1176 Ind. Eng. Chem. Res.

1997, 36, 1176-1180

Heat Removal from Gas-Phase Polyethylene Reactors in the

Supercondensed Mode

Yan Jiang, Kim B. McAuley,* and James C. C. Hsu

Department of Chemical Engineering, Queen’s University, Kingston, Ontario, Canada K7L 3N6

For gas-phase fluidized bed polyethylene reactors, heat removal is one of the controlling factors
that limits the production rate. Since the invention of condensed mode operation, several process
improvements for enhancing heat transfer have been discovered. In the current article, a
nonequilibrium model for multicomponent condensation in vertical heat exchangers described
by Jiang et al. has been used to simulate supercondensed mode operation and to test other new
designs for heat removal from polyethylene reactors. It appears that a larger heat exchanger
or a significant change in the inlet conditions of cooling water is not required for supercondensed
operation, in which substantially higher amounts of heat are removed and substantially higher
production rates are achieved. It is found that operating at higher reactor temperatures can
lead to a 1.1%/°C increase in both heat removal and production rates. Decreasing the operating
pressure of the heat exchanger inhibits heat transfer. Makeup ethylene should be added after
the heat exchanger, and makeup hexene should be added before the exchanger to maximize
heat removal.

Introduction
The discovery of the gas-phase fluidized bed polym-
erization process in the late 1970s lead to a dramatic
reduction in capital investment for polyethylene plants
and to new possibilities for polymer properties. Since
that time, industrial research has continued toward
further process improvements, including increases in
production rates. The production rate in commercial
gas-phase polyethylene reactors is restricted by the
maximum rate at which heat can be removed from the
reactor. The preferred method for removing the heat
of polymerization is through removing the unreacted gas
from the reactor and cooling it by passing it through
an external heat exchanger, before recycling it to the
bed at a temperature lower than the desired polymer-
ization temperature (see Figure 1). Obviously, the rate
of heat removal can be increased by reducing the
temperature of the gas recycled to the reactor. How-
ever, it had long been assumed (Jenkins et al., 1986)
that the temperature of the recycle gas could not be Figure 1. Industrial gas-phase polyethylene reactor system
lowered any further than its dew point, because the scheme.
introduction of liquid into a gas-phase fluidized bed
reactor would inevitably result in plugging of the recycle encourage greater levels of condensation, as suggested
lines or gas distributor plate or accumulation of liquid by Jenkins et al. (1986).
at the bottom of the reactor, which would interfere with
continuous operation or result in complete reactor To satisfy the requirement that the gas-to-liquid ratio
shutdown. in the recycle stream be maintained at a level sufficient
Contrary to this widely held belief, Jenkins et al. to keep the liquid phase of the two-phase flow entrained
(1985, 1986) discovered that the recycle gas can be in the vapor, Jenkins et al. (1986) recommended that
cooled below its dew point and the resulting liquid/vapor the level of liquid in the recycle stream be in the range
mixture returned to the reactor without plugging or between 2 and 12 wt % and not exceed 20 wt %.
other problems. The introduction of this “condensed Recently, DeChellis and Griffin (1994) demonstrated
mode” operation can lead to substantial increases in that gas-phase polyethylene reactors can be safely
production rate without enlarging the reactor. In operated at even greater levels of condensation, thereby
condensed mode operation, the extent to which the leading to even greater increases in the production
recycle gas can be cooled is limited by the temperature rates. However, if too much condensable inert is added
of the industrial cooling water available on site. This to the reaction gas, an undesirable fluidization regime
constraint can be alleviated by adding condensable can be established in the reactor. DeChellis and Griffin
material to raise the dew point of the recycle steam and (1994) recommend using pressure measurements to
monitor the fluidized bulk density in the bed to ensure
* Author to whom correspondence should be sent. E-mail: that the condensation rates are kept low enough to
mcauleyk@cheemat.chee.Queensu.ca. Fax: 613-545-6637. Tele- prevent this problem. In this improved process, the
phone: 613-545-2768. level of liquid in the recycle stream can be greater than
S0888-5885(96)00485-X CCC: $14.00 © 1997 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997 1177
Table 1. Model Equations
differential material balance for each species of the mixture
dVi dLi
) -Ni ) - i ) 1, 2, ..., n (1)
dA dA
molar flux (i.e., multicomponent mass-transfer) equations

