant bubble size model of Choi and Ray (1985)
was extended to account for the varying bubble size with

3246

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

and temperature in the bubble phase. Assuming that no

reaction takes place in the bubbles, the molar balance for
the `i a monomer in the `na compartment can be written
as follows:
[M ] "[1#(K d /u )]\
G @L
@CL @L @L
d
u
K d
; @L\ @L\ [M ]
# @CL @L [M ]
G @L\
G C
d u
u
@L @L
@L
(49)

where d is the bubble size corresponding to the `na

@L
compartment.
The last term in Eq. (49) accounts for the overall mass
transfer of monomer `i a from the bubbles to the emulsion phase. Eq. (49) can be solved explicitly, to calculate
the variation of the monomer concentration in the bubbles along the bed height. Notice that the initial bubble
phase void fraction (d ) and the super"cial velocity
@
(u ) are calculated at the exit of the gas distributor.
@
Accordingly, the energy balance equation for the `na
compartment will be given by

Fig. 3. The bubble-growth model.

respect to the bed's height. The emulsion phase is assumed to be perfectly backmixed, at incipient #uidization
conditions (e "e ). Following the developments of


KD
Kato and Wen (1969), the bubble phase is divided into
`Na well-mixed compartments in series. The size of each
compartment is set equal to the bubble diameter at the
corresponding bed height. Since the bubble size increases
from a minimum value, at the gas distributor, to a maximum stable size as it travels along the bed, the local heat
and mass transfer coe$cients (e.g., H
and K ) be@CL
@CL
tween the bubble and emulsion phases, the local bubble
volume fraction, d , and the bubble rise velocity, u ,
@L
@L
will depend on the bubble diameter and, thus, on the
corresponding bed height. A schematic description of the
bubble-growth model is presented in Fig. 3.
The present model does not account for mass and heat
transfer limitations between the solid particles and the
surrounding gas in the emulsion phase, although these
limitations can become signi"cant for high particle polymerization rates. Based on the above simplifying assumptions, the mass and energy balance equations for the
bubble and emulsion phases are subsequently derived.
As in the case of the constant bubble size model,
steady-state mass and energy balances are derived to
describe the spatial variation of monomer concentration

\
H d
,K
" [M ] C G # @CL @L
G @L N+
@L
u
@L
G
u
d
,K
; @L\ @L\ [M ]
C (
! )
G @L\ N+G @L\

u d
@L @L G
,K
H d
# [M ] C G # @CL @L .
(50)
G @L N+ 
C
u
@L
G
Notice that no heat production term appears in Eq.
(50) since no polymerization occurs in the bubble phase
(e.g., the bubble phase is assumed to be free of solids).
Furthermore, the enthalpy term associated with the
monomer mass transfer from the bubbles to the emulsion
phase will be negligible.
Following the developments of the constant bubble
size model, the emulsion phase is considered to be wellmixed. Thus, the dynamic molar balance for the `i a
monomer in the emulsion phase will satisfy the following
equation:

u
KD
([M ] ![M ] )
G 
G C
(H! , d d )
KD
L @L @L
Q

!
[M ]
G C
A(H! , d d )
L @L @L
, d d K
([M ] ![M ] )
G @L
G C
# L @L @L @CL
e (H! , d d )
KD
L @L @L
1!e
KD R .
!
(51)
+G
e
KD
The third term on the right-hand side of Eq. (51)
accounts for the overall mass transfer of monomer `i a
from the bubbles to the emulsion phase.
d[M ]
G C"
dt
e

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Similarly, one can derive the dynamic mass balance for

the catalyst:
dC
F
Q C
 "

 
!
(52)
dt
< (1!e )o
< (1!e )
C
KD  
C
KD
where < is the emulsion phase volume de"ned by
C
,
< "A H! d d
.
(53)
C
@L @L
L
Accordingly, the mass balance for the potential active
sites of type k can be written as

F SI
Q SI
dSI
  N 
 N
N"
!RI !
(53)

dt
< (1!e )o
< (1!e )
C
KD  
C
KD
where RI is the consumption rate of potential active

catalyst sites of type k, given by Eq. (6), and
SI "[Me]AI .
N 

The dynamic molar balances for all other species XI in
the emulsion phase (e.g., PI , jI , jI , jI , kI , kI , kI ) can be
      
expressed as
dXI/dt"RI !Q XI/(< (1!e )).
(54)
V

C
KD
Assuming that the volumetric product removal rate is
equal to the rate of polymer production, the steady-state
polymer mass balance in the bed will be given by

,K
Q (1!e )o #e [M ] MW

KD 
KD
G C
G
G
,K
"< (1!e ) MW R G .
(55)
C
KD
G +
G
Finally, the dynamic emulsion phase energy balance
can be expressed as

