Pergamon Chemical Engineerin9 Science, Vol. 51, No. 21, pp.

4859 4886, 1996

Copyright 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
P I I : S0009-2509(96)00258-8 0009 2509/96 $15.00 + 0.00

REACTOR RESIDENCE TIME DISTRIBUTION EFFECTS ON

THE MULTISTAGE POLYMERIZATION OF OLEFINS--I.
BASIC PRINCIPLES AND ILLUSTRATIVE EXAMPLES,
POLYPROPYLENE

JORGE J. ZACCA, JON A. DEBLING and W. H. RAY*

Department of Chemical Engineering, University of Wisconsin-Madison, Madison, WI, U.S.A.

(First received 7 August 1995; revised manuscript received and accepted 27 February 1996)

Abstract--Manypolyolefinsare produced by catalyzed olefinpolymerization over solid catalysts. A variety

of processes are currently in use including loop, continuous-stirred tank, horizontal stirred bed and
fluidized-bedtechnologies. In each of these continuous processes, the reactor residence time distribution is
unique and affects the resulting distribution of polymer properties. In this paper we present a population
balance modeling approach for modeling multistage olefin polymerization processes using catalyst resi-
dence time as the main coordinate. The catalyst may possess a broad particle size distribution and contain
multiple active sites with a comprehensive kinetic scheme involving multiple monomers, Diffusion limita-
tions during reaction may also be a consideration. A variety of reactor systems can be modeled each with
unique residence time distributions and having different internal and external residence time distribution.
In addition, the modeling allows the consideration of particle size selection effects within the process. These
effects are implemented in a model of a fluidized-bedreactor. The population balance model is illustrated
with examples of propylene polymerization in the four major commercial processes listed above, with a high
activity TiCL~/MgC12 catalyst. Comparisons of total production capacity, catalyst yield distribution,
polymer particle size and porosity distribution are made. It is found that significant differences exist
between the differentindustrial processes. It is also found that the performance of the fluidized-bedreactor
is highly sensitive to fluidization conditions, particle size selection effects and the catalyst particle size
distribution. Differences in product quality are discussed and issues such as fines generation and particle
sticking are addressed. Copyright 1996 Elsevier Science Ltd

Keywords: Population balances, olefin polymerization, residence time distribution, propylene,

Ziegler-Natta, fluidized bed, stirred bed, loop, multistage polymerization.

I. INTRODUCTION complex and may involve multiple sites on the cata-

One of the most important methods for the produc-
tion of polyolefin resins is by solid-catalyzed olefin
polymerization. In this process, small catalyst par-
ticles (10-200 pm diameter) are continuously fed into
a reactor that is operated at controlled temperature,
pressure and composition. The catalyst particles
themselves are porous and composed of small sub
fragments containing active metal. As the monomer
diffuses through the porous catalyst pellet, it polymer-
izes via a coordination-insertion mechanism on
active sites present on the catalyst surface. As the
polymerization proceeds, the catalyst fragments are
dispersed and the particle expands in size, ultimately
growing into a final polymer particle ranging between
100 and 5000 pm diameter [see Hutchinson (1990) for
more details].
Industrially, many different catalysts have been
and are currently used for olefin polymerization.
The most significant groups include supported or
unsupported Ziegler-Natta, chromium oxide and
recently Metallocene-based systems. The kinetics
that control the polymerization process are quite
* Corresponding author.
lyst surface, reactions with cocatalyst and donor,
poisoning and site transformation effects. In addition,
the polymerization may involve chain transfer
agents such as hydrogen for molecular weight control
and several monomers may be simultaneously poly-
merized. Further complicating this process is the fact
that diffusion resistances may be present during the
growth of the polymer particle.
Traditionally, there have been two approaches
taken to model these systems depending on the scope
of interest. When the primary interest is in under-
standing the influence of diffusion on reaction rate,
composition and molecular weight distribution, de-
tailed reaction diffusion models for individual cata-
lyst-polymer particles are studied. Several of these
models have been published in the literature (Debling
and Ray, 1995; Ferrero and Chiovetta, 1987; Floyd
and Ray, 1986; Galvan and Tirrel, 1986; Hutchinson
et al., 1992; Sarkar and Gupta, 1991). Single-particle
models can provide some useful information about
a continuous process by running the model repeatedly
to account for reactor residence time distribution,
reactors in series and catalyst particle size distribu-
tion. However, this can become time consuming and
computationally intensive.

