242 | Macromol. Symp. 2013, 333, 242247 DOI: 10.1002/masy.

201300092

Condensed Mode Cooling in Ethylene

Polymerisation: Droplet Evaporation
Arash Alizadeh,1,2,3 Timothy F.L. McKenna*1

Summary: A simplified model is used to explore the mechanisms for droplet

vaporisation in fluidised bed reactors used for the production of polyethylene in the
gas phase. Both homogeneous and heterogeneous vaporisation models are
considered. It is shown that for a reasonable range of droplet sizes (less than 1 mm in
diameter), droplet vaporisation will be essentially complete at bed heights on the
order of 1 m.

Keywords: condensed mode cooling; fluidised bed reactor; polyethylene

Introduction exchanger unit of the condensed mode

The rate of production in gas phase olen
polymerisation reactors, and in particular
uidised bed reactors (FBR) for ethylene
polymerisation, is limited by the rate at
which the heat of reaction can be removed.
Condensed mode operation, where a par-
tially liqueed recycle stream containing a
compound such as i-pentane or n-hexane
(inert condensing agents ICA) is injected
into the reactor with the feed. The liquid, in
the form of droplets is thought to evaporate
at hot spots in the bed, thereby using the
associated latent heat of evaporation in the
reactor to help cool the bed.
Therefore we would like to understand
where/how this takes place inside the
reactor. Obviously parameters like droplet
size, size distribution, heat of vaporisation
and properties of solid particle phase (like
solid ux inside bed, size distribution, and
heat capacity) as well as eventual contact
between these two phases will control the
overall vaporisation process of the liquid
droplet in the presence of uidising solid
particles. Jiang et al. studied the heat
process in a series of papers.[13] Their
analysis provides some interesting recom-
mendations from process point of view. For
example, it has been found that the lower
operating pressure of heat exchanger
inhibits the rate of heat transfer, or for
optimizing the heat removal rate the
makeup ethylene should be added after
the heat exchanger while makeup hexene as
condensable agent should be before the
heat exchanger. While very useful, this
global analysis does not explain what
happens inside the reactor at the level of
the droplets.
However, despite extensive experimen-
tal and modeling studies in FCC and the
combustion literature, to the best of our
knowledge, there is no single modeling
approach which captures effect of all the
parameters inuencing the droplet vapor-
isation in the uidised bed with a phenom-
enological description. The objective of the
current paper is to attempt to quantitatively
understand what inuences the rate of
evaporation of droplets of ICA injected
into the bottom of a uidised bed reactor
for the production of polyethylene.[4]

1
C2P2 - LCPP Group, UMR 5265 CNRS, Universit de
Lyon, ESCPE Lyon, Bat 308F, 43 Bd du 11 novembre
Results
1918, F-69616, Villeurbanne, France
E-mail: timothy.mckenna@univ-lyon1.fr Droplet Vaporisation: How Long Do
2
Dutch Polymer Institute DPI, POBox 902, 5600, AX,
Droplets Exist?
Eindhoven, the Netherlands
3
Department of Chemical Engineering, Queens Different scenarios for the liquid droplets
University, Kingston, ON, Canada, K7L 3N6, Canada introduced to a hot environment of

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Macromol. Symp. 2013, 333, 242247
uidising particles can be found in the
literature. If the droplet is small enough
there is a chance that it will vaporise
homogenously before making any con-
tact with the solid particles uidising in the
bed. Otherwise, liquid-solid contact will be
inevitable and we nd heterogeneous
evaporation.
We therefore need rst to analyse the
relative time scales for droplet heat up and
vaporisation compared in case of homoge-
nous vaporisation of the droplet. For
heterogeneous vaporisation we consider
heat transfer during (1) sticky collision
between droplet and particles and (2)
elastic collisions between droplet and
particles. Elastic collisions will be important
when the temperature of the particle
approaches the Leidenfrost temperature.
This value is approximately 150
C above
the saturated vapour temperature of the
droplets.[5] Thus it is not expected that this
will occur during ethylene polymerisation,
the vaporisation time obtained in this case
will be representative of upper limit of the
vaporisation time of droplet in presence of
solid particles, while vaporisation time
assuming fast heat transfer between drop-
lets and particles will be representative of
lower limit of it.
Homogeneous Vaporisation
In the case of homogeneous vaporisation,
the lifetime of the cold droplet introduced
to a hot environment is split to two
overlapping periods. First the droplet heats
up rapidly, then the droplet vaporises at
constant temperature i.e. the wet-bulb
temperature in our case. It is assumed that
droplet composition is pure isopentane and
gas phase is of composition given in Table 1
at 80
C and 20 bars, and the properties of
Table 1.
Representative gas phase composition for
condensed mode.
Component Mole fraction
Ethylene 0.5
Hydrogen 0.1
Nitrogen 0.25
Iso-pentane 0.15
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| 243