,K
1!e
d
KD o C
C
[M ] C G #
G C N+

N
e
dt
KD
G
,K
d[M ]
G C ( ! )
"! C G
N+ dt
C

G
\
,
u
# KD H! d d
@L
@L
e
KD
L
,K
; C G ([M ] ( ! )![M ] ( ! ))
N+
G  

G C C

G
,
# H d d ( ! )
@CL @L @L @L
C
L
\
,
; e
H! d d
KD
@L @L
L
Q 1!e
,K
KD o C
! 
# [M ] C G
 N
G C N+
<
e
C
KD
G
1!e ,K
KD MW DH
;( ! )#
R .
C

G
P"LG +G
e
KD G
(56)





3247

The third term on the right-hand side of Eq. (56)

represents the enthalpy exchange rate between the
bubble and emulsion phases. Notice that the enthalpies
associated with the catalyst feed stream and monomer transfer from the bubble to the emulsion phase are
negligible.
For the solution of model Eqs. (49)}(56), one should
specify the boundary and initial conditions for all state
variables:
Boundary conditions:
[M ]
"[M ] ,
G @L
G 
Initial conditions:

@L

" .


[M ]
"[M ] ,
(t"0)" ;
G CR
G 
C

C (t"0)"SI (t"0)"XI(t"0)"0.

N

(57)

(58)

4. Estimation of the reactor model parameters

The accurate prediction of all FBR model parameters
(e.g., u , d
, u , H , etc.), is crucial to the design and
KD @  @ @C
mathematical modeling of the reactor. The estimation of
the key bed properties is based on the use of semiempirical and empirical correlations available in the
open literature. These correlations can predict the critical
bed properties, including the minimum #uidization velocity, bubble volume fraction, bubble size, emulsion and
bubble phase gas velocities and mass and heat transfer
coe$cients in terms of the process parameters (e.g., gas
super"cial velocity, average particle size, transport properties of the reactants, etc.).
In what follows, a brief survey of some well-known
correlations, employed for the estimation of the bed
properties in gas-phase catalytic ole"n polymerization
FBRs, is presented. It should be pointed out that these
correlations are strongly dependent on the type of solids
in the bed. According to Geldart classi"cation of solids
(Geldart, 1972), beds of type A, B and C are commonly
encountered in conventional FBRs. In general, gas-phase
catalytic ole"n FBRs will largely contain solids of type B.
4.1. Minimum yuidization conditions
Most correlations employed for the estimation of the
minimum #uidization velocity for isotropic-shaped solids
are variations of the modi"ed Ergun equation. In the
present study, the Lucas, Arnaldos, Casal and Puigjaner
(1986) simpli"ed solution to the Ergun equation for
round Geldart particles of type B, was employed:
Re
"[(29.5)#0.0357Ar]!29.5.
(59)
.KD
Furthermore, it was assumed that, the emulsion phase
remained at minimum #uidization conditions (Bukur,
1974; Kunii & Levenspiel, 1969; Choi & Ray, 1985;

3248

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

El-Halwagi & El-Rifay, 1988; Shiau & Lin, 1993). The

respective value of the emulsion phase voidage, e , can
KD
be estimated by the well-known correlation of Broadhurst and Becker (1975). Unfortunately, this correlation
will be inaccurate for beds containing large size particles,
therefore, a value of 0.5 was assigned to e in all model
KD
simulations (Talbot, 1990; McAuley et al., 1994).

height (Horio, 1987; Hilligardt & Werther, 1987; Choi,

Son & Kim, 1998). It should be noted that most correlations do not take into account the maximum bubble size.
Thus, a maximum bubble size should be used whenever
a bubble size correlation predicts values larger than those
obtained by Eq. (60).
4.3. Bubble rise velocity and bubble volume fraction

4.2. Bubble size

In #uidized beds, bubbles can continuously grow due
to pressure drop and bubble coalescence, till they reach
a maximum bubble size. Above this maximum size, bubbles become unstable and can break up into smaller
bubbles. Davidson and Harrison (1963) postulated that
bubbles can become unstable if their rising velocity, u ,
@
exceeds the terminal velocity of the particles in the bed.
They suggested that the maximum bubble size should be
calculated using the following simple equation:
d
"2u /g
(60)
@ 
2
where u is the terminal velocity of the particles, given by
2
the Haider and Levenspiel (1989) correlation:
u "uH [k o\(o !o )g]
2
2 E E

E
where

(61)

uH "[18(dH)\#(2.335!1.744
)(dH)\ ]\
2
N
Q N
for 0.5(
)1,
(62)
Q
dH"d [k\o (o !o )g].
(63)
N
N E E 
E
Eq. (60) usually leads to conservative estimates of the
maximum stable bubble size. Grace (1986) suggested the
use of a correction factor of 2.7 for the particle size (e.g.,
d "2.7d ), in Eq. (63). As a result, larger values of the
N
N
maximum stable bubble size can be obtained.
In general, the bubble size will vary with respect to bed
height. Three of the most common correlations, used for
the calculation of bubble size with respect to bed height,
are given in Table 3. Recently, new expressions were
proposed to describe the bubble size variation with bed

Based on the two-phase #uidization theory, Davidson

and Harrison (1963) proposed the following widely used
correlation for the calculation of the bubble rise velocity:
u "u !u #0.711(gd ).
(64)
@

KD
@
Since u depends on the bubble size, d , it will vary
@
@
with the bed height. It should be noted that the bubble
rise velocity will also depend on the bed diameter, D .