4859
4860
When the main interest is in studying the macro-
scale properties of the process such as dynamics of the
reactor unit, control, scaleup of pilot plant data,
grade transitions and average polymer properties,
a macroscopic dynamic model of the reactor vessel is
usually studied. Various models have been developed
for several commercially important reactors such as
the loop (Zacca and Ray, 1993), continuous-stirred
bed (Choi and Ray, 1988; Demel, 1989), fluidized bed
(Choi and Ray, 1985a; Lagemann, 1989; McAuley,
1991; Talbot, 1990) and continuous-stirred tank (Ar-
riola, 1989). However, the main limitation of most of
these models is that they can only calculate average
properties of the polymer product leaving the reactor,
such as molecular weight, composition and yield and
do not account for the distributed nature of the prob-
lem as a result of reactor residence time distribution
effects.
To capture rigorously these effects, population bal-
ances on the growing particles are necessary. Popula-
tion balances have been used in chemical engineering
to study particulate processes (Hulburt and Katz,
1964; Ramkrishna, 1985) and are well known in the
field of emulsion polymerization where computing the
latex particle size distribution is important (Min,
1976; Prindle, 1989; Rawlings, 1985). However, the
application of population balances in catalyzed olefin
polymerization is not very common. Caracotsios
(1989) has used the concept of residence time distribu-
tion to study average yield and degree of polymeriz-
ation for propylene polymerization in a horizontal
stirred bed reactor at steady state. Choi et al. (1994)
have applied population concepts to a continuous-
gas-phase reactor at steady state for ethylene
copolymerization and studied the effects of catalyst
deactivation, catalyst particle size distribution and
catalyst feed rate on polymer particle size distribution,
comonomer content and average molecular weight.
Polymer particle radius was chosen as the internal
coordinate. Kim (1995) has used population balances
to simulate the unsteady behavior of a CSTR for
propylene polymerization with two active sites. In
Kim's work, polymer volume was used as the internal
coordinate and a quasi-steady-state assumption was
applied to the total number of active sites.
In this paper we present a population balance
modeling approach for modeling multistage olefin
polymerization processes using catalyst residence
time as the main coordinate. The catalyst is allowed to
possess a broad particle size distribution and contain
up to two active sites with a simple kinetic scheme
involving up to two monomers and including diffu-
sion. A variety of reactors can be studied each with
unique residence time distribution. The internal resi-
dence time distribution can also be different from the
external distribution.
2. PROCESSES F O R O L E F I N P O L Y M E R I Z A T I O N
Many processes have been developed for the pol-
ymerization of olefins. They differ in both the physical
J. J. ZACCAet al.
state of the reactor media and in the mechanical
operation of the unit. The choice of process is deter-
mined by economics, feedstock availability, catalyst
and desired range of products to be produced. Signifi-
cant improvements in catalyst design over the past
years have led to improvements in process design and
simplification. Modern supported catalysts are able to
produce polymer with high yields and stereospecific-
ity (for polypropylene) such that removal of catalyst
residue and atactic polymer from the resin is no lon-
ger required. Control of polymer particle morphology
via catalyst morphology has also allowed the produc-
tion of high bulk density, spherical particles directly in
the reactor. An overview of the main methods for the
production of polyolefin resins is shown in Fig. 1.
Comprehensive reviews have also been published
(Choi and Ray, 1985b; 1985c).
2.1. Slurry-phase processes
Slurry-phase processes may involve either an inert
diluent such as iso-butane or heptane, or condensed
monomer such as propylene. In either case the cata-
lyst particles are suspended and well mixed in the
liquid medium. Monomer concentrations are high
and the liquid provides good removal of the heat of
polymerization from the polymer particles. The two
main reactors for slurry-phase olefin polymerization
are the loop reactor and continuous-stirred tank.
Slurry-phase processes are very attractive for high-
crystalline homopolymer products such as poly-
propylene and polyethylene but have limited applica-
tions for low-density, amorphous copolymers. For
these products, the liquid phase can dissolve the
amorphous copolymer making the resin tacky in na-
ture and hard to process. Also the solubilization of
amorphous material may cause operational problems
such as increases in slurry viscosity and reduction of
the reactor heat transfer coefficient.
2.2. Gas-phase processes
Gas-phase processes for olefin polymerization in-
clude the vertical stirred bed reactor (VSBR), horizon-
tal stirred bed reactor (HSBR) and fluidized-bed reac-
tor (FBR). They provide an attractive environment for
olefin polymerization with no liquid inventory. To be
competitive with liquid-phase processes, gas-phase re-
actors must operate close to the dew point of the
monomer mixture to obtain high monomer concen-
trations and high yields. Today a full range of polymer
products ranging from polyethylene and polypropy-
lene (homopolymer and impact polypropylene) to
random copolymer products are produced in gas-
phase processes.
In both the ttuidized-bed and stirred-bed reactors,
the catalyst morphology must be closely controlled to
prevent particle overheating and melting due to the
poor heat transfer characteristics of the gas. Over-
heating is most serious for large catalysts with high
activity, precisely the desired catalyst characteristics
for maximizing polymer yield and minimizing fines
production.
 Multistage polymerization of olefins--I 4861
I II
[ Particulate Processes ~

I I
SlurryPhase Gas Phase

I I I I
LiquidDiluent LiquidMonomer Fluidized Vertical Horizontal
bed stirred bed stirred bed

i
I I I I
Loop Stirred Loop Stirred
Tank Tank

not considered in this paper

I I
Tube Stirred
Tank

Fig. l. Classification of polyolefin processes.

2.3. Solution processes
Solution processes include free radical initiated poly-
merization under supercritical conditions and cata-
lytic processes where the solvent temperature is high
enough to dissolve the polymer material. Although
these processes are not particulate in nature, the con-
cepts of population balances may also be applied to
fluid elements of the reactor volume. Although not
explicitly considered in this paper, the equations de-
veloped for particulate processes may be easily ex-
tended to the solution reactors.
2.4. Illustrative examples
To illustrate the concepts discussed in this paper,
four major processes for propylene homopolymeriz-
ation are used as comparative examples. These in-
clude the loop reactor, vertical and horizontal
stirred bed reactors and fluidized-bed reactor.
Typical operating conditions are shown in Table
1 and process schematics are given in Figs 2-5.
Note that the processes shown also include the
possibility of a second copolymerization stage used
for making impact polypropylene. The second stage
is the subject of a future paper in this series (Debling
et al., to appear); however, here we consider only
the homopolymerization stage for purposes of
illustration.
3. BASICMODELING EQUATIONS
3.1. Probability distributions
Since population balance models inherently involve
statistical distributions, it is prudent here to define the
probability density functions (also known as 'distribu-
tions') used in this paper. The distributions presented
below may be defined on a variety of distinct bases
depending on the property of interest. In this work we
focus on three types of bases: (1) mass of the catalyst,
(2) number of particles, and (3) weight of the polymer.
We denote the type of distribution by a superscript.
A superscript 'w' denotes weight of catalyst basis, 'n'
denotes number of particles basis and 'p' denotes
weight of polymer basis. The distributions may also
be defined at the reactor inlet, reactor outlet or
inside the reactor. We denote these by another super-
script. A superscript 'R' denotes inside the reactor,
4862 J. J. ZACCAet al.
Table 1. Processes for propylene homopolymerization
BASF* Amoco/Chiso* Union Carbide t MontelP
Process Novolen - UNIPOL SPHERIPOL
Medium Gas Gas Gas Slurry-liquid
monomer
Reactor VSBR HSBR FBR Two loops in series
Size 25-50 m 3 n/a n/a 45 m 3 each loop
Catalysts used TiCI3 TiCI4/MgCI2 TiCI4/MgCI2 TiCI4/MgCI2
TiC14/MgClz
Temperature (C) 50-100 57-93 n/a 70
Pressure (atm) 20-35 19 23 n/a 35-40
Reported 10,000-20,000 Up to 30,000 Up to 40,000 Up to 50,000
yield (g/g cat)
*Jaggard (1989), Ross and Bowles (1985), Schill and Buchner (1988).
*Caracotsios (1992), Brockmeier and Koizumi (1991), Hattori (1986). Brockmeier (1987), Brockmeier
(1991).
~Hussein and Nemzek (1989), Sawin and Baas (1985).
~Di Drusco and Rinaldi (1984), Galli and Ali (1987), Simonazzi et al. (1991).

Purge

Hydrgen 5 ~'~'4~= ~ CW~tI~= !

