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Fluidized bed reactor for polyethylene production. The influence of polyethylene

prepolymerization

Article  in  Brazilian Journal of Chemical Engineering · June 2000

DOI: 10.1590/S0104-66322000000200004 · Source: DOAJ

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Fabiano A N Fernandes Liliane Lona

Universidade Federal do Ceará University of Campinas
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Published in: BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, 17(2), 163-170, 2000.

FLUIDIZED BED REACTOR FOR POLYETHYLENE PRODUCTION.

THE INFLUENCE OF POLYETHYLENE PREPOLYMERIZATION.

Fabiano A.N. Fernandes and Liliane M.F.Lona

Departamento de Processos Químicos - Faculdade de Engenharia Química

Universidade Estadual de Campinas
13081-970 Campinas - SP - BRAZIL
e-mail: fabfer@feq.unicamp.br and liliane@feq.unicamp.br

ABSTRACT

This work addresses the influence of the prepolymerization of the catalyst particle on the
fluidized bed reactor for polyethylene production. The influence of prepolymerization on the
temperature and concentration gradients throughout the reactor was studied. The results obtained
through simulations confirm industrial observations of the advantages of prepolymerization and
extend these observation, showing the viable operational conditions for different superficial gas
velocities and gas feeding temperatures as a function of the degree of prepolymerization.

1. INTRODUCTION

Great progress has been made in ethylene polymerization kinetics (Galvan and Tirrel,
1986; deCarvalho et al., 1989; McAuley et al., 1990), the resistance of polymer particles to mass
and heat transfer (Galvan and Tirrel, 1986; Floyd et al., 1986a, b, 1987; Hutchinson and Ray,
1987) and prediction of polymer particle growth (Hutchinson et al., 1992).
In the area of fluidized bed reactor modeling, two key articles have presented a steady-
state model for the reactor: Choi and Ray (1985) and McAuley et al. (1994). These two models
assume temperature and concentration gradients in the bubble phase and the interaction of
separate emulsion and bubble phases within the reactor bed. Both studies assume that the
emulsion phase behaves as a continuous stirred tank reactor (fully mixed).
More recently, the fluidized bed polymerization reactor model has been futher developed
to consider two phases (bubble and emulsion), flowing in plug flow at different velocities with
polymer particles segregated, according to size and weight within the reactor (Fernandes and
Lona Batista, 1998).
This modeling technique has allowed a more complete understanding of the fluidized bed
polymerization reactor, thus permitting the study of reactor behavior (polymer yield and
concentration and temperature gradients for both bubble and emulsion phases) and the prediction
of the physicochemical properties of the polymer.
A thorough survey of the potentialities and limitations of the fluidized bed reactor can be
carried out with better precision using new computer-aid techniques prior to lab and pilot-plant
scale tests saving thereby time and money.
In this work we have studied the influence of the degree of prepolymerization on the
behavior of the fluidized bed reactor. The basic operational conditions were simulated in order to
study the limitations of the system.
Published in: BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, 17(2), 163-170, 2000.

2. FLUIDIZED BED REACTOR FOR POLYMER PRODUCTION

The fluidized bed reactor has an unique physical design (Figure 1). Gas and polymer
particles flow in opposite directions. The gas is fed at the base of the reactor and splits into two
phases: bubbles and emulsion.
The catalyst is fed in near the top of the reactor. In this way, as the catalyst moves
downwards, the ethylene polymerization reaction takes place. The polymer grows on the catalyst,
increasing its weight and size. Particle segregation occurs in the reactor according to particle
weight. Polymer particles are removed from the reactor at the base. Nonreacted gases leave the
reactor after passing through the disengagement zone.

Figure 1. Fluidized bed reactor for polyethylene production.

Prepolymerization is used in fluidized bed systems for two main reasons: to produce
specific polyethylene grades and to prevent the formation of hot spots inside the reactor.
Prepolymers are generally made in CSTRs located before the fluidized bed reactor.
Catalyst particles are fed into the CSTR along with ethylene and comonomers to yield
prepolymer. Afterwards, these prepolymerized catalyst particles are fed into the fluidized bed
reactor to complete the ethylene polymerization. An industrial diagram for the fluidized bed
reactor system using prepolymers is shown in Figure 2.