That is, a bubble will travel faster in larger diameter beds,
due to large-scale mixing patterns leading to acceleration
of the bubble swarms (Werther, 1983). Werther suggested
the use of the following alternative correlation to account
for the bed diameter:
u "u !u #u(gd ).
@

KD
@
For type-B solids, u is de"ned as follows:
u"0.64

(65)

for D

)0.1 m,


u"1.6D  for 0.1(D )1 m,




u"1.6
for D '1 m.


According to Shiau and Lin (1991) correlations based
on the two-phase #uidization theory tend to overpredict
the bubble rise velocity. Moreover, Kunii and Levenspiel
(1991) showed that for u u , u predictions obtained

KD @
by Eq. (64) can signi"cantly deviate from experimental
observations for both A and B type of Geldart beds.
Table 4 shows four well-known correlations employed
for the prediction of the bubble phase volume fraction
(Kunii & Levenspiel, 1991) in terms of the super"cial gas
velocity, the bubble rise velocity and the minimum #uidization velocity.

Table 3
Bubble size correlations used in the present study
Reference

Correlation

Initial value

Kato and Wen (1969)

d "1.4o d (u /u )h#d
@
. .  KD
@

d "[6(u !u )/nn ] g\ 

@

KD

(perforated plate)

Mori and Wen (1975)

d
!d
@ 
@ "exp (!0.3h/D )


d
!d
@ 
@

d "0.347[A(u !u )/n ] 
@

KD 
(perforated plate)
d "0.00376(u !u )
@

KD
(porous plate)

Rowe (1976)

d "(u !u )(h#h )g\

@

KD


h
d

@

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

3249

Table 4
Estimation of the bubble phase volume fraction (Kunii & Levenspiel, 1991)
Bubble volume fraction
u !u
KD
d " 
@ u #2u
@
KD
u !u

KD
d " u@ #uKD
@
u !u

KD
u
@
u !u
KD
d " 
@ u !u
@
KD
u
d " 
@ u
@

when u
u /e
@
KD KD

Bubble velocity

Applicability

Slow

u (u
@
C

Medium

5u
u
KD (u ( KD
@
e
e
KD
KD

Fast

5u
u ' KD
@
e
KD

Vigorous bubbling

u u

KD

when u
5u /e
@
KD KD

Table 5
Common correlations employed for the calculation of mass and heat transfer coe$cients
Reference

Mass transfer coe$cients (s\)

Davidson and Harrison (1963)

Kunii and Levenspiel (1969)

Sit and Grace (1981)

Peters, Fan and Sweeny (1982)

Note: K

@A








g 
K
K "0.975D
@C
@A
E d
@
u
Dg
K "4.5 KD #5.85 E
@AL
d
d
@L
@L
D e u

K "6.77 E KD @L
ACL
d
@L







u
4D e u 
E KD @
K " KD #
@C
3
pd
@
u
K "2 KD
@A
d
@
D e u 
K "12 E KD @
AC
pd
@

Heat transfer coe$cients (cal/cm bubble s K)



g 
H
H "0.975 (o C k )
@C
@A
E NE E
d
@
u o C
(k o C )g
H "4.5 KD E NE #5.85 E E NE
@AL
d
d
@L
@L
e u

H "6.77 (o C k ) KD @L
ACL
E NE E
d
@L





o C u
4o C k e u
E NE E KD @
H " E NE KD #
@C
3
pd
@
u o C
H "2 KD E NE
@A
d
@
e u 
H "12(k o C ) KD @
AC
E E NE
pd
@

and K are in cm/s. H and H are in cal/cm bubble s K.