gas phase at 80 C and 20 bars and liquid
phase at 80
C are given in Table 2.
It is essential to have reasonable estima-
tion of relative velocity of liquid droplet and
surrounding gas phase (the gas-liquid slip
velocity) during the course of heating up
and evaporation in our calculations. The
gas-liquid slip velocity for the injection
devices are reported ranging from 7-30 m/s
in the literature.[15] By considering the fact
that liquid droplets are introduced to a slow
moving environment of uidising particles
where supercial gas velocity[4] is in the
order of 1 m/s, the gas-liquid slip velocity of
uslip 10 m/s has been used through our
analysis in this section as a compromise. We
could not nd an indication about gas-liquid
slip velocity in case of introduction of liquid
droplets entrained in the gas phase in the
literature nor patents, so will test the
sensitivity of the calculations to this value.
The droplet size distribution depends on
the type of injection devices with average
size ranges being reported to be between
50-4000 mm[8]. In the case of the introduc-
tion of liquid as entrained droplets the holes
of the distributor are of a maximum
diameter of one half inch (12500 mm), so
maximum droplet size of diameter 5000 mm
seems a reasonable approximation. As a
result our analysis will cover droplet size
distribution of 50-5000 mm.
In order to calculate the time scale for
heat up and vaporisation of droplet in the
second step, it is essential to estimate the
temperature of the droplet during the
vaporisation. In our analysis, this will be
approximately by the wet-bulb tempera-
ture. At this temperature the rate of heat
transfer from the gas phase to the liquid will
be equal to the rate of heat removal from
droplet by evaporation:
hT g T w km Ceq Cb DH v 1
where Tg and Tw are the gas phase and wet-
bulb temperatures; Ceq and Cb are concen-
tration of isopentane in gas phase in
equilibrium with liquid isopentane and
concentration of isopentane in bulk gas
phase. Ceq can be obtained from isopentane
vapour pressure. km, the mass transfer
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244 | Macromol. Symp. 2013, 333, 242247

Table 2.
Properties of gas phase of composition given in Table 1 at 80
C and 20 bars and liquid isopentane and
polymer particles at 80
C.
Property Symbol Value Units
Density - liquid[7] rl 553.4 kg/m3
Density - gas[7] r 21.8 kg/m3
Density - particle rp 900 (estimate) kg/m3
Heat Capacity - liquid[7] CpL 2593.5 J/kg.K
Heat Capacity - gas[7] Cp 1734.7 J/kg.K
Heat Capacity - particle[7] Cpp 2000 J/kg.K
Kinematic viscosity gas[6,7] n 6.2  107 m2/s
Thermal conductivity - gas[7] kf 3.1  102 W/m.K
Latent heat of vaporisation

[7]
DHv 21077 kJ/kmol
Diffusivity isopentane[6 ] Di-C5 5  107 m2/s
Vapor Pressure isopentane[7] Pvp 4.6 bar

Diffusivity of isopentane in gas phase of composition mentioned in Table 1.