(N) ) [kV][Ξ](yV - yI) + Nt(yV) (2)

liquid phase assumed completely mixed with regard
to composition

xiI ) xiL ) Li
/∑ Lj (3)

assumed equilibrium between the liquid and vapor phases at

the interface

yiI ) KixiI i ) 1, 2, ..., n (4)

energy balance for the vapor phase

dTV
mVcPV ) -qV (5)
Figure 2. Separator introduced into the gas-phase polyethylene dA
reactor system to split the recycle stream into a liquid stream and energy balance at the liquid/vapor interface
a vapor stream.
ho(TI - Tc) ) qV + ∑N i
L
cPiV(TV - TI) + ∑N i
L
∆hi (6)

20% by weight and the production rates are typically
85% greater than in the traditional condensed mode.
The amount of liquid that can be condensed in the
recycle stream and, consequently, the amount of heat
that can be removed also depend on the concentrations
of certain components in the recycle gas, such as hydro-
gen, nitrogen, and light comonomers, which are difficult
to condense and can impede heat transfer (Jiang et al.,
1996b). Gas-phase polymerization processes are now
being operated with new metallocene catalysts that
require significantly lower levels of hydrogen and
comonomer in the gas phase than traditional Ziegler-
Natta catalysts to produce a polyethylene product with
specified properties. When these new catalysts are used
and heavy inert components are added to augment heat
removal in the external exchanger, condensation levels
of up to 50%, most preferably between 25 and 40 wt %,
can be obtained (DeChellis et al., 1995). Operation at
such high condensation levels has been called the
“supercondensed mode” (Morgan-Grampian, 1995).
Because the polymer particles produced using met-
allocene catalysts can have higher sticking tempera-
tures than the polyethylene produced using Ziegler-
Natta catalysts, gas-phase reactors can be safely operated
at slightly higher temperatures with metallocenes with-
out risking particle agglomeration. As shown in Figure
1, an increase in the reactor temperature will naturally
lead to a higher gas inlet temperature to the heat
exchanger and to a greater driving force for heat
transfer to the cooling water. This greater driving force
should lead to greater heat-removal rates from the
reactor system for a given cooling water inlet temper-
ature and flow rate.
An additional improvement that has been suggested
for condensed mode operations is to divide the recycle
stream into two or more separate streams (Jenkins et
al., 1986; DeChellis and Griffin, 1994). For example,
the recycle stream can be divided into a liquid and a
gas stream which can then be separately introduced into
the reactor (see Figure 2). A more recent patent (BP,
1994) fully focuses on this issue and gives a detailed
description about how and where the separating and
reintroducing could be done. By separating the liquid
from the gas and then feeding the liquid directly to the
fluidized bed at several locations, the total amount of
liquid which can be reintroduced into the fluidized bed
energy balance at the wall
hL(TI - TW) ) hWc(TW - Tc) (7)
energy balance for the coolant
dTc
mccPc ) -hWc(TW - Tc) (8)
dAouts
might be increased without introducing fluidization
problems. Splitting the liquid and vapor stream also
gives some flexibility in the location of the compressor
which is used to pressurize the recycle gas before it is
fed to the bottom of the reactor. The compressor could
either be placed before the heat exchanger as in Figure
1 or on the vapor line following the heat exchanger as
in Figure 2 if the liquid and vapor are separated. These
two placements of the compressor result in different
pressures in the heat exchanger and may result in
different heat-removal rates. There is also considerable
flexibility in where the makeup monomer and comono-
mer can be added to the system. It could be added to
the recycle stream before the exchanger or after the
exchanger to the liquid or gas feed stream.
From the above overview, it can be seen that many
improvements and new designs have been introduced
for condensed mode operation of gas-phase polyethylene
reactors. The objective of this article is to use the model
developed by Jiang et al. (1996a,b) to simulate these
proposed new designs and to determine which factors
lead to greater improvements in heat-removal and,
hence, production rates. For example, can a heat
exchanger used for traditional condensed mode opera-
tion remove enough heat to operate at significantly
higher rates in the supercondensed mode, how does the
potential temperature increase in the reactor affect the
amount of heat that can be removed, how does the
operating pressure in the heat exchanger affect the
heat-removal rate, and where should the makeup
monomer be added to the system?
Model Equations
The complete model equations are summarized in
Table 1. A detailed description of the model develop-
ment can be found in Jiang et al. (1996a). Two equa-
tions in Table 1, eqs 3 and 4, are model assumptions.
1178 Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997

