Pergamon

Chmtiol

Engineering

Srirnce. Vol. 49. No. 13. pp. 2035-2045,

1994
Copyright
0 1994 Elsetier Science Ltd
Printed in Great Bntain All rights reserved
@X9-2SOY/Y4 %7.m + 0.00

OOOS2509(94)EOO30-T

A COMPARISON
MODELS
FOR

OF TWO-PHASE
FLUIDIZED-BED
REACTORS

AND WELL-MIXED
POLYETHYLENE

K. B. MCAULEY,
J. P. TALBOT
and T. J. HARRIS
Department of Chemical Engineering, Queens University, Kingston, Ontario, Canada K7L 3N6
(First

received

12 duly

1993;

accepted

in reuised

,form

17 January

1994)

Abstract-A steady-state model incorporating interactions between separate bubble and emulsion phases
in a fluidized-bed polyethylene reactor was developed by Choi and Ray [Chem. Engng Sei. 40,2261-2279
(1985a)]. Correlations for maximum stable bubble size indicate that bubbles within the bed arc considerably smaller than those in their original model. In the paper, the influence of bubble size and superficial
velocity on reactor operation are examined. It is shown that bubble size critically influences the rate of heat
and mass transfer within the bed, and when the bubbles are as small as those predicted by the maximum
stable bubble size correlations, there is little or no resistance to the transfer of monomer and heat between
the phases. A simplified welt-mixed mode1 is developed to describe reactor operation in the limiting case
where there is no difference between bubble and emulsion gas temperatures and concentrations. The
differences between the predictions of temperature and monomer concentrations of the two-phase and
simplified models are less than 2 or 3 K and 2 mol%, respectively, in the operating range of industrial
interest. Therefore, a simple back-mixed model is appropriate for predicting temperature and concentration
in the gas phase of industrial fluidized-bed polyethylene reactors.

1. INTRODUCTION
The
modelling
of
polyethylene
production
in
fluidized-bed
reactors has received considerable
attention in recent years. At the molecular level, kinetic
models have been developed to predict the molecular
weight and short chain branching distributions of the
polymer
molecules
(Galvan
and Tirrell,
1986; de
Carvalho
et al., 1989; McAuley
et al., 1990). At the
larger scale of the individual polymer particles, resistances to heat and mass transfer within the particles
and in the boundary layer surrounding the particles
have been analysed by Galvan and Tirrell (1986),
Floyd et al. (1986a, b, 1987) and Hutchinson and Ray
(1987). It has been established that, under many conditions, heat transfer and diffusional
resistances do
not play an important
role at the particle level in
gas-phase
polyethylene
reactors.
Nevertheless,
for
very young particles with highly active catalysts, heat
and mass transfer resistances can become significant,
leading to multiple steady states and particle overheating. Modelling
at the particle level is useful for
predicting polymer particle growth and morphology
(Hutchinson et al., 1992) and, if diffusional or temperature gradients within the particles are significant, for
predicting the effects of intraparticle temperature and
concentration
gradients on the molecular properties
of the polyethylene
produced.
For many catalyst systems in which heat and mass
transfer resistances do not influence monomer
concentrations and temperatures within the polymer parCurrent address: Northern T&corn,
185 Corkstown
Road, Nepean, Ontario, Canada K2H 8V4.

titles, the monomer concentration

at the catalyst sites
is determined
by the equilibrium
sorption
of the
monomer
within the polymer particles. Hutchinson
and Ray (1990) have developed
thermodynamic
models to predict equilibrium
monomer
concentrations at the catalyst sites from external gas-phase
monomer
concentrations
in the vicinity of the polymer particles.
The research in the current article focuses on the
modelling
of gas-phase polyethylene
reactors at an
even larger scale, that of fluidization phenomena and
heat and mass transfer within the bed. It is important
to determine whether heat and mass transfer resistances between the bubbles and the emulsion phase are
significant in typical industrial reactors, or whether
the entire contents of the fluidized-bed
reactor can
reasonably be treated as well-mixed. If the well-mixed
assumption is valid, experimental results and correlations developed from well-stirred gas-phase laboratory reactors [e.g. Lynch and Wanke (199111 can be
applied directly to industrial-scale fluidized-bed
reactors. McAuley
et al. (1990) and McAuley
and MacGregor (1992, 1993) assumed a well-mixed bed in the
development
of the reaction rate expressions used in
their models to predict gas compositions,
temperature
and polymer properties in fluidized-bed
polyethylene
reactors.
Choi and Ray (1985a) developed the only fluidizedbed polyethylene
reactor model in the literature that
considers temperature
and concentration
gradients
within the gas in the bed. Their model considers the
interaction
of separate emulsion and bubble phases
within the reactor bed. The current article updates

K. B. MCAULEK et al.

2036

and extends their work. The existence of a maximum

stable bubble size, and revised assumptions regarding
heat and mass interchange mechanisms within the bed
are incorporated in the mathematical model. A sensitivity analysis is performed to determine the influence
of key parameters, such as particle size, bubble size,
superficial velocity and catalyst feed rate, on predicted
steady-state reactor operating conditions. A simplified model of the process, corresponding to the wellmixed assumption, is developed, and the predictions
of the two-phase model and simplified model are
compared.

