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Chemical Engineering Science 61 (2006) 3997 4006

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Two-phase modeling of a gas phase polyethylene uidized bed reactor


Ali Kiashemshaki, Navid Mostou , Rahmat Sotudeh-Gharebagh
Department of Chemical Engineering, Process Design and Simulation Research Center, Faculty of Engineering, University of Tehran,
P.O. Box 11365/4563, Tehran, Iran
Received 13 February 2005; received in revised form 28 December 2005; accepted 27 January 2006
Available online 20 March 2006

Abstract
A two-phase model is proposed for describing the behavior of a uidized bed reactor used for polyethylene production. In the proposed
model, the bed is divided into several sequential sections where ow of the gas is considered to be plug ow through the bubbles and perfectly
mixed through the emulsion phase. Polymerization reactions occur not only in the emulsion phase but also in the bubble phase. Voidages of
the emulsion and bubble phases are estimated from the dynamic two phase structure hydrodynamic model. The kinetic model employed in this
study is based on the moment equations. The hydrodynamic and kinetic models are combined in order to develop a comprehensive model for
gas-phase polyethylene reactor. The results of the model are compared with the experimental data in terms of molecular weight distribution
and polydispersity of the produced polymer. A good agreement is observed between the model predictions and actual plant data. It has been
shown that about 20% of the polymer is produced inside the bubble phase and as such cannot be neglected in modeling such reactors.
2006 Elsevier Ltd. All rights reserved.
Keywords: Polyethylene; Fluidization; Modeling; Hydrodynamics; Gel permeassion chromatography; Molecular weight distribution

1. Introduction
Gassolid uidized bed reactors have a wide range of industrial applications. Production of linear low density polyethylene
(LLDPE) and high density polyethylene (HDPE) using heterogeneous ZeiglerNatta catalysts are example of an industrial
application of uidized beds reactors. Gas-phase polymerization of ethylene in a uidized bed has several advantages over
both high pressure and slurry polymerization techniques due to
lower operating pressure and temperatures, no need to solvent
and better heat removal, compared to the other polyethylene
production processes. Industrial polyolen uidized bed reactors typically operate at temperature range of 75110 C and
pressure of 2040 bar (Xie et al., 1994). The supercial gas
velocity can vary from 3 to 8 times the minimum uidization
velocity.
Several models have been proposed to describe the performance of gas-phase ethylene polymerization reactors. The
uidized bed reactors in this process have been modeled as
Corresponding author. Tel.: +98 21 696 7781; fax: +98 21 646 1024.

E-mail address: mostou@ut.ac.ir (N. Mostou).


0009-2509/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2006.01.042

single-, two- or three-phase reactors (Choi and Ray, 1985;


McAuley et al., 1994; Fernandez and Lona, 2001). In all of
these models, it was assumed that the reactions take place only
in the emulsion phase due to the assumption that the bubbles are
solid-free. McAuley et al. (1994) considered the polymerization reactor to be a well-mixed reactor (or continuously stirred
tank reactor, CSTR). Choi and Ray (1985) divided the reactor
into two sections: emulsion phase and bubble phase. Fernandez
and Lona (2001) assumed a heterogeneous three-phase model
(i.e., gas in bubble, gas in emulsion and solid polymer particles) where plug ow was assumed for all phases. Hatzantonis
et al. (2000) considered the effect of varying bubble size on the
dynamic and steady state behavior of reactor. They divided the
reactor into two sections: emulsion phase and bubble phase.
They also assumed that the emulsion phase is perfectly mixed
while the bubble phase was divided into N well-mixed compartments in series. In their model, the size of each compartment was set equal to the bubble diameter at the corresponding bed height. Recently, Alizadeh et al. (2004) developed a
pseudo-homogeneous model for predicting the performance
of an industrial-scale gas-phase polyethylene production reactor. They employed a tanks-in-series model to represent the