Table 2. Comparison of Simulation Results for a mode operation and its benefits. We have used the
Traditional Condensed Mode Operation (Run 1) with or nonequilibrium model developed by Jiang et al. (1996a)
without the Impurities
to simulate several of the examples from DeChellis et
without with al.’s patent (1995). Because the information about the
impurities impurities heat-exchanger unit is not provided, a typical vertical
base case pat.a simul pat.a simul heat exchanger (Jiang et al., 1996b) employed in a
TinV, °C 78.9 78.9 traditional condensed mode operation is used to see
pressure, kPa g 2110 2110 whether it is adequate for providing cooling under
ethylene, mol % 32.5 32.5 supercondensed mode operation. Run 1 in Table 2 was
ethane, mol % 0.65 chosen as a base case, because it presents traditional
iC5, mol % 1.0 1.0 condensed mode operation and is actual plant data. As
H2, mol % 11.8 11.8
N2, mol % 48.6 48.6
described by DeChellis et al., the patent data of runs 2
hexene, mol % 4.3 4.3 and 3 of Table 3 were prepared by extrapolating
hexane, mol % 1.15 information from actual operations using thermody-
total mol fract, mol % 98.2 100 namic equations, well-known in the art, to project actual
Tdew, °C 64.3 57.20 64.34 conditions and production rates in the supercondensed
% condensed 11.6 6.32 9.98 mode.
ToutV, °C 40.4 40.43 40.42 For run 1, from the computation results shown in
prod rate, tons/h 26.1
Table 2, it can be seen that the calculation results of
heat removed/tube, MJ/h 74.891 90.922 the dew-point temperature are quite different between
Tinc, °C 36.13 36.21
Toutc, °C 51.31 52.80 the patent data (64.3 °C) and this simulation (57.2 °C
water flow rate, kg/s 550.7 550.7 calculated by normalizing the mole fraction of the
recycle gas rate, tons/h 1100 1100 components), because the total mole fraction of the
a Data in bold are from Table 1, run C-1, in DeChellis et al. recycle gas mixture is only 98.2%. Impurities which are
(1995). not shown in the patent were probably included in dew-
point calculations by DeChellis et al. (1995). Two
The model equations are completed by the following possible impurities which are present in gas-phase
additional two assumptions: polyethylene reactors but are not listed in the patent
(i) The pressure is assumed to be constant throughout information are ethane and hexane. In the third column
the heat exchanger. of Table 2 (and in Table 3), appropriate amounts of
(ii) The bulk temperature in the liquid phase is ethane and hexane were added to the recycle stream to
approximated by the arithmetic mean of the interfacial match the dew point with that provided by DeChellis
temperature and the tube wall temperature: TL ) (TI et al. The inlet cooling temperature, Tinc, and the
+ TW)/2. coolant flow rate were not provided by DeChellis et al.
Numerical methods for solving the model equations (1995). The values shown in Table 2 were adjusted so
are reported by Jiang et al. (1996a). that the simulation results can match the outlet vapor-
phase temperature, ToutV, for run 1. A typical value of
Simulation of the Supercondensed Mode the recycle gas flow rate was selected based on the gas
Operation velocity, the gas density provided in the patent, and the
geometry of a typical industrial reactor. Using the same
DeChellis et al. (1995) employed several examples to coolant flow rate as in the case without adding impuri-
provide a better understanding of the supercondensed ties, Tinc was adjusted so that the simulation results for