Z MODEL

DEVELOPMENT

To obtain a clear understanding of the fluidizedbed model, the assumptions that have been made in
its development are summarized below. With the exception of the assumption regarding the maximum
stable bubble size, these assumptions were also made
by Choi and Ray (1985a).
2.1. Model assumptions
(9 The fluidized bed comprises two phases, the
bubble phase and the emulsion phase. Reactions occur only in the emulsion phase which
is at minimum fluidizing conditions.
(ii) All gas in excess of that required for minimum
fluidization passes through the bed in the
bubble phase.
(iii) The bubbles grow only to their maximum
stable size. Because the bubbles reach this
maximum size near the base of the bed, all
bubbles are assumed to have a uniform size
throughout the bed. The bubbles travel up
through the bed in plug flow at constant
velocity. Heat and mass interchange coefflcients are average values over the height of
the bed.
(iv) The emulsion phase is perfectly back-mixed.
In reality there will be a temperature gradient
over the first 10 cm above the distributor
(Wagner et al., 1981), but above this level the
axial temperature gradient is very small.
(v) Radial concentration and temperature gradients within the bed are negligible because the
emulsion phase is well-mixed and the bubbles
are distributed uniformly across the bed. The
assumption of uniform radial distribution of
bubbles is supported by the work of
Glicksman et al. (1987), who observed uniform bubble distribution across the bed surface in similar large-particle systems with
small bubbles relative to the bed diameter.
(vi) There is negligible resistance to heat and mass
transfer between the gas and solids in the
emulsion phase. This assumption is valid
when the catalyst particles are sufficiently
small and the catalyst activity is not extremely high (Floyd et al., 1986a).

(vii) A mean size has been used for the polymer

particles and neither elutriation of fines nor
particle agglomeration are considered in the
model.
(viii) The only gas-phase component considered in
the model is ethylene. Talbot (1990) developed a more comprehensive model that
also considers inert components in the gas
phase.
2.2. Bubble-phase material and energy balances
Since the bubbles are assumed to be non-itteracting spheres, consideration of an individual bubble
can be used to infer the behaviour of the entire bubble
phase. The only mechanism by which mass can be
transferred from the bubbles to the emulsion phase is
by diffusion through the bubble clouds. Energy is
transferred between the phases due to the temperature
gradient between the bubbles and the emulsion and
also by the diffusing gas. Writing the material
and energy balances for a single bubble (Kunii and
Levenspiel, 1969) gives

dcb
=
dz

$(C, -

C,),

dTb
-=
dz

(2)

where the concentration of the monomer is expressed

in moles of ethylene per unit volume of bubble. The
variables in equations (1) and (2) are defined in the
notation.
2.3. Emulsion-phase material and energy balances
The steady-state mass and energy balances on the
emulsion phase are described by algebraic rather than
differential equations, since the emulsion phase is perfectly back-mixed. A mass balance on the interstitial
gas in the emulsion phase may be written as

+ mn(Cb - C-2)
(1 - 8)&,,

= O. (3)

The first term considers the flow of gas into the

emulsion phase at the base of the bed and the outflow
of gas at the top. The second and third terms are the
rates of ethylene outflow with the product stream and
ethylene consumption by polymerization, respectively. The final term is the rate of mass transfer of
ethylene from the bubble phase to the emulsion phase.
c is an average concentration of ethylene in the
bubbles, over the height of the bed.
The solid-phase mass balance is shown below:
R, + qcat - QU - +-)p,

= 0.

(4)

The three terms in eq. (4) are the solids production

rate by polymerization, the catalyst feed rake to the
reactor and the rate of solids outflow in the product

Comparison

of two-phase and well-mixed models

stream. A mass balance on the catalyst gives

4cnr - X,&(1

- =%I&%= 4

2037
V, = AH&

(5)

where X,,, is the mass fraction of catalyst in the solid

phase.
The steady-state energy balance on the emulsion
phase is

R, = &C,X,,,PJH(~

+ RPC - AH - (c, - c,)(T,

- 7cDHU,,(T, -

T,)

- T,,r)l

= 0.