@C
@A
@C

4.4. Mass and heat transfer coezcients

In bubbling #uidized beds, bubbles exchange mass and
heat with the emulsion phase. Kunii and Levenspiel
(1969) assumed that mass is transferred from the bubbles
to the surrounding clouds and from the clouds to the
emulsion phase. For exothermic reactions, heat is transferred from the emulsion phase to the bubble phase by
means of the cloud region. Following the developments
of Kunii and Levenspiel (1969), one can de"ne the following overall mass and heat transfer coe$cients:
K "(1/K #1/K )\,
@C
@A
AC

(67)

H "(1/H #1/H )\,

@C
@A
AC

(68)

where the subscripts be, bc and ce denote the mass and

heat interchange processes between the bubble and emulsion, the bubble and the cloud and the cloud and emulsion phases. Table 5 summarizes some well-known heat
and mass interchange correlations used in the present
study.
Since the catalytic ole"n polymerization in an FBR is
characterized by extremely low conversions (e.g., 2}5%
per pass), the rate of mass transfer between the emulsion
and the bubble phase will not signi"cantly a!ect the
dynamic behavior of the reactor and the overall properties of the polyole"n. Actually, as will become apparent in
the discussion section, the mass transfer term, accounting
for the monomer transfer from the bubbles to the emulsion phase can be set equal to zero for typical industrial
operating conditions.

3250

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

velocity, monomer feed molar ratio, feed stream temperature, etc.) on the reactor temperature, monomer conversion and the molecular properties of the polyole"n.
Furthermore, comparative simulation studies were carried out using the well-mixed, constant bubble size and
bubble-growth models, in order to investigate the e!ect
of the mixing conditions on the dynamic and steady-state
behavior of commercial ole"n polymerization FBRs (see
Table 6). It should be pointed out that a constant average
particle size was assumed in the simulations following the
developments of Choi and Ray (1985) and McAuley et al.
(1994). The nominal operating conditions, the physical
and transport properties of the reaction mixture used in
all simulation studies, are reported in Table 7. The numerical values of the kinetic rate constants appearing in
Eqs. (1)}(10) and (14)}(19) are given in Table 8. It should
be noted that in the various model comparison simulations (e.g., well-mixed, constant bubble size and bubble
growth), the same average bed voidage value was used.
However, since the bubble gas holdup de"nition is di!erent for each model, the bubble phase volumes of the
well-mixed and constant bubble size models were appropriately adjusted so that the bed height expansion for all
three models remained the same. Accordingly, for the
constant bubble size model, an e!ective maximum

4.5. Particle size

The average particle size is an important process variable which is used in the calculation of several key properties of the #uidized bed (e.g., minimum #uidization
velocity, bubble size). Therefore, variations in the average
particle size should be accounted for in an FBR model in
order to obtain an accurate description of the dynamic
behavior of a catalytic ole"n polymerization FBR
(Hatzantonis & Kiparissides, 1998). To predict the size
distribution of the polymer particles in the bed, a particle
population balance should be simultaneously solved together with the above FBR model equations to obtain
a more accurate description of the dynamic and steadystate behavior of the reactor. This problem is the subject
of a subsequent publication.

5. Simulation results and discussion

To demonstrate the predictive capabilities of the
bubble-growth model, extensive simulations were carried
out in order to assess the relative e!ects of the main
process parameters (e.g., catalyst feed rate, super"cial gas

Table 6
Correlations used in the constant bubble size and bubble-growth models
Physical parameter

Theoretical or empirical expression

Reference

Minimum #uidization velocity

Re
"[(29.5)#0.0357Ar]!29.5
.KD
d
"2u /g
@ 
2
u "u !u #0.711(gd )
@L

KD
@L

Lucas, Arnaldos and Casal (1986)

Bubble phase volume fraction

u !u
KD
d " 
@L
u
@L

Kunii and Levenspiel (1991)

Emulsion gas velocity

u "
CL e

Maximum stable bubble size

Bubble rise velocity

u
KD
(1!d )
KD
@L






Heat transfer coe$cients

H "4.5
@AL


Kunii and Levenspiel (1969)

D e u

E KD @L
d
@L

K "6.77
ACL

Davidson and Harrison (1963)

Bukur et al. (1974)

u
Dg
K "4.5 KD #5.85 E
@AL
d
d
@L
@L
Mass transfer coe$cients

Grace (1986)

u o C
(k o C )g
KD E NE #5.85 E E NE
d
d
@L
@L

e u

H "6.77( o C k ) KD @L
ACL
E NE E
d
@L
For the constant bubble size model n"1; for the bubble-growth model, n"1,2N'1.