Table 3. Comparison of Supercondensed Mode Operation with Traditional Condensed Mode Operation (Assuming
Ethane and Hexane as Impurities To Make Up the Total Composition of the Recycle Gas Mixture to 100 mol % and To
Match Up the Dew Point in the Patent)
run 1, base case run 2, removing run 3, replacing
(trad condensed mode) most of H2 H2 and N2 by iC5
pat.a simul pat.a simul pat.a simul
V,
Tin °C 78.9 78.9 78.9
pressure, kPa g 2110 2110 2110
ethylene, mol % 32.5 39.8 39.8
ethane, mol % 0.65 0.15 0.886
iC5, mol % 1.0 8.5 21.1
H2, mol % 11.8 0.010 0.010
N2, mol % 48.6 50.1 37.6
hexene, mol % 4.3 0.6 0.6
hexane, mol % 1.15 0.84 0.004
Tdew, °C 64.3 64.34 46.9 46.90 73.4 73.82
% condensed 11.6 9.98 4.70 3.73 30.59 29.20
ToutV, °C 40.4 40.42 40.6 41.02 40.6 41.71
gas density, kg/m3 21.1 21.21 25.1 24.33 30.9 29.84
prod rate, tons/h 26.1 22.7 59.7
heat removed/tube, MJ/h 90.922 62.356 170.179
heat-removal rate/prod rate, (MJ/tube)/ton 3.484 2.747 2.851
Tinc, °C 36.21 36.21 36.21
Toutc, °C 52.80 50.28 58.89
water flow rate, kg/s 550.7 550.7 550.7
recycle gas rate, tons/h 1100 1100 1100
a Data in bold are from Table 1, runs C-1, -3, and -6 in DeChellis et al. (1995).
 Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997 1179
Table 4. Effects of Operating Conditions on the Cooling Capacity
base case increase and increase adding 30 tons/h C2 adding 0.9 tons/h C6
(traditional decrease in and decrease at 20 °C before/after at 20 °C before/after
condensed mode) TinV by in pressure by heat exchanger heat exchanger
pat.a simul -1 °C +1 °C -5% +5% before after before after
V,
Tii °C 78.9 77.9 79.9 78.9 78.9 77.70 78.9 78.86 78.9
pressure, kPa g 2110 2004.5 2215.5 2110 2110 2110 2110
ethylene, mol % 32.5 34.320 32.5 32.491 32.5
ethane, mol % 0.65 0.632 0.65 0.650 0.65
iC5, mol % 1.0 0.973 1.0 1.000 1.0
H2, mol % 11.8 11.482 11.8 11.797 11.8
N2, mol % 48.6 47.290 48.6 48.586 48.6
hexene, mol % 4.3 4.184 4.3 4.326 4.3
hexane, mol % 1.15 1.119 1.15 1.150 1.15
% condensed 11.6 9.98 10.03 9.95 9.58 10.35 9.45 9.98 10.07 9.98
ToutV, °C 40.4 40.42 40.29 40.52 40.50 40.33 40.53 40.42 40.40 40.42
Tdew, °C 64.3 64.34 64.34 64.34 63.06 65.56 63.40 63.34 64.48 64.34
gas density, kg/m3 21.1 21.21 21.28 21.14 22.30 21.30 21.21 21.22 21.21
heat removed/tube, MJ/h 90.922 89.942 91.926 89.179 92.434 89.636 91.732 91.278 91.145
Tinc, °C 36.21 36.21 36.21 36.21 36.21 36.21 36.21 36.21 36.21
Toutc, °C 52.80 52.52 53.08 52.65 52.92 52.68 52.80 52.82 52.80
a All data in bold are from Table 1 in Dechellis et al. (1995).