(6)

The first term is the enthalpy associated with gas Row

to the emulsion phase at the base of the bed and the
enthalpy of the gas stream leaving the emulsion at the
top of the bed. We assume that the heat capacity of
the gas is the same in the inflow and outflow streams.
The second term is the enthalpy associated with the
mass transfer of gas from the bubble phase into the
emulsion. The third term is the convective and conductive heat transfer between the emulsion and
bubble phases, and the fourth is the rate of heat
generation by the polymerization reaction. The final
term is the rate of heat loss to the surroundings
through the reactor wall. The enthalpy associated
with the catalyst feed to the reactor has been neglected
because it is small relative to the other terms in eq. (6).
All symbols in eqs. (l)-(6) are defined in the notation
The volumes of the emulsion and bubble phases in the
bed can be calculated from the total volume of the bed
and the bubble fraction, 6:
v, = AH(1 -a),

(7)

Table
Minimum fluidizing
(Lucas et al., 1986)

1. Fluidization

velocity

Bubble velocity
(Davidson and Harrison,
Bubble fraction
(Kunii and Levenspiel,

1969)

Emulsion velocity
(Bukur et al., 1974)
Mass interchange
(Kunii and Levenspiel,

1969)

Heat interchange
(Kunii and Levenspiel,

1969)

Used

by Choi and Ray (198%).

- @(I - ~,f)Mw-

(9)

This rate expression assumes that the ethylene concentration at the catalyst sites is proportional to C,,
the concentration in the emulsion gas. Since monomer
diffusion rates, both to the polymer particles and
within them (Floyd et al., 1986a, b, 1987), are fast
relative to the reaction kinetics, the ethylene dissolved
in the polymer phase is in equilibrium with the ethylene in the emulsion gas. Hutchinson and Ray (1990)
have shown that Henrys law applies to the solubility
of ethylene in polyethylene at the conditions in the
reactor. Hence, the proportionality
assumption is
valid. The rate constant, k,, includes the Henrys law
constant for ethylene partitioning between the two
phases. We neglect the mild effect of temperature on
the Henrys law constant and assume that k, displays
Arrhenius behaviour. The effect of catalyst deactivation is not included in the model.
Correlations used to predict the bubble fraction in
the bed, the voidage of the emulsion phase, bubblephase and emulsion-phase gas velocities, and mass
and heat interchange coefficients in eqs (l)-(9) are
listed in Table 1. The correlation for the minimum
fluidization velocity, U,/. assumes that the particles
are spherical. The majority of these correlations were
used by Choi and Ray (1985a), although it appears
that the dimensions of the overall material and energy

and interchange
Re,,

correlations

= (29.F + 0.0357 Ar). - 29.5

u,=u,1963)

(8)

Reaction rates in gas-phase ethylene polymerization are generally modelled as first-order in both
monomer concentration and in the quantity of catalyst in the reactor (Choi and Ray, 1985a; de Carvalho
et al., 1989; McAuley et al., 1990), so that

u,,+0.711&z

K. B. MCAULEY

2038

interchange coefficient correlations that they used are

inconsistent with their model.
Both Choi and Ray (1985a) and Talbot (1990) included a cloud to emulsion heat interchange coefficient, H,,, in their models:
.

(10)

This interchange coefficient is similar in structure to

K,, and was meant to account for the resistance to
heat transfer between the cloud and the emulsion. In
bubbling fluidized beds, the mechanism for mass
transfer between the bubbles and the emulsion involves gas diffusion through the cloud. Hence, the
interchange coefficient K,, in Table I is required to
account for this diffusional resistance. Use of H,, as in
eq. (10) incorrectly implies that the main path for heat
transfer is by conduction through the gas in the cloud.
Since the clouds contain particles with large thermal
mass, and the transfer of heat between gas and the
particles is fast, heat transfer through the cloud is
rapid. It is governed primarily by heat transfer between the cloud gas and polymer particles and by
subsequent movement of the particles between the
cloud and the emulsion. Hence, the resistance to heat
transfer between the cloud and the emulsion is small
compared to the bubble to cloud resistance (Kunii
and Levenspiel, 1969) and is neglected in our model.
Choi and Ray used Broadhurst and Beckers (1975)
correlation for the voidage in the emulsion phase.
This correlation can be inaccurate for large particles,
giving values of E,~ near 0.38 for this system (Talbot,
1990). Calculations of the voidage in settled polyethylene particles using measured bulk densities (Wagner
et al., 1981) give values ranging from 0.46 to 0.65.
Hence, we have used a more reasonable value of
E,,,~= 0.5 in the model. Other physical parameters
used in the mode1 are listed in Table 2.

Table 2. Standard operating conditions

and parameters
Parameter
flc,

P#

(poise)

Wcm3)

ppol Wm3)
PEPt
w~31
cp (J/g/K)
k,0 (cm/8 cat/s)

& (J/mol)
AH (J/g)
d, (cm)
db(cm)
H (cm)
D (cm)
P (atm)
&ml
Co (mol/cm3)
To (K)
i-, (K)
T6.r (K)
U. @m/s)

Value
o.oc0115
0.024
0.95
2.37
4.004
4.16 x 106
37,260
3829
0.05
15

1097
396
20.42
0.5
0.00085
316
293
273.15
34.8

et al.