3998

A. Kiashemshaki et al. / Chemical Engineering Science 61 (2006) 3997 4006

ethylene polymerization reactor. Kiashemshaki et al. (2004)


adopted the model of Alizadeh et al. (2004) and provided correlations for estimating the properties of the polymer product,
such as melt index and density, from the operating conditions
of the reactor.
In the present study, a uidized bed for polyethylene production is divided into several segments, according to the procedure proposed by Jafari et al. (2004). Each segment of the bed
consists of two phases, i.e., emulsion phase and bubble phase
and the reaction is considered to progress in both phases. The
bubble phase ow pattern is assumed to be plug ow while
the emulsion phase is considered to be completely mixed. This
model has the privilege of being a two-phase model with the
reactions considered to take place in both phases.
2. Reactor modeling
A simplied ow diagram of gas-phase polyethylene production process is shown in Fig. 1. As shown in this gure, the catalyst is fed into the reactor as pre-polymer, which
is the catalyst coated with a thin layer of the polymer. Prepolymer particles are continuously fed into the reactor at top
and react with the incoming uidizing reaction medium (i.e.,
monomers and hydrogen) to produce a broad distribution of
polymer particles. The polyethylene product is continuously
withdrawn from the reactor at a point above the gas distributor and preferably close to the bottom of the bed. Unreacted
gases together with ne particles enter into the disengaging
zone where separation of solids from the gas is facilitated.
This gas then enters a cyclone in order to separate the remainder of particles. The solid-free gas is subsequently combined with fresh feed stream after heat removal in the heat
Recycle Stream

exchanger and recycled back to the base of the reactor. The


single-pass monomer conversion in the reactor can vary from
2 to 5%, whereas, the overall monomer conversion may be as
high as 98% (Xie et al., 1994).
2.1. Kinetics
In the present study, a comprehensive mechanism is considered to describe the copolymerization kinetics of ethylene and
1-butene over a ZieglerNatta catalyst with two different catalyst sites based on the kinetic model proposed by McAuley et
al. (1990). Rates of formation, initiation, propagation and chain
transfer are different for each type of site. This mechanism is
comprised of series and parallel elementary reactions listed in
Table 1. Reactions with poisons are neglected in the present
work.
Characterization of polymer properties is modeled using the
method of moments. The moment equations are given in Table
2. Application of the method of moments allows for the prediction of the physiochemical characteristics of the polymer
such as molecular weight, polydispersity, branching frequency,
density and melt index, as well as other useful information of
the system such as polymer production rate, monomer conversion and active site information. Once the moment equations
are solved, the rate of reaction for each component, assuming
the monomers are mainly consumed through the propagation
reactions, was obtained from McAuley et al. (1990):
Rk =

m
NS 

j

[Mk ]Y (0, j )kpik ,

k = 1, 2,

(1)

where NS is the number of types of active sites and m is the


number of types of monomers. According to this model, the
cumulative rate of polymer production can be calculated from
Rp =

m


mw k Rk .

(2)

k=1

2.2. Hydrodynamics
Compressor

Reactor

Pre-Polymer
Water
Heat Exchanger

Product

In the present study, the uidized bed reactor is modeled


by the procedure developed by Jafari et al. (2004), using the
sequential modular approach. In this model, the uidized bed
reactor is divided into several segments in series. In each segment, the ow of gas is considered as plug ow through the
bubbles and perfectly mixed through the emulsion phase. According to Jafari et al. (2004), the number of the segments at
different operating conditions can be determined from Table 3
in which
J = Ha

Fresh Feed
ethylene
1-butene
hydrogen
nitrogen
Fig. 1. Industrial uidized bed polyethylene reactor.