coefcient, and h, the heat transfer coef- droplet decreases when there is a substan-
cient, are obtained from the Ranz- Marshall tial vaporisation from droplet.[15] As a
correlations: result, the heat transfer coefcient for a
vaporising droplet must be calculated
km d differently than for a particle:[8]
Sh 2 0:6Re1=2 Sc1=3 2
D 
hd  hd Nu
Nu 2 0:6Re1=2 Pr1=3 3 Nu 7
kf kf 1 Bn
With a gas phase temperature of 80
C, where Nu is the Nusselt number obtained
the wet-bulb temperature is estimated to be from Ranz-Marshall correlation, h and
61
C. Nu are the effective heat transfer coef-
It can be shown that the governing cient and Nusselt number for droplet in the
equation during the heat up period of an presence of vaporisation. n is a constant
isolated droplet is given by equal to 0.7 and B is given by
dT  
t T g T 4 cp T g T QR
dt B 1 8
DH v Qc
where cp is heat capacity of gas phase, ~Hv is the
t r1 Cpl d=6h 5 heat of vaporisation of liquid. QR/QC is the
ratio of heat transferred to the droplet by
In this approach, a uniform temperature radiation to convection, which can be
inside the droplet is assumed. The solution assumed to be equal to zero in operational
to equation (4) is: conditions of condensed mode polyolen


T g T reactors.
t t ln 6 Assuming that all the heat transferred to
T g T o
the droplet is consumed for evaporation of
Where Tg and T0 are the gas and initial liquid from the droplet, it is possible to write
droplet temperature. For the droplet heat the governing equation for evaporation as
up step, the time needed for a droplet
initially at 50
C to reach a wet-bulb dV 
DH v rl h AT g T 9
temperature of 61
C is shown in Table 3 dt
for different conditions. where V and A are droplet volume and
It is found empirically that the heat surface area. T is the evaporation tempera-
transfer coefcient from gas phase to a ture of the droplet which (wet-bulb

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Macromol. Symp. 2013, 333, 242247 | 245
Table 3.
Estimation of time scales for isopentane droplet heat up and homogeneous vaporisation (uslip 10 m/s).
Droplet Size (mm) 50 100 300 1000 3000 5000
Heat up Time (sec) 5.0  104 1.5  103 7.8  103 4.9  102 0.26 0.55
Vaporisation Time (sec) 1.3  102 3.9  102 2.1  101 1.4 7.1 15.4

Heat up time from 50
C to the wet-bulb temperature of 61
C.

temperature). Substituting for V and A particles, Buchanan[15] considered two limit

allows us to rewrite equation (9) as: cases of heat transfer between droplets and
 particles. In the rst limit, all of the heat
dd 2h T g T
10 possible from particles is transferred to
dt DH v rl droplet instantaneously. The formulation
The solution to equation (10) results in for this limit results in following correlation
following correlation for vaporisation for estimation of droplet vaporisation

 
DH v rl 2 1 3 1
tvap 0 0 1v 3
1v2
31y0 ln 11
A T g T B 4 3
0
2 0
y0

where A and B are clustered functions dd yrp 1eCpp T p T

dened as
0 kf
A l m 12
C T T 0:7
1 p DHg v
 u 0:5
0 It is assumed that the particle tempera-
B 0:6Pr1=3
2v
and v0 1 Br00.5 in which ro is the initial
droplet radius.
The time needed for droplets of size
between 50-5000 mm to vaporise homo-
geneously at slip gas-liquid velocity of
uslip 10 m/s are given in Table 3. By
comparing the time scale for droplet heat
up and vaporisation, it can be concluded
that the heat up time is negligible compared
to vaporisation step. As a result, in our
discussion about heterogeneous droplet
vaporisation in the presence of solid
particles we will focus on the vaporisation
step assuming that droplet reaches steady
state temperature of vaporisation instan-
taneously. It can also be seen that the time
scale for vaporisation is relatively rapid as
well, except for the largest droplets.
Heterogeneous Droplet Vaporisation
In order to estimate the time scale for the
vaporisation of droplets in the presence of
14
dt 2rl DH v
where e is the bed porosity and we use the
value of bed porosity at minimum uid-
isation of 0.5 as an estimation.
13
ture (Tp) is the same as the temperature of
the gas phase (Tg) and that the particle is
cooled down immediately to the droplet
vaporisation temperature when particles
and droplets collide. The rst assumption is
not always valid, especially for the small
active polymer particles. However, the
correction for this will only result even
shorter time scales for vaporisation of
droplets. Consequently it is decided to
keep this assumption despite its obvious
imperfections. Similar to the case of
homogeneous vaporisation, the vaporisa-
tion temperature of the droplet is estimated
as wet-bulb temperature. In this event we
are able to calculate the lower limit of
vaporisation time as given in Table 4 for 2
different slip velocities.
In the second limiting case (upper
limiting time, or lower limit of heat
transfer), the collisions between droplet
and particles are assumed to be elastic.
Considering the observed trend of a
decrease in heat transfer coefcient to