Ethylene
Propylene
Catalyst
Ni~ogen
Cocatalyst ~i Steam

Prepolyme

Propylene
Ethylene ~ Finishing
Fluidized
Bed Reactor
Loop Reactors

Fig. 2. Himont spheripol loop process.

a superscript 'F' denotes at the reactor feed and In this work all the distributions are normalized,
a superscript '0' denotes at the reactor outlet. Sub- therefore;
scripts are used to denote the type of distribution.
The fraction of particles with a given property , in
any space of interest is denoted by the distribution, f.
This is equivalent to stating that the probability of
min
t~ d e =
fT;?mln min
f,, d e dv = 1,

where the minimum and maximum terms in the inte-

(2)

finding a particle with property in the range to
+ de is fd~. The probability that a randomly
chosen particle in the entire space of interest has
a certain property ~ and property v, is termed the
~ioint" probability. This is denoted by the joint distri-
bution f~. v. Note the comma separating the two prop-
erties of interest. The probability of finding a particle
with property ~, 'from the subset' of particles having
a property v, is termed the 'conditional' probability
and denoted by the conditional distribution f~l,. The
relationship between the two distributions is easily
found by
grals define the region of feasibility for the variable of
interest.
3.2. Population balance modeling of the catalyst and
polymer particles
Consider a population of particles within a con-
tinuous-reactor process. A population balance over
the mass fraction of catalyst particles in the reactor,
having a property ~ and initial catalyst radius teat at
chronological time t, fw......
,R
can be made:
wR ~ wR
g(Wcat, R f,',-o.,)+ ~-~(rW~at,Rf,',-o.,)

= qcat.r f w.....
,F w,O
-- qcat,of ...... (3)
 Multistage polymerization of olefins--I 4863

To Recycle

Cyclone
7---~ Condenser

cTR

Catalytic System
Hydrogen
Propylene

To Recycle

Cyclone
[ CW ~ Condenser

Fines 2nd REACTOR

Hydrogen
Propylene
Ethylene ~ Polymer
I Product

_ J

Fig. 3. BASF vertical stirred bed processes.

where f~,R ..... is the probability density function on Expanding and choosing the internal coordinate to be
catalyst weight fraction basis within the reactor, the catalyst residence time, z, eq. (3) can be rewritten
fw,O
..... is the probability density function on catalyst as
weight fraction basis at the reactor outlet, f~,'~, is the
probability density function on catalyst weight frac- we 0 0 ? w,R
tion basis at the reactor feed stream, re is the rate of
change of property ~ with time and Wc~t,R, q~,,r,
q~t,o, are the mass of catalyst in the reactor, catalyst = q~at.v f ~ ' ~ , - q~.t.o f~,,o,. (5)
mass feed rate, and catalyst mass exit rate from the
reactor, respectively. Substitution of eq. (4) into eq. (5) leads to
The property ~ in eq. (3) is known as the internal
coordinate. In the above equation it has been assumed
t h a t there is no particle breakage or agglomeration It ~ t ( f ...... ) + & f ...... )
is furthermore assumed t h a t the reactor fluid phase is
well mixed so that the continuous fluid phase is uni- q.t,r ( f['~,- f~'~,) -- q~.t.o(f~'~ , -- f~.'~,)
form. These assumptions are reasonable for all pro- (6)
Wear,R
cesses considered here and necessary to apply the
concepts of residence time distributions (Shinnar and From eq. (6) we note the following. For well-mixed
Rumschitzki, 1989) systems where f~;~, = f~;o the unsteady-state popu-
A balance on total mass of catalyst in the rcactor lation balance takes the form
yields
d W~at. R
w.R - ( r w , R~_ - , / ...... ), (7)
dt q~t,F - - qcat,O. (4) ~.t ( f ...... ) + ?Jr ........ _ ~(f~,;,., "w,o
4864 J. J. ZACCAet al,

Powder
Gas
Separator
Propylene
Cocatalyst

Catalyst

L i
Purge
I Column

Propylene ~ r "~
Ehtylene ~-- ~ ~ Nitrogen
Steam
GasLock

\/
REACTOR Hydrogen Extruder }

t ' Pelletized
Product
Fig. 4. AMOCOhorizontalstirredbed processes.

Purge Purge

Catalyst
Feeder

Prop Propylene
Hydrogen Cocatalyst Ethylene
Hydrogen

Product
Product
Fig. 5. Unioncarbidefluidized-bedprocesses.
 Multistage polymerization of olefins--1
where the mean catalyst residence time ? is based on
the inlet feed rate and is time dependent:
-~ = ~(t) = wo.,,R(t)
qeat.r(t) "
At steady state q~t.v = qat.O and eq. (6) is simplified
to
d wR 1 wF
d r (f";"') = f ( f~';" - f~;0o).
Equation (9) can also be written as a differential
equation with initial condition (Zacca, 1995) shown in
eq. (10):
d w.R 1 w o
d--~( f ...... ) = - - f " ; ~ " z
= ~f,2, ,
where again the mean catalyst residence time is more
appropriately based on inlet feed rate to the reactor.
Equation (10) above is used to relate the exit age
distribution to the internal age distribution of the
process for a system at steady state.
Many processes consist of a train of reactors in
series, each operating at identical conditions of pres-
sure, temperature and composition. The catalyst par-
ticle passes from each reactor adding an additional
polymer in each stage. The exit age distribution of the
catalyst particles after the nth reactor of a process is
given by a convolution of the exit age distributions of
n reactors, For example, the exit age distribution after
two reactors in series is
fw, o~
~,rv,l~ r
, ~
cat/ ~ l rw':tz--O,ra,)
d t . r e a t ~, f~.'~:(O,r~t)dO.
It is useful to remark at this point that the formulation
of the population balance model in terms of catalyst
residence time has several advantages. First, the
modeling equations are simpler and do not involve
growth terms that appear when the main coordinate
is particle volume or radius. Catalyst mass never cha-
nges with time. Secondly, residence time is a logical
choice, since all of the kinetic reactions are time de-
pendent.
3.3. Derivation of polymer properties from the resi-
dence time distribution
To calculate the expected distribution of any prop-
erty when the distribution of another property v is
known, the following relationship is used as shown by
Rawlings (1985):
dv
f(~) = [f~(v)-d-~]~=~(~.
This formula may be used when there is a one-to-one
relationship between the two properties ~ and v. Since
4865
the properties of the entire distribution must be con-
served,
(8)
;-
rain
f,.dv = ?rain
fcd~ = 1. f13)
It is sometimes more convenient to base the probabil-
ity distributions in terms of weight fraction of polymer
particles or number fraction polymer particles instead
of catalyst particles. Derivations of some important
(9)
properties from the three bases are presented in this
work.
3.4. Reactor residence time distribution functions
In order to apply the population balance model to
specific processes, the residence time distribution
functions must be derived or measured. We illustrate
this with the four polypropylene processes introduced
(lO)
earlier. For a more complete review of the determina-
tion and application of residence time distributions to
other reactor design problems, the interested reader is
referred to the work of Shinnar (1987).
3.4.1. Vertical stirred bed reactor (BASF). When
the system is well mixed with no particle size selectiv-
ity at the exit there is no dependence of residence time
on polymer particle size or catalyst radius, therefore
the internal and external distribution functions are
identical. Therefore, the solution of eq. (10) can be
easily recognized as the residence time distribution
function of a CSTR. The catalyst residence time distri-
bution of the BASF-type reactor is modeled in this
manner:
Mean catalyst residence time in the reactor can be
calculated from known parameters such as the weight
(11) of the polymer bed Wb(g), the catalyst feed rate
qeat.v(g/s) and mean catalyst yield in the reactor YR
(g polymer/g catalyst):
We,,, R Wb
= - - ~15)
qcat, V qcat,F(1 + 17R)'
where the mean yield in the reactor is given by
YR =
f/Tfo
~a,. i.
f ......
w , R Y d z d r .... (16)
Here Y is the yield of polymer in g polymer/g catalyst
that is formed at residence time z from a particle
originating from a catalyst of size r~,. Yield at time
may be a function of catalyst radius if monomer
diffusion plays a role in the polymerization. Since
mean yield in the reactor is a function of the residence
time distribution, eqs (14)-(16) comprise a nonlinear
set of equations that must be solved for catalyst mean
residence time. Thus, catalyst mean residence time is
(12) a function of the overall production in the reactor,
catalyst feed rate and catalyst activity in the reactor.
It is interesting to note that in cases where the
external distribution is equivalent to the internal
4866 J. J. ZACCA et al.