U0
,
Umf

(3)

where Hata number for the second order propagation reaction


is dened as
Ha =

(DAB kpik (j )Ni (r, j ))0.5


.
Kbe

(4)

A. Kiashemshaki et al. / Chemical Engineering Science 61 (2006) 3997 4006

3999

Table 1
Elementary reactions of ethylene polymerization system
Reaction

Description
ki (j )

i
N (0, j ) + Mi
Ni (1, j )

Initiation reaction with monomers

kpik (j )

Ni (r, j ) + Mk Nk (r + 1, j )

Propagation

kf m (j )
ik

Ni (r, j ) + Mk Nk (1, j ) + Q(r, j )


kf h (j )

Ni (r, j ) + H2 i NH (0, j ) + Q(r, j )


kf r (j )

Ni (r, j ) + AlEt3 i N1 (1, j ) + Q(r, j )


kf s i (j )

Ni (r, j ) NH (0, j ) + Q(r, j )

Transfer to monomer
Transfer to hydrogen
Transfer to co-catalyst
Spontaneous transfer

k (j )

Ni (r, j ) ds
Nd (j ) + Q(r, j )

Deactivation reactions

Table 2
Moment equations


Rv
dY (0, j )
= [MT ]{kiT (j )N (0, j ) + khT (j )NH (0, j )} + khr (j )NH (0, j )[AlEt 3 ] Y (0, j ) kf hT (j )[H2 ] + kf s T (j ) + kds (j ) +
dt
Vp
dY (1, j )
= [MT ]{kiT (j )N(0,j )+kh (j )NH (0, j )} + khr (j )NH (0, j )[AlEt 3 ] + [MT ]kP T T (j )Y (0, j )
T
dt

+ {Y (0, j ) Y (1, j )}{kf mT T (j )[MT ] + kf r T (j )[AlEt3 ]} Y (1, j ) kf hT (j )[H2 ] + kf s T (j ) + kds (j ) +

dY (2, j )
= [MT ]{kiT (j )N (0, j ) + khT (j )NH (0, j )} + khr (j )NH (0, j )[AlEt 3 ] + [MT ]kP T T (j ){2Y (1, j ) Y (0, j )}
dt

+ {Y (0, j ) Y (2, j )}{kf mT T (j )[MT ] + kf r T (j )[AlEt3 ]} Y (2, j ) kf hT (j )[H2 ] + kf s T (j ) + kds (j ) +

Rv
Vp

Rv
Vp

dX(n, j )
= {Y (n, j ) NT (1, j )}{kf mT T (j )[MT ] + kf r T (j )[AlEt3 ]} + {Y (n, j ) NT (1, j )}{kf hT (j )[H2 ] + kf s T (j ) + kds (j )}
dt
Rv
X(n, j )
n = 0, 1, 2
Vp

Table 3
Number of segments proposed by Jafari et al. (2004)
J

11.1 < J
5.62 < J < 11.1
0.63 < J < 5.62
J < 0.63

1
2
3
4

The equations of the hydrodynamic model of Jafari et al. (2004)


are given in Table 4.
Jafari et al. (2004) adopted the dynamic two-phase model for
estimating the void fractions of bubble and emulsion phases.
So far, most researchers have employed only the simple two
phase concept for modeling the gas-phase ethylene polymerization (e.g., McAuley et al., 1994; Fernandez and Lona, 2001),
in which it is assumed that all gas in excess of that required
for minimum uidization passes through the bed as solid free
bubbles while the emulsion stays at minimum uidization con-

ditions. They further assumed that, there are no catalyst particles in the bubbles and the reactions considered to occur only
in the emulsion phase. In a real uidized bed however, the concentration of particles in the emulsion phase can be less than
that at minimum uidization and the bubbles can contain various amounts of particles. Consequently, the dynamic two-phase
model, which considers the progress of the reaction in both the
bubble and the emulsion phases, will result in a better estimation of the reactor behavior.

2.3. Model equations


The assumptions made in developing the equations of the
model are summarized below:
Reactions occur in both bubble and emulsion phases.
Mass and heat transfer resistances between the solid polymer particles and emulsion gas are negligible (i.e., low to
moderate catalyst activity) (Floyd et al., 1986).