2.4. Maximum stable bubble size

When choosing a correlation for bubble size, it is
important
to consider the maximum
size that
a bubble can reach before it becomes unstable and
breaks up into smaller bubbles. Davidson and
Harrison (1963) established that the settling velocity
of the bed particles should be greater than or equal to
the bubble rise velocity, U,. The maximum bubble
size could then be obtained from
2tJ:
d hmal= -3
9

(11)

where Ur is the terminal velocity of particles of diameter d,. Grace (1986a) postulated the same equation
form, but used instead the terminal velocity of a particle of diameter 2.7d,, resulting in a larger stable
maximum bubble size than Davidson and Harrison.
Using the correlation of Flemmer and Banks (1986) to
predict terminal velocity, and the maximum stable
bubble size criteria of Davidson and Harrison (1963)
and Grace (1986a), polyethylene particles with a mean
diameter of 0.05 cm would result in maximum stable
bubble sizes of 9.77 and 24.2 cm, respectively.
The use of maximum stable bubble size correlations
is a major difference between this model and that of
Choi and Ray (1985a), who used a mean bubble size
predicted by Mori and Wen (1975) for a bubble halfway up the reactor bed. Mori and Wen (1975) caution
in their paper that bubble stability was not taken into
consideration. For the reactor dimensions in Table 2,
the Mori and Wen correlation predicts an average
bubble diameter of 89 cm (Talbot, 1990), which is
22% of the reactor diameter. This predicted bubble
size is clearly larger than the maximum stable sizes
predicted by either the Davidson and Harrison or the
Grace correlation. As we will demonstrate in this
article, bubble size is a critical parameter that affects
the predicted heat and mass transfer rates in fluidizedbed reactor models. Our model assumes that the
bubbles rapidly reach their maximum stable size near
the base of the bed, and that this bubble diameter is
the average bubble size within the bed.
2.5. Consequences ofthe model assumptions and potential improvements
The current model assumes that the emulsion phase
is perfectly back-mixed. According to Grace (1986a),
at least eight different assumptions have been adopted
in various fluidized-bed reactor models to describe the
axial mixing of the gas in the dense phase. These
assumptions range from upward plug flow of the
emulsion gas, through perfect mixing, to downward
flow of the emulsion gas. Some models, for example
that by Shiau and Lin (1993), divide the emulsion
phase into a series of well-mixed sections with both
upward and downward flow of emulsion gas between
adjacent stages. In many cases, the predicted conversions are relatively insensitive to the emulsion-phase
gas mixing pattern assumed, especially when conversions are low (Grace, 1986a). Therefore, adopting
a more complicated approach to mixing of the gas in

Comparison of two-phase and well-mixed

the emulsion phase is not warranted when modelling
fluidized-bed polyethylene reactors. In models used to
predict the properties of polymer produced in
fluidized-bed reactors, the assumptions made regarding the mixing and residence time distribution of the
particles in the bed are more important issues. In
product property models, especially those used for
product grade transition studies (McAuley et al., 1990;
McAuley and MacGregor, 1991, 1992; Ramanathan
and Ray, 1991), it is common to assume that the solid
phase is well-mixed. Imperfect mixing could have
a dramatic effect on the time required to change from
one polyethylene grade to the next. This problem is
beyond the scope of the current article.
The formulation of the interface mass and energy
interchange coefficients in Table 1 (Kunii and
Lcvenspiel, 1969) considers the existence of a cloud
phase between the bubble and emulsion which provides the main resistance to mass transfer. In the
current model, and in that proposed by Choi and Ray
(1985a), only a bubble phase and an emulsion phase
are considered in detail. The importance of the cloud
phase is largely neglected, although Grace (1971) postulated that the cloud can play an important role in
such large-particle systems. As a result, the current
model formulation ignores the effects of cloud shedding and is expected to underpredict mass transfer
rates at the cloud boundary. Talbots (1990) calculations of the volume of the cloud phase in gas-phase
polyethylene reactors suggest that it could be as large
as half of the bubble volume and that the cloud
comprises roughly 25% of the dense phase. Jones and
Ghcksman (1984) observed in their experiments with
large particles that the variation from two-phase
theory was due, not to the presence of clouds, but
rather to low-resistance paths for gas flow through the
bed provided by sequences of closely spaced bubbles
or bubble chains. Therefore, possible refinements to
the two-phase bubbling bed model developed in this
article include consideration of the clouds as a separate phase or consideration of gas through-flow effects
due to bubble chains. Still more complex models,
based on fundamental mass, momentum and energy
conservation equations, could be derived to predict
heat and mass transfer between the bubbles and the
emulsion (Kuipers et al., 1992) without resorting to
correlations for predicting bubble behaviour. Such
detailed models require considerable computation,
and are not justified by our current purpose, which is
to determine whether the well-mixed assumption is
appropriate for the gas phase in industrial fluidizedbed polyethylene reactors.
In some recent articles, Kunii and Ievenspiel
(1991a, b) have shown that in systems wherein the
fluidizing gas is absorbed by the particles in the bed,
larger bubbleemulsion
mass interchange rates are
experienced than are predicted by the correlations for
K, and H,,, in Table 1. Particles that rain through the
bubbles significantly enhance mass transfer rates by
absorbing gas from the bubbles wherein gas concentrations are higher than in the emulsion. Similarly,