distribution (i.e. a well-mixed system with no exit follows:

selection) the catalyst mean residence time is the same
as the polymer mean residence time: R e , - QR,~
Qo (19)

f Wcat,a _ fp = Wb. (17) vL

qcat, F qo Pe = - - . (20)

3.4.2. Horizontal stirred bed reactor ( A M O C O /
Chisso). When the process consists of several reactors
operating in series and under the same conditions
of pressure, temperature and composition, the resi-
dence time distribution is found by convolution of
the residence time distributions of each reactor as
illustrated in eq. (11). The solution to this problem
for n fully backmixed reactors in series having distinct
mean residence times is given by (Ogunnaike and Ray,
1994)
Blenke (1979) by means of superposition principles
proposed an expression for the outlet residence time
distribution of a loop reactor. Unfortunately, this
expression is inconsistent and the residence time dis-
tribution neither integrates to 1 as expected, nor does
it converge to the corresponding CSTR limit as the
recycle ratio tends to infinity. After careful reexamina-
tion of Blenke's expression the following corrected
equation for the outlet residence time distribution of
a loop reactor was rederived (Zacca, 1995):

o
= i=l exp . (18)
=3 lz(l + Rec)~q~7 I i : i,,, \ l~--R~eJ
j-1
j@i

The horizontal stirred bed reactor (AMOCOIChisso)

is a cylindrical reactor that contains a series of
paddles attached to a shaft for agitation of the powder
bed. The gas phase is expected to be well mixed but 4(1 +Rec)f-~ot ]
the powder flow acts as if it is flowing through be-
tween 3 and 5 fully backmixed CSTRs in series
(Caracotsios, 1992). In this paper we assume four The maximum and minimum integers used in eq. (21)
CSTRs is sufficient to model this process. The volume are given by

if floor (l+Rec)~~ --j] > 0

iml n (22)
1 otherwise

ceiling [(1 + Rec)~ot + J ] if ceiling (1 + Rec)~Gi + J > 0

imax = (23)
1 otherwise

ceiling \ ~/---~-) if ceiling ( 2 ~ >_-2,

\V 10 )
j= (24)
2 otherwise

of each reactor zone is equivalent and therefore the where the 'floor' of the argument is defined as the
mean residence time of each zone will steadily de- largest integer smaller than the argument and the
crease from zone to zone to reflect the cumulative 'ceiling' of the argument is the smallest integer larger
production of polymer from the previous zones. For than the argument.
each reactor zone, the mean residence time must be In the above equation, the mean residence time is
calculated by solving eqs (15), (16) and (18). Again, we based on a total mass basis, i.e.
assume no dependency of residence time on particle
size. riot = WR PR Va (25)
qF qv
3.4.3. Loop reactor (Himont). The two most impor-
tant mixing properties of a loop reactor are its recycle However, it can be shown that this quantity is identi-
ratio and the Peclet number which are defined as cal to the mean residence time based on the catalyst
 Multistage polymerization of olefins -1 4867
mass as indicated in eq. (8). At steady state a total the reactor:
mass balance around the unit is given by

qr = q0. (26) FR = 7 f o of ......

w,R Y dr dr~,t

The total mass outflow is calculated as (35)

f l + 17o~
qo = t ~ l q ~ a t , r " (27)
\ ~,o /
B = B(r,r~at)= ~ Y(r.r~,t)dz. (36)
Therefore,

(1 + 17o\ 3.4.4. Fluidized-bed reactor (Union Carbide). In

qF = / ~ - / q c a t . F" (28) fluidized-bed reactors the catalyst residence time dis-
\ 's,o /
tribution can be size dependent due to particle selec-
The total mass of material in the reactor can be tion effects along the reactor height. In this work, we
calculated as use a selection factor approach (Kunii and Levenspiel,
1991) in order to account for size selection effects. Let
(I + ITR)WCa~,R us define a particle size selection factor, ip(rp), such
WR (29) that
WS, R

From eq. (25), the mean residence time is

,ffTo = lis(rp)fv~ R. (37)

Equation (37) relates the probability (weight fraction

r i o t = , (1 +' 17R)
- , -Ws,
- r .o _
~,~ (30) polymer) of a polymer particle of radius rp being
(1 + 17o) w~.R
found in the exit product stream to the probability of
that size of particle existing in the reactor. For a given
Also, from an overall mass balance around the reactor
catalyst size, it is possible to convert particle size
it can be shown that
distributions from a weight fraction of polymer basis
to particle size distributions on a weight fraction of
I -~ Y R 1 + 17o
(31) catalyst basis. Also using the selection factor defini-
Ws, R Ws, 0 tion one can relate the outlet and internal particle size
distributions on a weight fraction of catalyst basis as
where Ws,R, Ws,0 stand for the solids content inside
follows:
and at the outlet of the reactor. Therefore,
( 1 -~- Yo \ wR
f , o , = f. (32) (38)
= I
Thus, for the case of a loop reactor the outlet resi-
A transformation of variables between particle size,
dence time distribution on a total mass basis equals
rv, and residence time, r, is possible through the rela-
the outlet distribution on a catalyst mass basis:
ftot. o = f~,.o. tions:
The reactor mixture density can then be calculated
.,R dr
as S,';:,L =