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246 | Macromol. Symp. 2013, 333, 242247
Table 4.
Heterogeneous vaporisation time estimates of time scales for isopentane droplet heterogeneous
vaporisation.
Droplet Size (mm) 50 100
uslip 10 m/s
Lower Limit (sec) 9.5  105 1.9  104
Upper Limit (sec) 2.4  103 6.8  103
uslip 1 m/s
Lower Limit (sec) 9.5  104 1.9  103
Upper Limit (sec) 9.7  103 2.8  102
immersed objects by dilution of uidised
bed,[912] Buchanan proposed a correction
for heat transfer coefcient for homo-
geneously vaporising droplet seen in equa-
tion (9). In this correction the gas phase
density r in Re number is replaced by gas-
solid density, rp(1-e). Taking this correction
into account will result in similar equation
for estimation of droplet vaporisation as
equation (11), except that the cluster
parameter of B in equation (13) is replaced
by B:
 between 1 and 2 m. As a result the heat of
00 0 rp 1e 1=2
B B 15
p from the particles uidising only in this
This vaporisation time is intended to be
representative of higher limit of droplet
vaporisation time in the presence of solid
particles. These results are also shown in
Table 4. Both the upper and lower
characteristic times are calculated at differ-
ent slip velocities because of the uncertain-
ties mentioned above.
Of course these time scales should be
treated as a qualitative estimation due to the
large number of assumptions used in their
calculation. Also, this approach also does
not take into account the local hydrody-
namics of the bed, the heat capacity of solid
phase, possibility of distribution of liquid
between particles and droplet surface defor-
mation. Nevertheless, it is not unreasonable
to assume that the real vaporisation time to
be between two limits of the heat transfer in
the heterogeneous vaporisation. If this is the
case, then it can be concluded that an
isopentane droplet of 5000 mm will vaporise
in a time of between 1 and 5 seconds. That
limit is for the largest droplets in the range
2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
300 1000 3000 5000
5.7  104 1.9  103 5.7  103 9.5  103
3.6  102 0.22 1.1 2.4
5.7  103 1.9  102 5.7  102 9.5  102
1.5  101 0.95 5.0 10.8
studied. It is much more likely that the
injected droplets are really an order of
magnitude smaller. This tells us that vapor-
isation is indeed almost instantaneous in
terms the time the ICA will spend in the bed.
Conclusion
Based on these calculations expect that the
major part of the liquid injected through the
bottom of an FBR is vaporised at a height of
evaporation enhances the heat removal
fraction of bed. Given the impressive
enhancement of productivity reported in
the patent literature, it is not unreasonable
to speculate that the presence of inert
ICA might have other effects.
It is well-known that the nature of the
gas phase in an FBR can have a signicant
impact on heat transfer if the standard inert
component of nitrogen is replaced by a gas
such as helium[13] or propane[14]. Since the
evaporation process is quite rapid the gas
phase will be quite rich in the heavier ICA.
This will enhance the thermal conductivity
and heat capacity of the gas phase.
It should also be noted that the alkanes
used as ICA are more soluble in polyethyl-
ene (PE) than is ethylene, and since the
feed will contain 10-30 wt% of such com-
pounds, the polymer particles will contain
considerable amount of them. The dissolu-
tion of heavier alkanes can have different
effects, including a cosolubility effect that
can increase the quantity of ethylene in the
particles, as well as a plasticizing effect that
might increase the diffusivity of the
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Macromol. Symp. 2013, 333, 242247
monomer through the polymer layer sur-
rounding the active sites (these inuences
will be discussed in forthcoming papers
from our group).
It can also be speculated that if the
temperature of a polymer particle begins to
increase, for instance due to the local
deuidisation inside the reactor, the partial
desorption of the sorbed ICA will also help
to improve heat transfer from the particles.
This would ultimately result in lower
uctuation of the temperature of growing
polymer particles inside the reactor while
lowering the risk of polymer fusion and
local formation of polymer agglomerates.
We will explore the signicance of these
different aspects in future papers.
Acknowledgement: The authors are grateful to
the Dutch Polymer Institute for nancial and
technical support.
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