models

2039

heat transfer can also be enhanced when heat generating particles traverse the cooler bubble phase. Since
large quantities of ethylene are first absorbed and then
consumed within the polyethylene particles to produce heat, industrial fluidized-bed polyethylene reactors provide an ideal example of a system with gas
absorbing, heat generating particles. Therefore, we
expect that our model may underpredict the actual
heat and mass interchange rates between the bubbles
and emulsion, and overpredict concentration and
temperature differences between the two phases.
An additional reason that our model may overpredict the true temperature and concentration differences between the bubble and emulsion phases is that
we have assumed the bubbles to be totally non-interacting spheres of constant size. Both bubble breakup
and coalescence can act to enhance heat and mass
transfer (Grace, 1986a). When bubbles coalesce, they
momentarily assume the local dense-phase composition. Coalescence between two bubbles can lead to
a complete and sudden renewal of the gas in the
bubbles by gas in the emulsion phase (Pereira et al.,
198 1).
2.6. Method OSsolution
Differential equations (1) and (2) can be integrated
analytically to determine both Cb and T, as functions
of z, the vertical position in the bed. These expressions
can then be used to determine the following equations
for CI, and T,,, which are average values required to
achieve the same total mass and energy transfer over
the height of the bed
E=&[l

-exp($+)].

Tb Te
:=~[l--crp(=-E=&
To

(12)

(13)

Te

Using the parameters in Table 2 and the correlations

in Table 1, eqs (3)-(6), (9), (12) and (13) form a set of
seven equations with the following eight unknowns:
C,, c,
T,, %, Q, R,, X,,, and qol. Talbot (1990)
developed a simple non-iterative technique to solve
this system to obtain steady-state operating conditions. First, values of Tb ranging from 325 to 400 K
are chosen, and then each of the other variables is
evaluated in turn. The analysis has been limited to this
temperature range because below 325 K the polymerization rate is very low and above 400 K polymer
particles melt and agglomerate.
3. PARAMETRIC

STUDIES

In this section, we investigate the effects of model

parameters and reactor operating conditions on
model predictions.
3.1. Efects of superficial gas velocity
Industrial fluidized-bed polyethylene reactors are
operated at superficial gas velocities ranging from 3 to

K. B.

2040

MCAULEY

6 times the minimum fluidization velocity (Wagner

et al., 1981). The major effect of an increase in the
superficial velocity, U,, is a reduction in tlae time
required for a given quantity of gas to pass through
the bed. For a specified catalyst feed rate, this smaller
residence time leads to a lower reaction rate, a lower
single-pass conversion and a lower emulsion temperature. Figure 1 shows that as U, decreases from 6U,/
to 3&f f the safe regime, in which the reactor can be
operated without a danger of particle melting, decreases accordingly. A major function of the gas passing through the bed is to remove the heat of reaction.
Small values of U. lead to high sensitivity of the
emulsion temperature to changes in catalyst feed rate
and to other potential operating disturbances. High
gas velocities are required to reduce the risk of particle
melting, agglomeration and subsequent reactor shutdown. However, high gas velocities reduce the conversion of monomer per pass through the reactor, and
can lead to greater elutriation of small particles from
the bed. Elutriated particles are prevented from passing out of the reactor and into the gas recycle system
using a velocity reduction zone at the top of the
reactor where entrained particles are given the opportunity to drop back into the bed. Particle return
may also be aided by a cyclone (Wagner et al., 1981).
Using a bubble diameter of 15 cm, we observe that
the model predicts temperatures in the bubble phase
that are 0.5-5 K lower than in the emulsion phase,
and ethylene concentrations that are 0.555% higher.
The size of these temperature and concentration differences depends to a great extent on the catalyst feed
rate, and hence on the rate of reaction. For low
reaction rates, corresponding to emulsion temper-

320

CatalystFeed Rate

Y,

(c)

Cata,,st

Feed Rate

atures below 340 K and conversions less than 2.5%

per pass, the temperature difference is less than 1.5 K.
At high polymerization rates corresponding to emulsion temperatures above 380 K and conversions
above 7% per pass, the temperature difference is approximately 4 K. This is true regardless of the superficial velocity at which the reactor is operated.