1 Ws, R 1 -- Ws, R
- - + (33) -w,o w,o dr
Pg Pp Pl ,lrr ..... = -- (39)
f ...... drp
Therefore, by combining eqs (25)-(33), the mean cata-
Therefore, it is possible to rewrite eq. (38) as:
lyst residence time can be expressed in terms of the
solids content in the reactor,
'1 + 17o)
f~wL' = , ~ / t~(rv) .fl~i;,~,. (40)
I VR 1 w~.o
= (W.~.R/pp) + (1 -- Ws.R)/pl (1 + ]70)qeat, r '
From the population balance equation (10) it is pos-
(34)
sible to write :
By specifying the outlet solids content, the internal d w.o
solids content can be calculated by eq. (31). Since .fr.r~at
-- .1 ...... ) =
it would be too cumbersome to find an analytical d r ( "~'"
expression for the internal residence time distribution,
we apply integration by parts to eq. (16) making f~.: R ,= o - f w:vg (41)
use of eq. (10) in order to get the average yield inside
4868 J. J. ZACCAet al.
Solving for the outlet residence time distribution obtained:
(Zacca, 1995) one obtains
~b(rp) = exp [b(rp - ro,~t)] (46)
~,,o ~( r p)f ....
w,F /' ~ ~(rp) d'r'~ (42) where b is a parameter that depends mainly on fluidiz-
f ...... ~, exp k ~ ,) ation conditions, rp,~t is the particle cutting radius
corresponding to a selection factor of ~k(rp) -- 1. rp,~t
wb
is not a free parameter but is established by imposing
q~,t.v(1 + Yo) the condition that the internal particle size distribu-
Wb tion integrates to 1. In our work we use the same slope
(43) 'b' as used in Kang's work so that the particle selec-
q~t,v(1 + JPlt,
f ........ f ~ fw' Yd~dr~t)
rain dO J ' teat tion sensitivity is roughly similar. It should be noted
rp = r,(~, ro~,). (44) that the range of particle sizes studied in Kang's work
is similar to that expected in solid-catalyzed olefin
The overall outlet residence time distribution of the polymerization.
process is given by
3.5. Polymerization kinetics
~r cat,
f~,o ma~

Jf~,,o dr c a t .
t , rml~ (45) 3.5.1. Kinetic model. The kinetic mechanisms used
~t,min
in this paper are based on a generalized Ziegler-Natta
The selection factor needs to be experimentally deter- kinetic scheme (Chen, 1993). The following reactions
mined by sampling the reactor internal and outlet are expected for the Ziegler-Natta multi-site catalyst.
particle size distributions. Not much experimental Notation is given at the end of this paper. Note that in
work has been done in his area. Kang et al. (1989) this paper we only consider time-dependent reaction
have measured the selection factor of a pilot scale mechanisms that are first order with respect to cata-
fluidized bed of mineral particles under different par- lyst sites. It is possible to model other complex reac-
ticle diameters and fluidization conditions. They were tions with cocatalyst, donor or reactions with hydro-
able to correlate the selection factor to the difference gen to fractional orders by application of pseudo-rate
between particle diameter and the mean particle dia- constants.
meter in the bed. Polynomial fits were performed
under different experimental conditions. The data of Site activation ~p k~ ~k
Kang et al. are shown in Fig. 6 with an exponential
data fit. Initiation P~ + Mi e~,, ~k
Pl.i
In this work, we model the selection phenomenon
in a similar method as Kang et al. Since for
the application considered here, larger particles Propagation ~ak J + Mi k~'u' ~k
, Pn+ l,i
are selected over smaller ones, the selection factor
must be a nonnegative monotonically increasing
Site deactivation [ak . k~j C a + Dk.
function of particle size. An exponential correlation n,J
is used to relate the selection factor and particle
radius, giving the same shape of the curve as Kang Site transformation ~ k P,, v l
Pn.j ~ P.,j

Chain transfer [ak, j + H2 V,,, ~k + ~)k.

I Kanget al. (1989) 10.3 /
-- a = 0.8481; b =3.5269 x

~2
3
ag= a * exp( b * (dp - draeart) / The kinetic scheme gives rise to a system of linear
equations on the catalyst sites of the following form:

d_~C= K(~
dt
(47)

(2 = [~,, ~o, ~o,,Y,

o i = 1. . . . . N . . . . k = 1. . . . . Nsite , (48)

where 'K' represents a matrix involving all the kinetic

terms. It can be shown (Lancaster and Tismenetsky,
1985) that for any generic kinetic matrix K e R ' ~
having a certain number of nz distinct eigenvalues, the
0 i I i i i I I
solution of system (47) can be expressed as
-300 -200 -100 0 100 200 300 400 500 C(t) = exp(Kt)(2(0) (49)
~ . dmean(r,,icrons)
n~ ml-- 1
(2(0 = ~ ~ Z,j tiexp(2,t)(2(O), (50)
Fig. 6. Size selection factor vs particle diameter. i=1 1=0