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A. Kiashemshaki et al. / Chemical Engineering Science 61 (2006) 3997 4006

Table 4
Correlations and equations used in the hydrodynamic model
Parameter

Formula

Reference

Minimum uidization velocity


Bubble velocity
Bubble rise velocity

Remf = [(29.5)2 + 0.357Ar]1/2 29.5


Ub = U0 Ue + ubr
ubr = 0.711(gd b )1/2
U0 Ub
Ue =
1
db = db0 [1 + 27(U0 Ue )]1/3 (1 + 6.84H )
db0 = 0.0085 for Geldart B


1
1 1

Lucas et al. (1986)


Kunii and Levenspiel (1991)
Kunii and Levenspiel (1991)

Emulsion velocity
Bubble diameter
Mass transfer coefcient

Heat transfer coefcient

Bubble phase fraction for Geldart B particles


Emulsion phase porosity for Geldart B particles
Bubble phase porosity for Geldart B particles
Volume of the emulsion phase in each stage
Volume of the bubble phase in each stage
Volume of PFR in each stage

Kbe =

+
Kbc
Kce

 
1/2
Dg g 1/4
Ue

Kbc = 4.5
+ 5.85
5/4
db
db


Dg e ubr
Kce = 6.77
db


1
1 1
Hbe =
+
Hbc
Hce


Ue g Cpg
(kg g Cpg )1/2 g 1/4
Hbc = 4.5
+ 5.85
5/4
db
db

1/2
e ubr
Hce = 6.77(g Cpg kg )1/2
db3



U0 Umf
 = 0.534 1 exp
0.413


U0 Umf
e = mf + 0.2 0.059 exp
0.429


U0 Umf
b = 1 0.146 exp
4.439
Ve,(n) = V (1 )
Vb,(n) = V 
VPFR,(n) = Vb,(n) b

Radial concentration and temperature gradients in the reactor


are negligible.
Elutriation of solids at the top of the bed is neglected.
Catalyst is fed continuously into the reactor as pre-polymer.
Constant mean particle size is assumed throughout the bed.
Overall direction of movement of polymer particles is considered downward for both phases.
Based on the above assumptions, monomers and hydrogen mass
balances in the nth stage of the bed are given by the following
equations:
For bubbles:
[Mi ]b,(n1) Ub Ab [Mi ]b,(n) Ub Ab Kbe ([Mi ]b,(n)
 z(n)
Ab
[Mi ]e,(n) )Vb,(n)
Ri
dz = 0.
(5)
VPFR,(n) z(n1) b,(n)
For emulsion:
[Mi ]e,(n1) Ue Ae [Mi ]e,(n) Ue Ae + Kbe ([Mi ]b,(n)



Rie,(n) = 0
[Mi ]e,(n) )Ve,(n)
1

Mostou et al. (2001)


Hilligardt and Werther (1987)
Kunii and Levenspiel (1991)

Kunii and Levenspiel (1991)

Cui et al. (2000)


Cui et al. (2000)
Cui et al. (2000)

For bubbles:
m


[Mi ]b,(n1) Ub Ab Cpi (Tb,(n1) Tref )

i=1

m


[Mi ]b,(n) Ub Ab Cpi (Tb,(n) Tref )

i=1


Ab HR z(n)
Rp
dz + Hbe (Te,(n) Tb,(n) )Vb,(n)
VPFR,(n) z(n1) b,(n)
+ Rpb,(n+1) Cppol (Tb,(n+1) Tref )
(7)
Rpb,(n) Cppol (Tb,(n) Tref ) = 0.

For emulsion:
m


[Mi ]e,(n1) Ue Ae Cpi (Te,(n1) Tref )

i=1

(6)

in which the direction of mass transfer is assumed to be from


bubble to emulsion phase. Furthermore, the energy balances
can be expressed as

m

i=1

[Mi ]e,(n) Ue Ae Cpi (Te,(n) Tref ) Rpe,(n) HR





Hbe (Te,(n) Tb,(n) )Ve,(n)
1
+ Rpe,(n+1) Cppol (Te,(n+1) Tref )
Rpe,(n) Cppol (Te,(n) Tref ) = 0

(8)