the base case with impurities can match ToutV as well.
It can be seen from Table 2 that after adding ethane
and hexane into the recycle stream, a better match with
the amount of condensate reported in the patent was
obtained. Using almost the same conditions of the inlet
cooling water, a significantly higher heat-removal rate
was obtained because of the higher dew-point temper-
ature of the recycle vapor and the resulting larger
amount of liquid condensed. The level of liquid con-
densed obtained by this simulation, 9.98 wt %, is still
less than the value reported in the patent. Most likely,
the value in the patent was obtained by a flash calcula-
tion assuming that the vapor and liquid are in equilib-
rium at the exit conditions of the exchanger, whereas
the simulated values reported in Table 2 were deter-
mined using the more rigorous nonequilibrium tech-
nique described by Jiang et al. (1996a).
Using the new metallocene system described by
DeChellis et al. (1995), significantly less hydrogen and
comonomer are required in the reactor to produce
polyethylene with a specified melt index and density or,
alternatively, with a specified weight average molecular
weight and comonomer content. For run 2, in Table 3,
it can be seen that by replacing most of the hydrogen
and hexene (which decreased from 11.8% and 4.3% to
0.01% and 0.6%, respectively) by isopentane and eth-
ylene, the dew point of the recycle stream is decreased.
Hence, the heat-removal rate is reduced, as is the
production rate, compared with run 1.
If some of the noncondensable nitrogen is replaced
by condensable isopentane (run 3), i.e., the system is
operated in supercondensed mode, much more liquid is
condensed in the recycle stream, and substantially
higher heat-removal rates are obtained. If we look at
the ratio of the simulated heat-removal rate per tube
to the reported production rate for runs 1-3, it can be
seen that these three values are of similar magnitude
for the same recycle gas flow rate under the same
cooling conditions (the same inlet cooling water tem-
perature and the same water flow rate). If it is possible
to remove enough heat to operate the reactor system at
22.7 tons/h using the conditions in run 2, then it will
most certainly be possible to operate at 59.7 tons/h using
the recycle gas composition suggested in run 3. It
appears that a larger exchanger or access to colder
cooling water is not required for supercondensed opera-
tion.
Effects of Operating Conditions on
Heat-Removal Rates
As mentioned in the Introduction, both DeChellis et
al. (1995) and the BP patent (1994) suggested some new
process operating conditions and designs that could
affect the ability of the external heat exchanger to
provide cooling for the reactor system. For example,
higher reactor and heat-exchanger inlet temperatures
can be tolerated using new metallocene catalysts. These
higher temperatures could enhance cooling and heat
removal. Also, as shown in Figures 1 and 2, whether
the compressor is placed before the heat exchanger or
following the heat exchanger on the vapor line will affect
the actual operating pressure in the exchanger and will
result in different heat-removal rates. Where the
makeup monomers are added to the system may also
result in different heat-removal rates. How these new
designs affect the heat-removal rate from the reactor
will be investigated in this section.
Run 1 in Table 2 is still used as a base case for
examining these potential improvements. As shown in
Table 4, for a 1 °C disturbance in the reactor temper-
ature with the cooling water inlet conditions held
constant, the exchanger will automatically remove 1.1%
more heat if the reactor temperature is increased or
1.1% less heat if the reactor temperature is decreased.
As a result, for every 1 °C increase in reactor operating
temperature that becomes possible due to higher poly-
mer sticking temperatures, the production rate can be
increased by approximately 1.1%.
In Table 4, it can also be seen that the cooling
capability of the recycle stream increases as the pres-
sure is raised and decreases as the pressure is reduced.
Compared to the base case, there will be a 1.7% increase
in the heat-removal rate if the pressure increases by
5% and a 1.9% decrease in the heat-removal rate if the
pressure decreases by 5%. This result shows that it is
better to compress the recycle vapor before rather than
after the exchanger in order to maximize the heat-
removal and production rates. It can be seen that
adding 30 tons/h of ethylene at 20 °C after the heat
exchanger (normal situation) is better than adding the
same ethylene before the heat exchanger (which reduces
TinV to 77.7 °C), because introducing more ethylene
reduces the dew point of the recycle stream. There is
about a 2.3% decrease in heat removal obtained by
1180 Ind. Eng. Chem. Res., Vol. 36, No. 4, 1997
adding the makeup ethylene monomer before the heat
exchanger compared to adding the makeup monomer
after the exchanger. From the final column of Table 4,
it appears, however, that is is better to add makeup
hexene comonomer before the heat exchanger to en-
hance condensation and heat removal.
Conclusions
Using the nonequilibrium model for multicomponent
condensation described by Jiang et al. (1996), the
supercondensed mode operation introduced by DeChellis
et al. (1995) has been simulated. The effects of changing
the operating conditions on the cooling capacity of the
recycle gas for polyethylene reactor systems has been
investigated. The following conclusions can be drawn:
With little change in the cooling water temperature
or flow rates, a typical vertical heat exchanger used in
traditional condensed mode operation can be employed
in supercondensed mode operation, thereby removing
the extra heat generated at the resulting higher produc-
tion rates.
The possible production and heat-removal benefits
obtainable from operating with metallocene catalysts at
higher reactor temperatures without sticking are ap-
proximately 1.1%/°C.
Decreasing the operating pressure of the heat ex-
changer inhibits heat transfer. If reactor systems are
designed with the compressor after the heat exchanger,
a reduction of approximately 1.9% in heat removal and
production rates will result from each 5% reduction in
exchanger pressure.
Makeup ethylene should be added after the heat
exchanger and makeup hexene should be added before
the heat exchanger to maximize heat removal.
Acknowledgment
We thank Queen’s University and the Natural Science
and Engineering Research Council of Canada for sup-
port of this research.
Nomenclature
A ) interfacial area, m2
Aouts ) surface area of the tube outside, m2
cP ) molar heat capacity, J kmol-1 K-1
h ) heat-transfer coefficient, W m-2 K-1
hWc ) heat-transfer coefficient accounting for the heat-
transfer resistances in the tube wall and in the coolant,
W m-2 K-1
∆hi ) latent heat of vaporization of component i, J/kmol
[kV] ) matrix of zero-flux mass-transfer coefficients, m s-1
Ki ) vapor/liquid equilibrium constants
Li ) molar flow rate of component i in the liquid phase,
kmol s-1
mV ) total molar flow rate of the vapor mixture, kmol s-1
mc ) coolant mass flow rate, kg s-1
Ni ) molar flux of component i, kmol m-2 s-1
P ) operating pressure in the exchanger, kPa
qV ) conductive heat flux out of the bulk vapor phase, W
m-2
T ) temperature, K
Vi ) molar flow rate of component i in the vapor, kmol s-1
x ) mole fraction in the liquid phase
y ) mole fraction in the vapor phase
[Ξ] ) matrix of high flux correction factors
Subscripts and Superscripts
c ) coolant
i, j ) component indexes or section numbers
I ) interface
in ) inlet condition
L ) liquid phase
o ) referring to overall parameter
out ) outlet condition
V ) vapor phase
W ) tube wall
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