Kunii and Levenspiel (1969)

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

bubble size was calculated using the following equation:


2
H
KD (u !u )
d
"

KD
@   g H!H
KD
(69)
,
(H!H )" d d .
KD
@L @L
L
Eq. (69) can be derived by substituting the bubble rise
velocity (Eq. (64)), and the bubble phase volume fraction
(second correlation in Table 4), into the following height
expansion equation:
H"H /(1!d ).
(70)
KD
@
On the other hand, the average bed voidage of the
well-mixed model, was expressed in terms of the bubble
Table 7
Nominal operating conditions and numerical values of the physical and
transport properties of the reaction mixture
Reactor parameters

Physical parameters

H (cm)"600
D
(cm) "250


(K)"353.15

(K) "320

F (g/s) "5 ) 10\

[M ] (mol/l) "0.652
 
[M ] (mol/l) "0.13
 

k (g/cm/s)"1.14;10\
E
o (g/cm)"0.024
E
o (g/cm)"0.905

o (g/cm)"2.84

C (cal/g/K)"0.425
NE
C
(cal/g/K)"0.96
N
D (cm/s)"0.004
E
k (cal/cm/s/K)"7.6;10\
E
DH
(cal/g)"!916
P"L
d (cm)"0.05
N
d
(cm)"20
@ 

3251

gas holdup and the minimum #uidization voidage of the

constant bubble size model, according to the following
equation:
e "
"d #(1!d )e "
.
(71)

 U 
@
@ KD U 
Integration of the dynamic model equations was performed by means of the di!erential equation solver
DGEAR, while steady-state solutions of the model equations were obtained by means of the nonlinear algebraic
equation solver PITCON (Rheinboldt & Burkardt,
1991).
For the case of the constant bubble size model, the bed
properties were calculated using an e!ective maximum
bubble size, Eq. (60). On the other hand, for the bubblegrowth model, the bubble size and, thus, the corresponding height of each compartment, were calculated using
either the linear correlation of Kato and Wen (1969) or
the nonlinear correlations of Mori and Wen (1975) and
Rowe (1976). The respective discretized forms of the
bubble size correlations, shown in Table 3, can be obtained by replacing the bed height, h, by the following
discrete bed height equation:
L\
1
(72)
h " d # d , n'1.
L
@G 2 @L
G
In what follows, the e!ect of important reactor parameters (e.g., super"cial gas velocity, maximum stable
bubble size, mean particle size, catalyst injection rate,
monomer/comonomer feed ratio and temperature in the
feed stream), on the dynamic and steady-state behavior of
the bubble-growth FBR model is investigated. Finally,

Table 8
Numerical values of the kinetic rate constants
Rate constant (cm/mol/s)

Site type

Activation energy (kcal/mol)

Activation
kI
?
EI
?

10
8

10
8

Initiation
kI

EI

KI

EI


4.2;10
9
4900
9

1.6;10
9
160
9

Deactivation
kI
 
EI
 

Units in 1/s

0.001
8

0.001
8

Rate constant (cm/mol/s)

Site type

Activation energy (kcal/mol)

Propagation
kI
N
EI
N
kI
N
EI
N
kI
N
EI
N
kI
N
EI
N

8.26;10
9
8.26;10
9
1.2;10
9
1.2;10
9

5.2;10
9
4200
9
2.09;10
9
279
9

Chain transfer
kI
R  G
EI
R  G
kI
R&G
EI
R&G
kI
R+GH
EI
R+GH

0.0012
8
0.0012
8
0.0012
8

0.0012
8
0.0012
8
0.0012
8

3252

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Fig. 4. E!ect of catalyst feed step changes on (a) the emulsion phase
temperature and (b) emulsion phase ethylene concentration
(*F (g/s)" * 0.004, #0.007, 0.01).


Fig. 5. E!ect of catalyst feed step changes on (a) the weight average and
(b) number average molecular weight (*F (g/s) " * 0.004, #0.007,

0.01).

the dynamic and steady-state behavior of the bubblegrowth model is compared with those of the well-mixed
and constant bubble size models.
5.1. Ewect of catalyst feed rate
Figs. 4 and 5 illustrate the e!ect of step changes in
the catalyst feed rate on the dynamic behavior of the
bubble-growth model. Speci"cally, Fig. 4a shows the
e!ect of catalyst feed step changes on the emulsion phase
temperature. The initial catalyst feed rate is assumed to
be equal to 0.005 g/s. As can be seen, the catalyst feed rate

Fig. 6. Steady-state spatial variation of the bubble, emulsion and average bed temperatures (Note: Total bed height is 6 m), u "5u (

KD
bubble phase, * emulsion phase, * average bed temperature).

strongly a!ects the emulsion phase temperature. When

the catalyst feed rate increases, the temperature is increased too due to the higher polymerization rate. Notice
that for large step changes in the catalyst feed rate, the
temperature response exhibits an oscillatory behavior.
On the other hand, the ethylene consumption does not
signi"cantly increase, due to the low single-pass monomer conversions achieved in commercial ole"n polymerization FBRs. Fig. 5 depicts the e!ect of step changes
in the catalyst feed on the number and weight average
molecular weights of the polyole"n. It is clear that molecular developments are less sensitive to changes in the
catalyst feed.
Fig. 6 shows the steady-state spatial variation of the
bubble, emulsion and average bed temperatures in the
FBR, for two di!erent catalyst feed rates, using the Kato
and Wen (1969) bubble growth correlation. Notice that
the bed heatup occurs practically within the "rst
40}50 cm of the total bed height (e.g., 6 m). After this
initial heatup period, the temperatures in the two phases
remain the same. As can be seen, the di!erence between
the bubble and emulsion phase temperature becomes
signi"cant near the gas distributor. Notice that as the
catalyst feed rate increases, the temperature di!erence
near the distributor, increases too. Thus, for a catalyst
feed rate of 0.015 g/s, temperature di!erences as high as
153C are predicted by the variable bubble-growth model.
5.2. Ewect of monomer molar feed ratio
In a product grade transition, a step change in the
monomer molar feed ratio is usually introduced into the