A. Kiashemshaki et al. / Chemical Engineering Science 61 (2006) 3997 4006


Table 5
Operating conditions for producing different grades of polyethylene

GAS OUT

Parameter

Unit

LLDPE

HDPE 1

HDPE 2

HDPE 3

H
Dt
U0
Tin
P
dp
Ethylene
1-Butene
Hydrogen
Inert gas

m
m
m/s
K
bar(g)
m
%
%
%
%

14.5
4.8
0.57
317
20
1145
40
17
9
34

14.5
4.8
0.54
313
19.85
1061
40
2.36
30
27.64

14.5
4.8
0.56
310
19.91
1049
40
6.43
16
37.57

14.5
4.8
0.55
316
19.99
965
34
0.34
23.46
42.2

Pre-Polymer
CSTR4

Kbe

PFR4

Hbe

in which the direction of heat transfer is assumed to be from


emulsion to bubble phase. In order to solve the model equations,
one has to specify the values of concentrations and temperature
of the materials ow entering the rst segment. These variables
are known at the inlet of the reactor:

Tb,(0) = Te,(0) = T0 .

Pre-Polymer

Hbe

CSTR3

[Mi ]b,(0) = [Mi ]e,(0) = [Mi ]0 ,

4001

Kbe

PFR3

Hbe
CSTR2

Kbe

PFR2

(9)
(10)
Hbe

3. Experimental
Four grades of polyethylene from Tabriz Petrochemical Complex were used in this work. The operating conditions at which
these samples were produced as well as the properties of the
polyethylene samples are given in Table 5.
The samples were dissolved in 1,2,4-trichlorobenzene (solvent) at 145 C and then injected into a Waters Alliance GPC
2000 Series system equipped with three 500 mm 7.8 mm
ID columns. The columns were packed with microporous
crosslinked styrene-divinylbenzene copolymer (particle sizes
of 20, 10 and 5 m). A high-temperature GPC was used to
measure molecular weights and molecular weight distributions of polyethylene because polyethylene requires a high
temperature for dissolution.
4. Results and discussion
The model equations were solved for the operating conditions shown in Table 5. In both LLDPE and HDPE cases, the
value of J, calculated from Eq. (3), was found to be less than
0.63. Therefore, according to Table 3, the uidized bed reactor of polyethylene production was divided into four segments.
Each segment consist a CSTR (emulsion phase) and a PFR
(bubble phase) with heat and mass being exchanged between
the phases. The schematic of such an arrangement is illustrated
in Fig. 2.
Different catalysts are used for producing LLDPE or HDPE.
As far as catalyst chemistry is concerned, the only difference is
the small amount of electron donor, introduced in the catalyst
preparation procedure. However, this component introduces a
signicant difference in behavior of the catalysts of HDPE and
LLDPE during polymerization. Therefore, it is evident that al-

POLYMER

CSTR1

Kbe

PFR1

POLYMER

GAS FEED
Fig. 2. Schematic diagram of the modeling structure.

though the mechanism of polymerization is the same when employing either catalyst, their activities are different and, as such,
different kinetic constants must be used in each case.
The kinetic constants were determined by tting the calculated molecular weight distribution of the polymer to the experimental data. Among the ethylene polymerization reactions,
propagation and chain transfer reactions determine the polymer
properties and the other reactions are less important. Accordingly, in the present study, chain transfer to hydrogen kinetic
rate constants have been only tted based on the molecular
weight distribution of the polymer. Other kinetic rate constants
are the same as those reported by McAuley et al. (1990). The
kinetic rate constants employed in this study are listed in Table
6. It should be pointed out that the change of the kinetic rate
constant with temperature is considered by using energy of activation.
Figs. 3a and b show the comparison between calculated
molecular weight distribution and the molecular weight distribution measured by GPC for two sample grades of LLDPE and
HDPE. The vertical axis in these gures is the derivative of the
cumulative weight fraction with respect to log Mw, which is a

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A. Kiashemshaki et al. / Chemical Engineering Science 61 (2006) 3997 4006