3.2. Eflects of bubble size

Grace (f986a) and Davidson and Harrison (1963)
developed correlations
for the maximum stable
bubble size for a given particle size, based on the
terminal velocity. For polyethylene particles 0.5 cm in
diameter, the bubble diameters predicted from these
correlations are 24.42 and 9.77 cm, respectively.
Larger bubble diameters are predicted by bubble size
correlations that do not consider bubble stability. To
investigate the importance of using an accurate
bubble size, simulations were performed to determine
the effects of changing bubble size on model predictions. Figure 2 shows the variation of the steady-state
emulsion temperature when bubbles of sizes 5, 10, 20
and 40 cm were present in the bed. A superficial velocity of 34.8 ems or 6U,,,I was used in these simulations.
As bubble size decreases, the interfacial area between the bubble and emulsion phases increases, leading to a smaller resistance to heat and mass transfer.
As shown in Fig. 2(b) and 2(d), the temperature and
concentration differences between the bubble and
emulsion phases are much greater for large bubbles
than for small bubbles. Larger differences are predicted for higher catalyst feed rates and higher operating temperatures, and can be as large as 20 K and

0.1

cI.4

[Q/S]

0:3

012

0:1
O

0.3

0.2

0.1

(a)

et al.

[Q/S]

Catalyst

D.2
Feed Rat13 [Q/S]

Catalyst

FE&

0.3

0:4

(4

Fig. 1. The effect of superficial gas velocities ranging from 3U,,

& = 15 cm.

Rate[Q/S]

to 6C& on steady-state reactor operation.

Comparison of two-phaseand well-mixed models

as
L

-MB-=--rc*10*5

z
z
c
1

15
10

8
t
&
E

(W

0.1

Fig. 2. The

0.2
0.3
Catam Feed Rate [g/s]

effect

0.4
(d)

5
0
Catalyst Feed Rate

[O/S]

Catdysl Feed Rate

[g/s]

of bubble diameters ranging from 5 to 4Ocm on steady-state

uo=

15%, respectively, for 40 cm bubbles, but are less than

1 K and 1% for 5 cm bubbles.
Figure 2(a) and (c) shows the effects of catalyst feed
rate and bubble size on the emulsion temperature and
on the single-pass conversion of ethylene. As expected,
higher catalyst feed rates lead to higher polymerization rates and to higher emulsion temperature and
conversion. The effects of bubble size on emulsion
temperature and conversion are less obvious. Smaller
bubbles have a lower velocity through the bed compared with larger bubbles. As a result, smaller bubbles
lead to a larger bubble fraction, 6, in the bed and to
a reduction in the volume of the emulsion phase for
a given expanded bed height. Therefore, the residence
time for both the solid phase and the catalyst decreases with decreasing bubble size, reducing the
quantity of catalyst in the reactor for a given catalyst
feed rate. This reduction in the quantity of catalyst
tends to reduce R,, the rate of polymerization, thereby
reducing the rate of heat generation in the emulsion
phase.
As shown in Fig. 2(a), at low catalyst feed rates, the
effect of a reduced bubble size is to reduce the emulsion temperature because smaller bubbles lead to improved heat removal rates, to less catalyst in the
reactor and to reduced heat generation. At high catalyst feed rates, the emulsion temperature for 4Ocm
bubbles falls below that for 20 and 10 cm bubbles.
This cross-over results when mass transfer effects become dominant for the large bubbles. As shown in
Fig. 2(d) for 40 cm bubbles, the ethylene concentration in the emulsion phase falls rapidly at catalyst feed
rates above 0.35 g/s.The lower concentration of ethylene in the emulsion reduces the polymerization rate,

0.4

reactor operation,

6U,,.

thereby reducing the heat generation rate. This mass

transfer effect for larger bubbles becomes more significant at higher catalyst feed rates and eventually
causes the T, vs qc., curve for 4Ocm bubbles to fall
below the curves for 20 and 10 cm bubbles.
At low catalyst feed rates and low conversions, Fig.
2(c) shows that smaller bubbles lead to lower singlepass conversions. This may seem counter-intuitive
because smaller bubbles lead to enhanced mass transfer and will result in higher ethylene concentrations in
the emulsion phase. However, small bubbles also lead
to less catalyst in the reactor and to lower emulsion
temperatures. At low catalyst feed rates and low conversions, the net effect is a reduction in the polymerization rate, and a reduction in the single-pass conversion as the bubbles become smaller. Only at higher
catalyst feed rates and high conversions does the mass
transfer effect become dominant, and the conversion
vs catalyst feed rate curve for 40 cm bubbles falls
below that for 10 cm bubbles. Typical single-pass conversions of ethylene in industrial fluidized-bed polyethylene reactors are on the order of 225% (Choi and
Ray, 1985b), but overall conversions can exceed 98%
(Sinclair, 1983), since most of the unreacted monomer
is recompressed, cooled and recycled to the bottom of
the reactor.
3.3. Eficts of particle size
The two-phase bubbling-bed model developed in
this article assumes that all particles have the same
mean diameter of 0.05 cm, whereas in actual fact the
continuous addition of catalyst and removal of product leads to a distribution of particle sizes ranging
from 0.005 to 0.2 cm. Talbot (1990) used population