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Fig. 7. E!ect of step changes in the monomer molar feed ratio on (a) the
emulsion-phase temperature and (b) emulsion phase ethylene concentration ([M ] /[M ] : * [1/5P1/2], # [1/5P1]).
 
 

3253

Fig. 9. E!ect of step changes in the monomer molar feed ratio on (a) the
ethylene mole fraction and (b) butene mole fraction in polymer
([M ] /[M ] : * [1/5P1/2], # [1/5P1]).
 
 

molar ratio increases. This is expected since ethylene is

more reactive than butene (e.g., the ethylene propagation
rate constant is larger than that of butene, see Table 8). It
should be pointed out that when the monomer feed ratio
changes from (1/5) to (1/1) the model predicts a temperature overshoot of about 73C, which might lead to some
particle agglomeration problems.
Figs. 8 and 9 depict the e!ect of molar feed ratio step
changes on the average molecular weights and the
copolymer composition respectively. Both molecular
weight and copolymer composition are signi"cantly affected during such transitions. Notice that as the ethylene
to butene ratio increases the ethylene content in the
copolymer increases as well as the number and weight
average molecular weights.
5.3. Ewect of superxcial gas velocity
Fig. 8. E!ect of step changes in the monomer molar feed ratio on (a) the
weight average and (b) number average molecular weight of the polymer produced ([M ] /[M ] : * [1/5P1/2], # [1/5P1]).
 
 

FBR. Bubble-growth model simulations were carried out

in order to assess the impact of step changes in the
monomer feed ratio on the reactor dynamics (Figs. 7}9).
In all cases, the total feed monomer concentration was
kept constant (e.g, 0.782 mol/l), while the ethylene to
butene molar feed ratio increased from (1/5) to (1/2) and
(1/1). Fig. 7 illustrates the e!ect of two step changes in the
monomer feed ratio, on the emulsion phase temperature
and ethylene concentration. As can be seen, the emulsion
phase temperature increases when the ethylene to butene

Super"cial gas velocity is an important process parameter since it is directly related to the heat removal rate
from the reactor. Fig. 10 illustrates the e!ect of super"cial
gas velocity on the steady-state emulsion phase temperature and ethylene concentration. As can be seen, the safe
catalyst feed rate considerably increases as the super"cial
gas velocity increases. This means that the reactor can be
operated over a wider range of catalyst feed rates without
the risk of polymer melt-down. On the other hand, an
increase in the super"cial gas velocity results in a decrease of the monomer conversion since the monomer
mean residence time decreases. In addition, an increase in
the super"cial gas velocity might result in an increase of
the particle elutriation rate with concominant the contamination of the recycle equipment.

3254

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Fig. 10. E!ect of super"cial gas velocity on (a) the emulsion phase
temperature and (b) emulsion phase ethylene concentration (u /u "
 KD
* 7, #5, 4, * 3).

Fig. 12. E!ect of maximum bubble size on (a) the emulsion phase
temperature and (b) emulsion phase ethylene concentration (d
(cm)
@ 
" * 40, #30, 20, * 15).

5.4. Ewect of the bubble size

Fig. 11. E!ect of super"cial gas velocity on the temperature di!erence

between the emulsion and bubble phase calculated near the bed distributor (u /u " * 7, #5, 4, * 3).
 KD

Fig. 11 depicts the e!ect of super"cial gas velocity on

the steady-state temperature di!erence between the
bubble and emulsion phase near the bed distributor. As
can be seen, the temperature di!erence can take values
up to 403C, depending on the catalyst feed rate and the
super"cial gas velocity. Although not shown here, the
corresponding interphase monomer concentration gradients (e.g., between the bubble and emulsion phase) are
less than 1%.