Table 6
Rate constants of the reactions given in Table 1
Reaction

Rate constant

Unit

LLDPE

kf (j )

s1

ki1 (j )
ki2 (j )
kh1 (j )
kh2 (j )
khr (j )

m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s

1
0.14
1
0.1
20

1
0.14
1
0.1
20

1
0.14
1
0.1
20

1
0.14
1
0.1
20

Propagation

kp11 (j )
kp12 (j )
kp21 (j )
kp22 (j )

m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s

85
2
64
1.5

85
15
64
6.2

85
2
64
1.5

85
15
64
6.2

Transfer

kf m11 (j )
kf m12 (j )
kf m21 (j )
kf m22 (j )
kf h1 (j )
kf h2 (j )
kf r 1 (j )
kf r 2 (j )
kf s 1 (j )
kf s 2 (j )

m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s
m3 /kmol s

0.0021
0.006
0.0021
0.006
0.1144
0.1144
0.024
0.048
0.0001
0.0001

0.0021
0.11
0.001
0.11
0.666
0.666
0.12
0.24
0.0001
0.0001

0.0021
0.006
0.0021
0.006
0.044
0.044
0.024
0.048
0.0001
0.0001

0.0021
0.11
0.001
0.11
0.37
0.37
0.12
0.24
0.0001
0.0001

Deactivation

kds (j )

s1

0.0001

0.0001

0.0001

0.0001

Site type 1
Formation
Initiation

typical output from GPC analysis. As it could be seen in these


gures, there is a good agreement between the calculated and
measured molecular weight distributions.
The polydispersity index (PDI) of the polymer is dened as
the ratio of weight average molecular weight to the number
average molecular weight:
PDI =

Mw

.
(11)
Mn
The polydispersity index is used extensively as a measure
of the width of molecular weight distributions (Hemmingsen,
2000). A comparison between the polydispersity indices evaluated from the model presented in this work and that of the
actual plant data is made in Fig. 4. As it could be seen in this
parity plot, there is a very good agreement between the calculated and measured PDI for LLDPE and satisfactory for HDPE.
The scattering of the data observed in the case of HDPE in
Fig. 4 may be contributed to the properties of the catalyst
which is produced in batches. The kinetic constants reported in
Table 5 were determined assuming the same catalyst in all operating conditions of HDPE production. However, the catalyst
produced in each batch could be slightly different from the
other batches. Therefore, scattering of PDIs in Fig. 4 could be
contributed to this difference.
A comparison between actual reactor temperatures and those
calculated based on the model presented in this work is made
in Fig. 5. As it could be seen in this parity plot, there is a good
agreement between the calculated and measured temperatures

HDPE
Site type 2
1

Site type 1
1

Site type 2
1

for HDPE and satisfactory for LLDPE. It could be suggested


that using better polymer physical properties would improve
the accuracy of the model.
Proles of the mole fraction of ethylene in the bubble and
emulsion phase along the bed height are shown in Fig. 6 for
two sample grades of LLDPE and HDPE. The cross sectional
average concentration of ethylene along the bed is also shown
in the same gure. As expected, the concentration of ethylene in
the bubble phase is higher and its slope (which is proportional
to the rate of consumption of ethylene) is lower than those
in the emulsion phase. This trend is established due to the
fact that the emulsion contains more catalyst. The calculations
indicate that the emulsion contains about 80% of the catalyst
while the bubbles carry about 20% of the catalyst introduced
into the reactor. Therefore, the apparent reaction rate is higher
in the emulsion than in the bubble phase. According to the
model presented in this work, only 50% of the change in the
concentration of monomers in bubbles is due to mass transfer
while the rest of monomers are consumed by the reaction inside
the bubble. This considerable amount of reacting monomers in
the bubbles is ignored in all previous models reported in the
literature.
The calculated overall production rates of polymer in the
reactor as well as the rates of production of polymer in bubble
and emulsion phases in the present model, over the polymer
residence time in the reactor are shown in Figs. 7a and b, for
sample grades of LLDPE and HDPE, respectively. Obviously,
the overall production rate of polyethylene in the bubble phase

A. Kiashemshaki et al. / Chemical Engineering Science 61 (2006) 3997 4006

0.8

4003

6
LLDPE
HDPE

Calculated
Actual

0.7

5
0.6
4
Calculated PDI

dW/d (Log Mw)

0.5

0.4

0.3

0.2

0.1
0
0

0.0
3

3.5

(a)

4.5
5
Log Mw

5.5

6.5

3
Actual PDI

Fig. 4. Comparison between plant and calculated PDI.