Figure 2. Industrial polyethylene production diagram (BP Chemical Technology).

Published in: BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, 17(2), 163-170, 2000.

3. METHODOLOGY

The study was carried out using the phenomenological model developed by Fernandes
(1999). This model describes a fluidized bed reactor with two phases (bubble and emulsion)
flowing in plug-flow regime and with segregation of polymer particles within the reactor
(Fernandes and Lona Batista, 1998).
Since the bubbles are considered to be non interactive spheres, a single bubble is used to
infer the behavior of the entire bubble phase. Mass transfer between bubble and emulsion phases
occurs by diffusion through the bubble clouds. Energy transfer between phases occurs due to the
temperature gradient between phases and also by diffusing gases.

.(C ei − C bi )
dC bi K m
= (1)
dz Ub

.(Tb − Te )
dTb Hm
= (2)
dz U b .CbT .c *pg
where i refers to the different gases fed into the reactor.

In order to consider axial temperature and concentration gradients and variations in the
physicochemical properties within the bed, the mass and energy balances of the emulsion phase
were expressed as differential equations that can be evaluated for any point in the reactor bed.
The mass balance of the emulsion phase assumes consumption of gas by the reaction and mass
transfer between bubble and emulsion phases by diffusion.

dC ei Rp'.(1 − ε mf ) Km.(Cbi − C ei ).δ

= + (3)
dz ε mf . A.U e (1 − δ ).ε mf .U e
The energy balance for the emulsion phase comprehends energy transfer due to
temperature gradient and for the diffusing gases, the heat of reaction and the heat loss to the
surroundings through the reactor wall.

dTe [c pg .Km.(C b − C e ) + Hm].(Tb − Te ).δ

* T T

= −
dz U e .(1 − δ ).ε mf .c *pg .C eT (4)

[
Rp'.(1 − ε mf ).M W . − ∆H − (c ps − c pg )( ]
. Te − Tref ) + π .D.U h .(Te − T∞ )
U e.ε mf .c *pg .CeT

The mass balances for polyethylene and catalyst were combined since the final polymer
particle grows on the catalyst particles and their masses cannot be separated. This mass balance
is given by the variable χ, which is the accumulated polymer mass produced by the mass of
catalyst fed into the reactor. Strictly speaking χ is the accumulated mass of the particle (polymer
+ catalyst) produced, but as the mass of polymer in the particle is much greater than the mass of
catalyst, then χ can be taken as the accumulated mass of polymer produced by the mass of
catalyst fed into the reactor.
Published in: BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, 17(2), 163-170, 2000.

(
dχ Rp'.A.(1 − δ ). 1 − ε mf .MW
=
) (5)
dz qcat (6)
kp.Ce .ρ s
where Rp' = .
χ

This variable allows the calculation of the total rate of polymer produced in the reactor
and the prediction of particle size all along the reactor height.
In the rate expression, the gas concentration at the catalyst sites is assumed to be
proportional to the gas concentration in the emulsion phase, since the gas dissolved in the
polymer phase is in equilibrium with the gas in the emulsion phase (Floyd et al., 1986a, b, 1987).
Several simulations were carried out and the influence of prepolymerization was
analyzed, paying special attention to the temperature of the bubble and emulsion phases,
observing whether or not they would rise above the polymer melting temperature (temperature at
which polymer melts, clogging the feeding and removal points of the reactor and resulting in the
shutdown of the reactor).
The data and operational conditions used in the simulations are summarized in Table 1
(McAuley et al., 1990).