For the operating conditions of Table 7, the Davidson}Harrison correlation predicts a maximum bubble
size of approximately 20 cm. However, this "gure should
be taken with caution since the maximum bubble diameter strongly depends on the type of the #uidized solids
as well as the #uidization mode (Grace, 1986; Doraiswamy & Sharma, 1984). Fig. 12, shows the e!ect of the
maximum bubble diameter on the steady-state model
predictions of temperature and ethylene concentration. It
can be seen that the e!ect of the maximum bubble diameter (e.g., 15, 20, 30, 40 cm) does not signi"cantly a!ect
the steady-state temperature and ethylene concentration
predictions up to a catalyst feed rate of 0.02 g/s. In
contrast to the "ndings of McAuley et al. (1994), bubblegrowth model simulations have shown that the maximum bubble size is not a critical system parameter.
Assuming that the total gas volume of the bubbles leaving the distributor remains constant, small size bubbles
will exhibit higher heat transfer rates than large bubbles,
due to their larger interphase area.
Fig. 13 illustrates the e!ect of various bubble growth
correlations on the unsteady-state emulsion temperature
for di!erent catalyst feed rates. Notice that the e!ect of
the selected bubble-growth correlation on the prediction
of the emulsion temperature is not signi"cant.
5.5. Ewect of average particle size
Fig. 14 illustrates the e!ect of the average particle size
on the steady-state emulsion phase temperature and

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Fig. 13. Prediction of emulsion phase temperature using di!erent

bubble-growth correlations: (a) F "0.005 g/s, (b) F "0.018 g/s


(# Kato & Wen, 1969; * Rowe, 1976; Mori & Wen, 1975).

3255

Fig. 15. E!ect of mass transfer coe$cient K on the prediction of

@C
emulsion phase temperature (* K "0; * Kunii & Levenspiel, 1969;
@C
Sit & Grace, 1981 u "4u ).

KD

This means that the super"cial gas velocity must increase

in order to maintain the ratio u /u
constant.
 KD
For example, when the average particle size increases
from 300 to 1500 lm, the minimum #uidization velocity
as well as the super"cial gas velocity increase by a factor
of 4.
Thus, FBRs producing small size polymer particles
will operate within a narrow safe catalyst feed range. On
the other hand, FBRs containing large size particles will
have a wider safe operation window but will exhibit
higher operational costs and lower monomer conversions due to increased super"cial gas velocities.

5.6. Ewect of mass transfer coezcient

Fig. 14. E!ect of average particle size on (a) the emulsion phase temperature and (b) emulsion phase ethylene concentration (d (lm)
N
" * 1500, #1000, 500, * 300).

ethylene concentration. It can be seen that the ethylene

concentration as well as the emulsion phase temperature
signi"cantly vary with the average particle size. It should
be noted that the results of Fig. 14 are similar to those of
Fig. 10, showing the e!ect of super"cial gas velocity on
the steady-state FBR reactor behavior. The similarity in
the results of Figs. 14 and 10 can be explained by noticing
that an increase in the average particle size results in
an increase in the minimum #uidization velocity.

Dynamic bubble-growth model simulations were conducted in order to assess the relative importance of the
monomer mass transfer from the bubbles to the emulsion
phase. The simulation results are depicted in Fig. 15. Two
well-known correlations, namely, the Kunii and Levenspiel (1969) and the Sit and Grace (1981) correlation were
employed to calculate the mass transfer coe$cient K . It
@C
can clearly be seen that in all cases, including the case of
zero mass transfer (e.g., K "0), the prediction of the
@C
emulsion phase temperature is independent of the value
of the mass transfer coe$cient. The results of Fig. 15 can
be explained by the fact that the polymerization rate is
not limited by the monomer mass transfer rate due to
the low single pass monomer conversion obtained in
commercial FBRs.

3256

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Fig. 16. E!ect of a catalyst feed step change on emulsion-phase temperature predicted by the three models (*F "0.005 g/s, * well-mixed,

# constant bubble size, bubble-growth).

Fig. 17. E!ect of a catalyst feed step change on (a) the weight average
and (b) number average molecular weight predicted by the three models
(*F "0.005 g/s, * well-mixed, # constant bubble size, bubble
growth).

5.7. Comparison of the well-mixed, constant bubble size

and bubble-growth models
Fig. 16 depicts the e!ect of a step change in the catalyst
feed on the emulsion phase temperature responses calculated by the three models. It can be seen that the
bubble-growth emulsion temperature lies between the
temperatures predicted by the other two models and, in
fact, it is closer to the response of the well-mixed model.
Notice that, the constant bubble size model shows an
oscillatory behavior, while the steady-state temperature
is about 103C larger than that predicted by the bubblegrowth model. Fig. 17 illustrates the e!ect of a catalyst
feed step change on the number and weight average
molecular weights of the polyole"n. Again, the constant
bubble size model overpredicts the average molecular
weights in comparison to the predictions of the bubble
growth model.
The e!ect of a step change in the monomer feed molar
ratio (e.g., from 1/5 to 1/2) on the emulsion phase temperature predicted by the three models, is presented in
Fig. 18. Notice that the total feed monomer concentration is kept constant during the grade transition. As can
be seen, the bubble-growth model temperature prediction clearly lies between the responses obtained by the
other two models and, once more, it is closer to the
well-mixed model response. On the other hand, the number and weight average molecular weight predictions,
calculated by the three models do not deviate signi"cantly.
Fig. 19 illustrates the e!ect of super"cial gas velocity
on the steady-state emulsion phase temperature pre-