0.8
95
0.7

LLDPE
HDPE

Calculated
Actual

90
Calculated Temperature (C)

dW/d (Log Mw)

0.6

0.5

0.4

0.3

0.2

85

80

75
0.1
70

0.0
3
(b)

3.5

4.5

5.5

6.5

Log Mw

Fig. 3. Comparison between calculated and plant molecular weight distributions: (a) LLDPE; (b) HDPE 1.

is less than that in the emulsion phase. The reason for such
behavior is the same as that discussed for Fig. 6, i.e., there is less
catalyst presented in the bubble phase compared to the emulsion
phase. As can be seen in Figs. 7a and b, the production rate of
polymer in the emulsion and bubble phases are roughly 80%
and 20%, respectively. Therefore, the contribution of catalyst

70

75

80

85

90

95

Actual Temperature (C)


Fig. 5. Comparison between plant and calculated temperatures.

inside the bubble phase is not negligible and should not be


neglected in any modeling attempt.
The calculated overall production rates of polymer in the reactor based on the simple two phase and actual production rate
are also include in Figs. 7a and b. In the simple two phase hydrodynamic model, which has been extensively used up to now
for modeling gas phase polymerization reactors, it is assumed
that the emulsion is at minimum uidization condition at any

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A. Kiashemshaki et al. / Chemical Engineering Science 61 (2006) 3997 4006


40.5

16
Emulsion

Rp_b
Rp_e
Rp (DTP)
Rp (STP)

Bubble
Overal

14
LLDPE

40

Actual Production Rate

Production Rate (ton/hr)

Ethylene mole fraction (%)

12

39.5

39

10
8
6
4

HDPE 1

38.5

2
0
0

38
0

12

15

Bed Hieght (m)

Rp_b
Rp_e
Rp (DTP)
Rp (STP)

12
Production Rate (ton/hr)

A uidized bed reactor for polyethylene production has been


modeled using the dynamic two-phase concept of uidization
and combined with proper kinetic model to provide a better
understanding of the reactor performance. The hydrodynamic
model of Jafari et al. (2004), in which the bed was divided into
four serial segments was employed in this work. The ow of
gas in each segment was considered to be plug ow through the
bubbles (which contain a small amount of particles) and perfectly mixed through the emulsion phase (which may contain
more gas than that at minimum uidization). Since the bubbles
were considered to contain solids, polymerization reactions occur not only in the emulsion phase but also inside the bubbles.
The new model is able to predict essential reactor parameters
such as monomer concentration proles, polymer productivity
and reactor temperature, as well as properties of the produced
polymer such as molecular weight distribution and polydispersity index. Results of the proposed model were compared with
experimental data for molecular weight distribution, polydispersity index, reactor temperature and real production rate of
different industrial grades of polyethylene. The agreement between the actual and calculated values was found to be satisfactory. It has been shown that about 20% of the polymer is
produced in the bubble phase.

16

14

5. Conclusions

2
Time (hr)

Fig. 6. Ethylene concentrations in the bubble and emulsion phase.

gas velocity and the bubbles are solid-free. As it could be seen


in Figs. 7a and b, polymer production in case of simple two
phase model is close to the amount obtained from the dynamic
two phase model. However, the simple two phase model does
not provide any production of the polymer in the bubble phase.

(a)

Actual Production Rate

10

0
0
(b)

3
4
Time (hr)

Fig. 7. Evolution of production rate of the polymer over the residence time
of the polymer in the reactor: (a) LLDPE; (b) HDPE 1.