where rn~ represents the multiplicity of the kth distinct
eigenvalue of matrix K and Z o are time-independent
matrices in ~R"". If K has only distinct eigenvalues the
previous equation reduces to
C.(t) = Pexp (At)a - t (2(0)
exp(At) = diag [exp (2x t). . . . . exp (,t,t)],
where P is a matrix of right-hand eigenvectors of K.
Equation (51) provides an analytic expression for any
site concentration profile corresponding to a given
kinetic scheme. For the purpose of this paper we now
make the following simplifications.
It is assumed that the catalyst is fully activated at
time t = 0. This is a reasonable assumption since
the time scales for activation by aluminum alkyl are
of the order of minutes. For propylene polymeriz-
ation, the catalyst system is usually precontacted in
a previous stage so that cocatalyst, donor and cata-
lyst may complex for high isotacticity polymer.
The long-chain hypothesis can be applied such that
the rate of chain transfer is small compared to the
total rate of propagation and initiation.
The initiation step proceeds at the same rate as the
propagation step.
There are two types of sites and only site of type
1 may transform into site of type 2 which sub-
sequently deactivates.
The QSSA for the live chains may be applied.
The fraction of vacant sites is small compared to
the occupied sites.
With the above assumptions the concentration of sites
of type k having a chain ending in monomer of type
1 or 2, respectively (i.e. a copolymer system) is given
by
]20,1
k M kk
i~kz = /)k k~,[M2]~
k~,~[M1], + k kP21[M2]s"
The concentration of active sites of type k can be
found by
- dt
- = - kd1Y1
p o -- kU
d/~2
= ktl 2/~~ - ka2 I~o.
-2
dt
Analytically, this can be expressed as
fi~(t) =/)~(0)exp(-- (k,~ + k~2)t)
~ ( t ) = ~ ( O ) ( k ~ + k~ )
kt22 - k 2 / { e x p ( - k 2 t )
- - exp [ -- (kd1 + k~2)t]} +/]~(0) e x p ( - k~t).
Multistage polymerization of olefins--I 4869
The rate of consumption of each monomer (g/g/s) can
be calculated by
kk v k ] T*WT
2 ( pijPo,J)l~[Mi]s Mwi. (56)
(51)
Monomer concentrations used in this paper are the
(52) concentrations of the monomer at the catalyst site.
These are not necessarily the same concentrations in
the bulk phase of the reactor. Assuming thermodyn-
amic equilibrium between phases, one can calculate
the concentration at the active site as a function of the
fluid-phase concentration. For example, Hutchinson
(1990) relates the two concentrations by a sorption
factor )'i. The sorbed monomer concentration is re-
lated to the bulk monomer concentration by
[ M i L = ?,[M,]~. (57}
For liquid-phase reactors, the methods of H utchinson
are used to calculate the sorption equilibria for each
monomer. The concentration of monomer in the bulk
fluid is calculated by the Benedict Webb-Rubin
equation of state. For all liquid-phase reactors, the
concentration of monomer at the catalyst site is less
than the bulk fluid. For gas-phase reactors, the
method of Chen (1993) is used to calculate monomer
sorption factors. Chen uses the theory of Heuer et al.
(1989) and Scbotte (1982) to calculate the solubility of
monomer in a multicomponent mixture. Sorption
from the gas phase can result in higher monomer
concentrations at the catalyst sites compared to the
gas phase. The BWR equation of state is also used to
calculate the gas-phase composition.
3.5.2. Kinetic parameters. Many kinetic models de-
scribing olefin polymerization with Ziegler Natta
catalysts have appeared in the literature (Burfield et
al., 1972; Carvalho et al., 1989, 1990: Chen, 1993:
Chien, 1987; van der Burg et al, 1993). With them
a broad scatter of kinetic parameters has been pro-
posed. This lack of agreement is due partly to intrinsic
differences in the proposed kinetic schemes, inconsist-
(53) ent volume basis for determining kinetic rate con-
stants, nonconsideration of sorption effects, and the
great variety of polymerization conditions and cata-
lyst types. All these factors combined make the task of
kinetic parameter evaluation a difficult one.
In this paper, simulations are chosen to reflect
Pol
a modern high-activity TiCI4/MgCI2 supported cata-
lyst to compare the different processes. The basic
(54) kinetic parameters were taken from data published on
an industrial catalyst used for propylene polymeriz-
ation in liquid propylene (Di Drusco and Rinaldi,
1984). The main goal was to establish kinetic para-
meters that match overall productivities and deactiva-
tion levels for an industrial catalyst system and not to
validate a generalized kinetic mechanism. To this end
a two-site kinetic model was fitted to their data with
the following assumptions:
The total mol fraction of Ti available as active sites
(55) is equal to 40% (Karol, 1984). The initial amounts
4870 J. J. ZACCAet al.
of sites of type 1 and 2 are 80.64 and 19.36%, Table 2. Kinetic parameters for two-site model used in the
respectively (Chien, 1987), reflecting precontacting simulations (base case)
of the catalyst system.
Kinetic parameter Value
Site 1 does not deactivate but transforms to site
type 2. Site type 2 deactivates with time. This model k~11 (l/mol/s) 342.8
is designed to reflect a change in oxidation state of k211 (1/mol/s) 34.28
the catalyst from Ti 3 + to Ti 2 +. Based on typical k~2 (l/s) 2.385 x 10-4
time scales for site transformation (Chien, 1987; k2 (l/s) 7.950 x 10- 5
XTi* 0.40
Rincon-Rubio et al., 1990) it was assumed that the
~o~(o) 0.8064
kinetic constant for site transformation of site 1 to ho~(o) 0.1936
site 2 is three times the kinetic constant for site
deactivation of the second site.
Site of type 2 was assumed to be 10 times less active
60-
than site 1 for propylene polymerization (Barbe et 1
Data of Di Druseo and Rinaldi ( 1988 ) I
al., 1987; Kissin, 1985). -- 2 Sitc Model used in thisW o r k
J
50
The final kinetic parameters at 70C used in this paper
can be seen in Table 2. In this work the same catalyst
system was used for all the simulations. We do not 40
make any attempt to change the kinetic parameters to
reflect differences in the catalysts used by each pro-
~a0
ducer. By keeping a consistent set of kinetic rate
coefficients, we are able to compare better the perfor-
mances of each process. 20
The fit of the kinetic model to the experimental data
can be seen in Fig. 7. Figure 8 shows the active-site
variation with time. Site 2 is clearly indicated as the 10

stable site.

3.6. Catalyst and particle effects o 1 2 3 4 5

Equation (56) represents the kinetic rates of con- Time ( hr )
sumption of the monomers evaluated at a point along
the particle radius. In the absence of monomer diffu- Fig. 7. Fit of kinetic data to two-site model.
sion resistances or temperature gradients, eq. (56) may
be used directly. However, in cases when significant
diffusion resistance or particle temperature increases 0.a5 J
occur, the net rate of production averaged across the
growing particle radius can be related to the kinetic 0.30 4/
rate at bulk reactor conditions by an efficiency factor
/~ob,
pi
/~pi~, (58) o.25

where (i = (i(z, rcat) and the index i is over the mono- ~ 0.20
meric species.
The total rate of polymerization at any residence -~
time can be found by ~ o.Is

dY N.o, 0.10
d-~- = ~ /~p'('" (59)
i=1 """'"'",..,,............
0.05
Yield of polymer is then calculated by
N=on t
f t ~ t
2 4 6 8 10
Time ( hr )
The effectiveness factors are functions of many vari-
ables including particle size, diffusivity and the kinetic Fig. 8. Active site fraction vs time.
rates of consumption. To solve rigorously the popula-
tion balance problem with diffusion and temperature
gradients in the particle would require solving The effectiveness factors are approximated by simple
a coupled set of nonlinear integral equations involv- functional forms that are obtained by fitting the data
ing residence time, yield, particle radius and catalyst from a detailed model of particle growth and morpho-
size. To avoid this arduous task, a simpler more logy. The heterophasic muitigrain model of particle
effective method is used here to capture these effects. growth (Debling and Ray, 1995) has been used in this