K. B. MCAULEY et al.

2042

balances and statistical distributions to develop mathematical models for predicting the particle size distribution in fluidized-bed polyethylene reactors.
If all particles in the reactor are of the same size,
then an increase in particle size leads to an increase in
terminal velocity and to a larger maximum stable
bubble size. A secondary effect is to increase the minimum fluidization velocity which allows a greater
superficial velocity without causing elutriation. Particle populations with a distribution of sizes can be
summarized using a number of different average particle diameters (Allen, 198 1); for example, the numberlength mean diameter, the number-volume mean
diameter, the length-surface mean diameter and the
surface-volume mean diameter. Each of these mean
diameters uses a single particle size to match the
original distribution in two properties. For example,
using the number-volume mean diameter, the original
distribution is approximated by a population of uniform particles with the same number of particles and
the same total volume. The total surface area and the
sum of all particle diameters will not match that of the
original distribution. Each of the different means
weights the contributions of small and large particles
differently.
The small particles in the distribution have a lower
terminal velocity and are expected to influence the
maximum stable bubble size more than larger particles. Thus, a particle population with a broad distribution of particle diameters may lead to a smaller
maximum stable bubble size than predicted using the
number-length or number-volume mean diameter.
These smaller bubbles would then lead to smaller
differences between emulsion and bubble-phase conditions than predicted by our model. The large particles in the distribution have a higher terminal velocity than the average particle, and have a greater
tendency to rain through the bubbles, thereby enhancing heat and mass transfer rates between the
bubble and emulsion phases. Thus, we expect that
a model that properly accounts for the effects of
a broad particle size distribution on the maximum
stable bubble size will predict enhanced heat and mass
transfer rates compared with our model for particles
raining through the bubbles, and would give predictions closer to those of the simplified well-mixed
model described in the next section.
4. A SIMPLIFIED

WELL-MIXED

MODEL

In the limiting case, where bubbles are very small or

interphase mass and energy transfer rates are very
high, c = C, and z = T,. To examine the validity of
this assumption, made by McAuley et al. (1990), we
derive a back-mixed model and compare its predictions with those of the detailed two-phase model.
4.1. SimpliJied model development
In the simplified model, there is unrestricted gas
and heat flow between the bubble and emulsion
phases, and the temperature and composition are uni-

form in the gas phase throughout the bed. This type of

model could be derived simply by setting K,,, and H,
in eqs (3), (6), (11) and (12) to very large values.
However, this approach leads to numerical difficulties
as (c, - C,) and (z - T,) approach zero. Rederiving
the model equations with the assumption of unrestricted mass and energy transfer between the bubble
and emulsion phases provides a more reliable numerical solution. Assuming that the gas composition, C, is
uniform in the emulsion and bubble phases, the following steady-state mass balance can be written for all
of the monomer in the bed:
0 = AU,(C,

- C) - QCE,,

- Rp/Mw.

(14)

As in eq. (3), we assume that the product stream

leaving the reactor is at its minimum fluidizing conditions. Since QC&,,,, is much smaller than the other
terms in eq. (14), the validity of this assumption is not
crucial.
Assuming that the bubbles and the emulsion are at
the same temperature, T, we can write the following
energy balance on the reactor contents:
0 = AU,C&(T,,

T)

+ RpC - AH - (c, - c,) (T -

- xDHU,(T - T,).

Tr,,)l
(15)

As in eq. (6), we have neglected the effect of concentration change on the enthalpy of the gas leaving the
reactor. We have also neglected the enthalpy associated with the catalyst feed stream because it is
small compared with the other terms in eq. (15). The
remainder of the simplified model consists of eqs (4),
(5) and (9). This set of five equations in six unknowns
can be solved for any steady-state temperature between 325 and 400 K by the following steps. First,
choose a value of T and solve for R, in eq. (15). Next,
assuming that q.., in eq. (4) is small, solve for Q. Given
R, and Q, solve eq. (14) for C and eq. (9) for X,,,.
Finally, obtain qea, from eq. (5).
The values of S and E,,,/ in eq. (9) must be the same
as those in the full two-phase model in order to obtain
the same solid-phase residence time in the bed. Information about the bubbIe fraction and voidage is
not required in back-mixed models that assume a constant mass of polymer in the bed rather than a constant bed height.
4.2. Comparison of two-phase and well-mixed models
For given monomer inlet conditions, particle size
and catalyst feed rates, the differences between the two
models depend on the superficial gas velocity and the
bubble diameter.
4.2.1. The effect of super$cial gas velocity. At low
to moderate emulsion temperature, Fig. 3 shows that
the difference between the predictions of the two
models is very small, approximately 3 K near temperatures of 370 K and less than 2 K near 360 K. At the
same operating conditions, the differences between
the predicted concentrations in the gas phase sur-