Notation
A
AlEt 3
Ar
Cpi
Cppol
Cpg

cross section area of the reactor, m2


triethyl aluminum
Archimedes number
specic heat capacity of i monomer, J/kg K
specic heat capacity of solid product, J/kg K
specic heat capacity of gaseous stream, J/kg K

A. Kiashemshaki et al. / Chemical Engineering Science 61 (2006) 3997 4006

db
dp
DAB
Dg
Dt
H
Ha
Hbc
Hce
Hbe
J
kg
kds
kf
kf hi
kf mik
kf r i
kf s i
khi
khr
kii
kpik

Kbc
Kbe
Kce
m
mw
[Mi ]0
[Mi ]n
Mi
Mn
Mw
N(0, j )
Nd (j )
NH (0, j )
Ni (r, j )
NS
p
PDI
Q(r, j )

bubble diameter, m
particle diameter, m
diffusion coefcient m2 /s
gas self diffusion coefcient, m2 /s
reactor diameter, m2
height of the reactor, m
Hata number
bubble to cloud heat transfer coefcient,
W/m3 K
cloud to emulsion heat transfer coefcient,
W/m3 K
bubble to emulsion heat transfer coefcient,
W/m3 K
dimensionless number (Ha U0 /Umf )
gas thermal conductivity, W/m K
spontaneous deactivation rate constant, s1
formation rate constant, s1
transfer to hydrogen rate constant for a polymer
chain with terminal monomer i, m3 /kmol s
transfer to monomer k rate constant for a polymer chain with terminal monomer i, m3 /kmol s
transfer to co-catalyst rate constant for a polymer
chain with terminal monomer i, m3 /kmol s
spontaneous transfer rate constant for apolymer
chain with terminal monomer i, m3 /kmol s
rate constant for re-initiation by monomer
i, m3 /kmol s
rate constant for re-initiation by co-catalyst
i, m3 /kmol s
rate constant for initiation by monomer
i, m3 /kmol s
propagation rate constant for a polymer chain
with terminal monomer i reacting with monomer
k, m3 /kmol s
bubble to cloud mass transfer coefcient, s1
bubble to emulsion mass transfer coefcient, s1
cloud to emulsion mass transfer coefcient, s1
number of monomers
molecular weight, kg/kmol
initial concentration of component i, mol/m3
concentration of component i in the nth reactor,
mol/m3
the ith monomer
number average molecular weight, kg/kmol
weight average molecular weight, kg/kmol
active site type j produced by formation reaction
spontaneously deactivated site of type j
active site of type j produced by transfer to
hydrogen
live polymer of length r growing on site of type
j with terminal monomer i
number of type of active sites
pressure, Pa
polydispersity index
dead polymer of length r produced at site of
type j

Rib,(n)
Rie,(n)
Rk
Rp
Rv
t
T
U0
Ub
Ue
Umf
V
Vp
X(n, j )
Y (n, j )

4005

instantaneous rate of reaction in nth stage for


monomer i inthe bubble phase, kmol/s
instantaneous rate of reaction in nth stage for
monomer i in the emulsion phase, kmol/s
instantaneous rate of reaction for monomer k,
kmol/s
polymer production rate, kg/s
volumetric ow rate of polymer from the reactor,
m3 /s
time, s
temperature, K
supercial gas velocity, m/s
bubble velocity, m/s
emulsion gas velocity, m/s
minimum uidization velocity, m/s
volume, m3
volume of polymer inside the reactor, m3
nth moment of dead polymer produced at site of
type j
nth moment of live polymer produced at site of
type j

Greek letters

HR
b
e
mf

g
pol

volume fraction of bubbles in bed


heat of reaction, J/kg
void fraction of bubble
void fraction of emulsion
void fraction of the bed at minimum uidization
gas viscosity, Pa s
gas density, kg/m3
polymer density, kg/m3

Subscripts and superscripts


1
2
3
b
e
g
in
i
j
mf
n
pol
ref

ethylene property
1-butene property
hydrogen property
bubble phase property
emulsion phase property
gas mixture property
feed property
monomer type no
active site type no
minimum uidization
number of stages
polymer properties
reference conditions

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4006

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