Table 1. Operational conditions and parameters used for the fluidized bed reactor.
Ethylene feed rate 0.85 mol/L 1-Butene feed rate 0.05 mol/L
Hydrogen feed rate 0.05 mol/L Inert feed rate 0.00 mol/L
Catalyst feed rate 0.20 g/s Cocatalyst feed rate 0.01 mol/L
Gas feed temperature 316 K Room temperature 340 K
Catalyst density 2.38 g/cm3 Catalyst diameter 0.05 mm
Activation energy 37620 J/mol ∆H -3829 J/g
Reactor diameter 396 cm Reactor height 1097 cm
Bubble fraction 0.214 Porosity 0.50
Umf 7.0 cm/s Emulsion velocity 34.8 cm/s
Bubble velocity 114.0 cm/s Bubble diameter 15 cm
Kinetics McAuley et al., 1990

4. RESULTS

The Ziegler-Natta catalyst has a higher activity in the propagation of young polymer
particles. This higher rate for young particles can lead to polymer overheating and melting in the
reactor catalyst feeding zone (top portion of the reactor) owing to the exothermic characteristic of
the polymerization reaction.
When fed into the reactor, prepolymerized catalyst particles when fed into the reactor
help to prevent reactor overheating, since the catalyst activity is less intense on prepolymerized
particles. The rise in temperature in the bubbles and emulsion phases, at the top portion of the
reactor, is inversely proportional to the extent of prepolymerization of the fed catalyst particles, as
shown in Figure 3.
In the case presented in Figure 3, the increase in emulsion temperature for the
nonprepolymerized particles is of 62 K and for the catalyst with a 3000gpol/gcat degree of
prepolymerization it is of 32 K, 48% lower than that occurring with no prepolymerization.
Lower increases in temperature can be useful to control the temperature inside the
reactor, which favors the use of prepolymerized particles.
Published in: BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, 17(2), 163-170, 2000.

400 400

375 375

Emulsion Phase
Temperature [K]

Temperature [K]
Bubble Phase
350 350

325 325

Degree of 300 300

Prepolymerization
0.0 4.0 8.0 12.0 0.0 4.0 8.0 12.0
No Prepol.
Reactor Height [m] Reactor Height [m]
1500g pol/g cat
Ethylene Concentration [mol/cm3]

Ethylene Concentration [mol/cm3]

3000g pol/g cat 0.850 0.850

0.840

Emulsion Phase
Bubble Phase

0.830

0.845 0.820

0.810

0.800

0.840 0.790

0 400 800 1200 0 400 800 1200

Reactor Height [cm] Reactor Height [cm]
Figure 3. Temperature and ethylene concentration gradients for bubble and emulsion phases
throughout the fluidized bed reactor.

The superficial gas velocity of the gas entering the reactor is an operational condition that
requires a lot of attention due to the risk of polymer melting. In industrial reactors, the superficial
gas velocity is set to 3 to 6 times the minimum fluidizing velocity. When the superficial gas
velocity is low, it directly affects the gas residence time in the reactor, lowering the heat transfer
rate between bubble and emulsion phases. Figure 4 shows the emulsion temperature in the
catalyst feeding zone as a function of the catalyst feed rate for three different degrees of
prepolymerization and for two different superficial velocities. Observe that when the superficial
velocity is low, not enough heat is removed from the system to prevent polymer melting. Higher
degrees of prepolymerization help to prevent this risk since the reactor temperature does not rise
above the polymer melting temperature.
A screening of the operational conditions was conducted to identify those which were
viable, which resulted in ranges of operational conditions for different degrees of
prepolymerization, as shown in Figure 5. The figure indicates the ranges where operational
conditions do not increase the emulsion and bubble temperature above the polymer melting
temperature, consequently risking a system shutdown.
When a polyethylene grade can only be produced under operational conditions that may
cause polymer melting, then prepolymerization must be employed and a study of the minimum
degree of prepolymerization for the catalyst needs to be carried out.
Published in: BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, 17(2), 163-170, 2000.

440.0 440.0

Emulsion Temperature [K]

Emulsion Temperature [K]

420.0 420.0
Polyethylene Melting Temperature

Degree of
Prepolimerization
400.0 400.0

No Prepol.
380.0 380.0
1500g pol/g cat

3000g pol/g cat 360.0 360.0

340.0 340.0

320.0 320.0

0.20 0.40 0.60 0.20 0.40 0.60

Catalyst Feed Rate [g/s] Catalyst Feed Rate [g/s]
(a) (b)
Figure 4. Emulsion temperature in the catalyst feeding zone as function of catalyst feed rate. (a)
U0 = 3.Umf ; (b) U0 = 6.Umf .