work. Note that this formulation allows a generic
approach to integrating the particle characteristics
into the population balance model without having to
include particle radius as an additional coordinate.
In addition to the particle diffusional and temper-
ature effects, one must also consider that catalysts are
never monodisperse but have a certain particle size
distribution. A log normal particle size distribution
(weight of catalyst basis) is often used to represent the
catalyst particle size distribution (since it does not
permit negative particle sizes as a normal distribution
does):
1 [ -- (In (rcat/fcat)) z ]
f r W j f = rcatO'cat N ~ exp
f~.f~:rdr = 1.
This implies the log weighted mean size is given by
~"m~"fwf ln(rcat)drcat = In (fc~t).
dr m onazzi et al., 1991). Hutchinson (1990) suggests that
We assume that the fraction of metal and the kin-
etic rate coefficients are independent of catalyst par-
ticle size. The distribution of catalyst particle sizes
affects the overall polymer particle size distribution
and also the effectiveness factors for diffusion and
temperature effects.
3.7. Calculation of polymer properties
3.7.1. Polymer yield. Using eq. (12) the relationship
between yield Y in g/g catalyst and catalyst residence
time r in the homopolymer stage can be found. Note
the dependency on catalyst particle size.
On a weight of catalyst basis,
wo d~
fr~',~, = f~, ;,., ~--~,
where in the above equation the f ~ ; o is evaluated at
the appropriate residence time that gives the desired
yield.
The polymer yield distribution on a catalyst weight
basis can then be calculated as
f~,o =
/,7
cat. in
f rw,o
..... dr ....
On a number of particles basis this is given by
fT;o =
f r . . . . . (lrca t
~ (66)
.~,. i. rcatlrcat
(.r.~t max w, F
" fr ,
lr~at = ] ~drcat.
) r~,.mi, rcat
On a weight of polymer basis,
f~.o
U
(I + 17o) .... ,. (1 + Y ) f r ..... dr ....
Note in the absence of diffusion limitations (polymer
yield is independent of the initial catalyst size) and for
Multistage polymerization of olefins I 4871
systems where the residence time distribution is inde-
pendent of catalyst size the number fraction and
weight of catalyst yield distributions are equivalent.
This is not true of the fluidized-bed reactor but is true
of the other reactors considered in this work when
there is no size selection upon exit. Note also in cases
where there is catalyst deactivation the catalyst yield
will reach a finite value. Thus, although the domain of
residence time is infinite, the domain of yield is not.
For solid-catalyzed olefin polymerization yield dis-
tribution on a weight of catalyst basis is more useful
than the other bases.
3.7.2. Polymer particle porosity. The phenomenon
20.2at A (61)
of particle growth and development of morphology is
quite complex. During the polymerization reaction,
(62) several forces act upon the growing polymer particle
to shape its ultimate morphology at the end of the
reaction. In the early stages of particle growth, con-
trolling the rate of polymerization may be essential to
avoid excessive fragmentation of the catalyst (Sim-
(63)
monomer diffusion limitations in the early stages of
particle growth can lead to concentration gradients in
lhe growing polymer particle. This causes stresses
along the particle radius and increases in porosity
causing particle fragmentation and poor bulk density
product.
As the polymerization proceeds, it is believed that
the porosity of the granule decreases with yield, and
can decrease far below that of the initial catalyst
porosity. Bukatov et al. (1982) measure the porosity of
polypropylene produced over a TIC13 A1C13 catalyst
system with mercury porosimetry. Porosity is re-
ported to decrease from 0.45 to 0.17 after a polymer
yield of 2000 g/g polymer. Tang (1986) reports in-
creasing bulk density with polymerization yield for
(64) polyethylene produced with a TiC14/MgCI2 catalyst
system, consistent with internal pore volume changes.
Simonazzi et al. (1991) suggest that with increasing
yield, all of the particle void space is progressively
filled with polymer.
Changes in polymer particle porosity are also no-
ticeable with copolymer systems. Chen (1993) has
conducted random copolymerization studies with
ethylene and propylene over an unsupported
(65)
TIC13 AIC13 catalyst in gas phase. Micrographs of the
copolymers produced show a great deal of fusing and
agglomeration within the particle leading to elimina-
tion of void space. Furtek (1993) indicates linear low-
density polyethylene produced with a Metallocene
catalyst is essentially nonporous. Nonporous ethy-
lene propylene copolymer particles are reported by
(67)
Hoel et al. (1994).
While it is difficult to determine precisely the rela-
tionship between yield of homopolymer and particle
porosity, it seems clear that the particle becomes less
p,O
(68) porous with time. Polymer composition, catalyst
structure and operating conditions play an important
role. In this work we assume an exponential relation-
ship between porosity and homopolymer yield for
 4872 J. J. ZACCA et al.
a polymer particle as shown in eq. (69). This relation- On a weight of polymer basis,
ship seems to fit the general trend found by Bukatov
et al. (1982) reasonably well. Other correlations for 1 f ....... (1 + Y) f , ,p.o
different systems can be applied as determined by the fp;o = (I + lTo)J, ....... ..... dr=at. (80)
experiment. The parameters will be varied in the pa-
For particle size, it is most useful to calculate the
per to study the effects of this assumption on the
polymer weight distribution since, in practice, poly-
resulting particle size distribution:
mer particle size is often calculated on a weight basis,
e = (~o -- e~i.)exp(- flY) + ~i.. (69) i.e. from mechanical sieving. However, it is also pos-
sible to calculate the number particle distribution by
Porosity distributions resulting from particles having particle imaging methods, or by computer imaging/
different yields are then found from the residence time microscopy methods.
distributions by
3.8. Statistical properties
,~.o ~ o dz d Y (70) In addition to the probability distributions, mean
f ...... = f~';" d'Y de and standard deviations are calculated by the stan-
dard formulae
de
d--Y = (eml, - eo)flexp(- flY). (71) m,

On a catalyst weight basis this is given by

=
ff ~min
~fcd~ (81)

a = (~ -- 02f~d~. (82)
f2/, o = r~,o
' ~,ritdr cat" (72) rain

~t, in These values are determined by application of

On a number of particles basis this is given by Simpson's rule to approximate the integrals.