Comparison

+
0

of two-phase and well-mixed models

,,h___
0.1

0.2

Catalyst

0.3

Fig. 3. Comparison of the predicted reaction temperatures

for the simplified and two-phase models at superficial
velocities of 3U,, and 6U,,,,, assuming 15 cm bubbles.

rounding
the particles are on the order of 1 or 2%.
Both models predict that multiple steady states can

occur. Like the model of Choi ad Ray (1985a), if

temperatures beyond the melting point of the polymer
are considered,
both models predict the existence of
up to three steady states for a given catalyst feed rate.
The difference between the simplified model predictions for the 3U,,,, and 6U,,,f cases is a result of the
change in the relative quantities of gas and solids in
the bed required to maintain a constant expanded bed
height. As the gas feed rate to the bed increases, the
solid-phase
residence
time is reduced
quantity of catalyst in the reactor.

as

is

the

Fig. 4. Comparison

CONCLUSIONS

The model of Choi and Ray (1985a) describing

ethylene polymerization in a fluidized-bed polyethylene reactor has been revised to account for a maximum stable bubble size in the reactor, and to better
model the resistances to heat transfer between the
bubble and emulsion phases. Our model does not
account for bubble coalescence and breakup, cloud
shedding, the influence of small particles in the particles size distribution on the maximum stable bubble
size, nor the presence of particles raining through the
bubbles. We expect that all of these phenomena lead
to smaller heat and mass transfer resistances between
the bubble and emulsion phases than is predicted by
our two-phase model, and that the true behaviour of
the gas concentration and temperature lies between
the predictions of the two-phase and simplified
models. Simulations show only minor deviations between the predictions of the two-phase and backmixed models for superficial velocities in the range of

----,
0.2
0.3
Catalyst Feed Rate
[g/s]

of the predicted

reaction

0.4

( 5

temperatures

for the simplified and two-phase models with bubble diameters of 10 and 40 cm, using a superficial velocity of 6U,,,,.

3U,, to 6U,,,I and for the small bubble sizes predicted

by the maximum stable size correlations. Based on
this analysis we recommend the use of a well-mixed
assumption
when
modelling
commercial
gas
fluidized-bed polyethylene reactors.
Acknowledgements-The authors wish to acknowledge the
financial support of the Natural Sciences and Engineering
Research Council and Queens University.
NOTATION

A
Ar

6
The effect of bubble diameter. As shown in
Fig. 4, there is very little difference between the wellmixed and two-phase model temperature predictions
if the bubble size is 10 cm. However, for large bubbles
at high operating temperatures, the difference can be
significant. The same result applies to the monomer
concentration in the gas surrounding the polymer
particles.
4.2.2.

5.

_~~
0.1

0.4

Feed Rate [g/s]

2043

G
d
D
9
9
H
HbC
H,,
H,
AH
k
k,
L
MW
P
ClCPl

Re
R,
T
z
u
u#%

reactor cross-sectional area, cm2

Archimedes number [ = dip&,
- pg)g/&]
heat capacity, J/gmol/K
heat capacity, J/g/K
concentration of ethylene, mol/cm3
average ethylene concentration in bubble
phase
diameter, cm
reactor diameter, cm
self-diffusion coefficient for ethylene, cm2/s
gravitational acceleration, cm/s
bed height, cm
bubble to cloud heat interchange coefficient,
J/cm3/s/K
cloud to emulsion heat interchange coefficient, J/cm/s/K
overall
heat
interchange
coefficient,
J/cm 3/s/K
heat of reaction, J/g
thermal conductivity, J/cm/s/K
rate constant, cm3/g cat/s
mass transfer coefficient, s-l
molecular weight, g/mol
pressure, atm
catalyst feed rate, g/s
product rate, cm/s
Reynolds number (Remf = peU,,,,D/u,)
reaction rate, g/s
temperature, K
average bubble temperature, K
velocity, cm/s
wall heat transfer coefficient, J/cm/K/s

2044
V

X -x1
Z

K. B. MCAULEY et al.

volume, cm3
catalyst mass fraction
height above distributor, cm

Greek letters
volume fraction bubbles in bed
S
&
voidage of emulsion phase
viscosity, poise
P
density, g/cm
P
Subscripts
bubble property
b
cloud property
c
cat
catalyst property
emulsion property
e
B
gas propew
minimum fluidization conditions
4
polymer property
PO1
reference value
ref
polymer property
s
terminal
T
entrance or superficial conditions
0
ambient condition
03
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