Fig. 18. E!ect of step changes in the monomer molar feed ratio on the
emulsion phase temperature predicted by the three models
([M ] /[M ] : 1/5P1/2; * well-mixed; # constant bubble size;
 
 
bubble-growth).

dicted by the three models. In all cases, the safe operation

window is considerably narrowed when the super"cial
gas velocity decreases. Notice that at u /u "5, the
 KD
bubble-growth model predictions are closer to those obtained by the well-mixed model. Fig. 20 illustrates the
e!ect of super"cial gas velocity on the constant bubble
size and bubble-growth model predictions of the temperature di!erence between the emulsion and bubble phase

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

Fig. 19. E!ect of super"cial gas velocity on steady-state emulsion

temperature model predictions (u "5u , # well-mixed, constant

KD
bubble size, * bubble-growth; u "7u , well-mixed, constant

KD
bubble size, bubble-growth).

3257

Fig. 21. E!ect of maximum bubble size on steady-state emulsion phase

temperature predictions (d
"20 cm, * constant bubble size,
@ 
bubble-growth; d
"40 cm, constant bubble size, bubble@ 
growth).

bubble-growth models. It is obvious that considerable

disagreement exists between the two models. However,
the impact of the maximum bubble size on the bubblegrowth model temperature predictions is signi"cantly
smaller than that calculated for the constant bubble size
model. Moreover, the safe operation window (e.g., safe
range of variation of catalyst feed rate) calculated by
the bubble-growth model is wider than that obtained by
the constant bubble size model. Notice that in the case of
d
"40 cm, the constant bubble size model predicts
@ 
a very sharp increase of the emulsion temperature
(e.g., above 380 K), even at low catalyst feed rates (e.g.,
0.006 g/s), whereas the bubble-growth model temperature predictions for the same catalyst feed rate are well
below the maximum safe bed operation temperature.

Fig. 20. E!ect of super"cial gas velocity on the steady-state temperature di!erence between the bubble and emulsion phase (u "5u ,

KD
# constant bubble size, bubble-growth; u "7u , constant

KD
bubble size, bubble-growth).

near the distributor. As can be seen, at relatively low

catalyst feed rates (e.g., (0.02 g/s), the temperature differences calculated by the two models do not signi"cantly
vary. On the other hand, at high catalyst feed rates,
signi"cant deviations exist.
Finally, Fig. 21 illustrates the e!ect of maximum
bubble size on the steady-state emulsion phase temperature predicted by the constant bubble size and

6. Conclusions
In the present study, recent developments in modeling
catalyzed gas-phase ole"n polymerization #uidized bed
reactors were critically reviewed. A new FBR model (e.g.,
the bubble-growth model) was developed to account
for the e!ect of varying bubble size with the bed height on
the reactor dynamics and the molecular properties of
the polymer product. Comparative simulation studies
were carried out between the well-mixed, constant bubble
size and bubble-growth models in order to investigate the
e!ect of the mixing conditions and bubble size variation
on the operational behavior of commercial ole"n polymerization FBRs. It was found that the maximum stable

3258

H. Hatzantonis et al. / Chemical Engineering Science 55 (2000) 3237}3259

bubble size, a critical constant bubble size model parameter, has a considerably smaller impact on the predictions of the bubble-growth model, regardless of the
bubble growth correlation used. It was shown that since
the bubble-growth model assumes a more realistic
bubble-phase mixing pattern, improved emulsion-tobubble heat transfer rates are obtained, and, thus, the
maximum stable bubble size does not signi"cantly a!ect
the emulsion temperature predictions. Finally, it was
shown that the mass transfer rate from bubbles to the
emulsion phase did not a!ect the dynamic behavior of
the FBR.
The well-mixed and constant bubble size models were
found to be limiting cases of the bubble-growth model.
The constant bubble size model was found to overpredict
the emulsion phase temperature, ethylene conversion and
average molecular weights. Furthermore, the constant
bubble size model predicted a narrower safe operation
window compared to that calculated by the bubblegrowth model. On the other hand, the well-mixed and
bubble-growth model predictions were in better agreement under typical operating conditions of commercial
interest. The e!ect of the particle size on the dynamic
behavior of the reactor was not considered although it
was shown that it is an important reactor parameter.
This is the subject of a follow-up publication.

Acknowledgements
The authors gratefully acknowledge the DGXII of EU
for supporting this work under the BRTTE/EURAM
Project BE96-3022.

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