Superficial Velocity [x Umf]

Viable Operational Points 5

No Prepol.

1500g pol/g cat

3000g pol/g cat

4

3
Figure 5. Possible operational points for different degrees of prepolymerization as a function of
catalyst feed rate and superficial velocity (U0).

Gas feed temperature is the second critical operational condition affecting the possibility
of polymer melting. The gas feed temperature increases the polymerization reaction rate, thereby
increasing even more the emulsion and bubble temperature throughout the reactor (Figure 6).
Screening the operational conditions resulted in viable gas feed temperatures for the
fluidized bed reactor. As can be seen in Figure 7, the gas feed temperature has limitations in the
region over 360 K and 0.4 gcat/s, where even where using high degrees of prepolymerization, the
temperature inside the reactor reaches the polyethylene melting temperature, making operation at
these points inviable.
440.0 440.0
Emulsion Temperature [K]

Emulsion Temperature [K]

Polyethylene Melting Temperature

420.0 420.0
Polyethylene Melting Temperature
Degree of
Prepolimerization
400.0 400.0
No Prepol.

1500g pol/g cat

380.0 380.0
3000g pol/g cat

360.0 360.0

340.0 340.0

0.20 0.40 0.60 0.20 0.40 0.60

Catalyst Feed Rate [g/s] Catalyst Feed Rate [g/s]
(a) (b)

Figure 6. Emulsion temperature in the catalyst feeding zone as a function of catalyst feed rate.
(a) T0 = 316 K ; (b) T0 = 360 K .
Published in: BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, 17(2), 163-170, 2000.

375

Gas Feed Temperature [K]

360
Viable Operational Points
345
No Prepol.

1500g pol/g cat

330
3000g pol/g cat

315

300

Figure 7. Viable operational points for different degrees of prepolymerization as a function of

catalyst feed rate and gas feed temperature (T0). U0 = 5.Umf .

As shown in Figures 5 and 7, the use of prepolymerized particles can broaden the range
of polymer grades produced in the fluidized bed polymerization reactor, without compromising
either polymer quality or the reactor itself.
The prepolymerization reactor (CSTR) does not exhibit problems of overheating or
polymer melting. The residence time inside the prepolymerization reactor and the amount of
polymer processed are small enough so as not to cause damage to the reactor or the quality of the
polymer.

5. CONCLUSIONS

This study showed the influence of prepolymerization on the behavior of the fluidized
bed reactor, related mainly to the temperature and concentration gradients throughout the reactor.
As was demonstrated, the use of prepolymerized catalyst particles in the reactor decreases the
reaction activity in the catalyst feeding region, leading to milder temperatures and lower
temperature gradients throughout the reactor. These conditions avoid the problem of hot spots
and polymer melting and consequently reactor shutdown.
These results confirm industrial observations of the advantages of prepolymerization in
the fluidized bed reactor, increasing the range of operability of the reactor to lower superficial gas
velocities and higher gas feed temperatures, without compromising the operation of the
prepolymerization reactor.
This work will be followed by new simulations to determine the influence of
prepolymerization and of the operational conditions of the reactor on the physicochemical
properties of the polymer.

NOMENCLATURE

A area
Cij concentration of gas i in phase j
cp heat capacity
Hm heat exchange coefficient
Km mass exchange coefficient
kp polymer propagation rate
MW molecular weight
Published in: BRAZILIAN JOURNAL OF CHEMICAL ENGINEERING, 17(2), 163-170, 2000.

qcat catalyst mass flow

Rp’ reaction rate
Ti temperature of phase i
U velocity
Uh wall heat coefficient
z height position [m]
δ bubble volumetric fraction
∆H heat of reaction
ε porosity
ρ density
χ accumulated mass of polymer produced per mass of catalyst fed into the reactor

subscripts

0 initial value
b bubble
e emulsion
g gas
i monomer
mf minimum fluidizing condition
ref reference
s solids
∞ ambient

ACKNOWLEDGEMENT

The authors would like to thank FAPESP – Fundação de Amparo à Pesquisa do Estado de
São Paulo - for its financial support of this work.

REFERENCES

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