(.r..,,~o~ fw, O 4. M O D E L I M P L E M E N T A T I O N
. / e , rca t
f~.o= | ~ dr<~t. (73)
J r,at,mi~ teat ~/rcat Simulations were conducted with the software
package Mathcad Plus 5.0*. The integrals were nu-
On a weight of polymer basis, merically solved by a successive Romberg (poly-
nomial interpolation) algorithm. The convergence of
ff'(e) (1 + 1 Yo) f ' ....... (1 + Y)f~;o dr~.t (74) trapezoidal approximations is accelerated by extra-
cat.rain
polation of intermediate estimates and the corres-
Weight of polymer basis is most useful since the ponding subinterval widths.
measurement of porosity is most likely carried out on If an integrand function f(x) is such that it cannot
the total mass or volume of polymer product, for be properly approximated by polynomials, the integ-
example, through mercury porosimetry. ration method will become inefficient in terms of
precision and computational speed. In those cases
3.7.3. Polymer particle size, Polymer particle a variable transformation s(w) often improves numer-
radius can be related to polymer yield by eq. (75) with ical integration by changing the shape of the function
porosity given by eq. (69) above: to be integrated and by shifting the integration do-
main to the interval (0,1).
= ( 1 - e0~1/3(1 Peal Y ) 1/3. (75)
rp Feat ~ -i--~-~-i8 ff ~k -I--- ~ dw
P.,,
The expected distribution of particle sizes from the s(0) = xl, s(l) = x~. (83)
process can be related to the residence time distribu-
tion as Many functional forms for the transformation s(w) are
possible depending on the specific shape of the integ-
,~.o -w s dr dY (76) rand function f(x). The only requirement is that s(w)
f'" ..... = J " ;" d'Y dr~ be a monotonically increasing function in the interval
(0, 1).
dr, ( 1 - eo~r~, [po., r~ de-] Another problematical situation arises when the
d-'--Y = \ 1 - e J3r~ L pp + (1 - ~o)r~a, d-Y_] (77) integrand approaches a delta-like function. In that
case the function 'spiky' behavior tends to cause nu-
~,0 merical errors in the integration routines. A way
= f,,w,O
..... dr .... (78)
cir. l. around that problem is to divide the integration inter-
val into two regions. The first one (xx,x*) corres-
On a number of particles basis this is given by ponds to an arbitrarily chosen interval in whichf(x) is
well behaved. The second one is the interval (x*, x2)
~,o= ;?7 ....3 frp,rc.t
-o 1
or .... (79) where f(x) changes abruptly over the integration vari-
,i, I. rcat//'cat able x. This is shown in Fig. 9.
 Multistage polymerization of olefins 1
f~x)
I J
x1 x* x2
Fig. 9. Delta-like-behavior of integrand functions.
The numerical integration is then split over the two
intervals:
f ( x ) dx = f ( x ) dx + f ( x ) dx.
i 1
The first integral in eq. (84) is evaluated in the usual
way. The second integral requires a variable trans-
formation aiming at a non-stiff integrand function.
That is accomplished by transforming the integration
variable, x, over to the residence time domain, r:
f ( x ) dx = J~x') f i r ( x ) ] dr.
Notice that in the residence time domain all the func-
tions are relatively well behaved.
Whenever variable transformations such as the one
in eq. (12) are used, it is necessary to solve numerically
for the residence time of the catalyst as a function of
the property of interest. In this work that task was
accomplished through a Levenberg-Marquardt
quasi-Newton method.
The computational speed corresponding to the cal-
culation of all the distributions and statistical
variables of interest was reasonably fast. Total simula-
tion times ranged from 20 rain to 2 h on a 90 MHz
Pentium computer.
5. RESULTS
5.1. Process operatin9 conditions
Simulation conditions for the reactors used in the
simulations are shown in Table 3. The operating con-
ditions are typical of those reported in the literature.
For all cases a temperature of 70C was used and the
same kinetic parameters were used for each reactor.
Sorption factors were also used so that each process
could be directly compared on a consistent basis. No
adjustment to the kinetic parameters was necessary.
4873
Table 3, Simulations conditions for base case
Gas-phase Loop
reactors
Temperature (C) 70 70
Pressure (atm) 25 35
Monomer conc (mol/1) 1.267 9.917
Sorption factor 1.474 0.479
Reactor
Bed weight (t) 17.04
Volume (m3} 50 45
Solids fraction wt% 50
Catalyst feed rate (g/s) 0.2 0.2
ac~t 0.25 0.25
rc,t (pm) 33.4 33.4
b x 103 (l//~m) 7.054
D
In the case of the gas-phase reactors the gas is not
x ideal at the pressure and temperature used in the
simulations. For propylene the concentration at the
catalyst site is higher than in the bulk fluid as in-
dicated by the sorption factor. Bed weight was cal-
culated assuming a reactor volume of 50m 3 with
32 m 3 solids volume and 0.415 bed voidage. A poly-
mer density of 0.91 g/cm 3 was assumed for polypropy-
lene.
(84) For the loop reactor a recycle ratio of 5 was chosen
to represent the low recycle ratio case. It has been
previously reported that a recycle ratio of below 30
marks the onset of significant deviations from an ideal
CSTR behavior (Zacca and Ray, 1993). For the high
recycle ratio case, we assume a CSTR model since
a typical recycle ratio for these processes is about 100.
Note in the loop reactor the concentration of mono-
mer at the catalyst surface is roughly 1/2 that of the
(85) bulk phase due to monomer sorption effects.
For the base case simulations, the log mean catalyst
particle radius was 33.4 ~m and catalyst spread stan-
dard deviation, ac,~ was 0.25 in eq. (61). We have
chosen to use the same catalyst size and distribution
for each process so as to compare better the effects of
the different reactor residence time distributions on
the product properties (see Fig. 10). We have also
neglected heat and mass transfer effects for the simula-
tions studied. In practice, the catalyst size distribution
is an important consideration for industrial processes.
Gas-phase processes typically operate with smaller
catalyst particles to avoid overheating and melting
under the high rates of polymerization. Prepolymeriz-
ing the catalyst under mild conditions, prior to injec-
tion into the main reactor is also used for the same
purpose. The population balance approach presented
here can be easily extended to study the effects of
continuous prepolymerization and catalyst particle
size distribution on the performance of multistage
processes and is the subject of another article (Debling
et al., 1996b).
5.2. Residence time distributions
Figure I 1 shows the reactor residence time distri-
butions for the gas-phase reactors studied in this
paper, on a catalyst weight basis. The residence
4874 J. J. ZACCAet al.
0.14 Table 4. Mean residence times for the base case
-- t~eat= 0. I0
Reactor Stage ? (h)
......... ac~ = 0.25
0.12 -

- - - a~.~ = 0.50 VSBR 1 2.096

0.10 - HSBR 1 0.846
2 0.571
3 0.475
2 0.08- 4 0.424
%
FBR 1 2.064
~ 0.06-
! Loop (high recycle ratio) l 1.016
2 0.695
0.04 - ../
Loop (low recycle 1 0.995
7- ratio = 5) 2 0.635
// /

0.00 "/"'' ' C7~7~"7---q. . . . r-

0 2O 40 60 80 100 120 would expect for 4 CSTRs in series. This is because
Catalyst Radius ( microns ) the HSBR is modeled as 4 CSTRs in series with equal
volumes, not equal residence times. As the catalyst
Fig. 10. Catalyst particle size distributions considered in the moves through the HSBR, the cumulative product
simulations (log mean catalyst radius = 33.4/~m). overflow increases from stage to stage. This causes the
mean residence time, each in stage, to form a strictly
1.6e-4 monotonically decreasing sequence. For a given bed

1.4e-4
1.2e-4
\ reactor (FBR) is a hybrid distribution that is not easily
~ 8.0e-5
6.0e-5
4.0e-5
2.0e-5
0.0e+0
0 10000 20000 30000
Residence Time ( s )
Fig. 11. Base case residence time distributions for the gas-
phase processes.
time distribution of the vertical stirred bed reactor
(VSBR) is the typical exponential curve of the CSTR.
An important consequence of this is that a significant
fraction of the catalyst particles leaves the reactor at
very early times. These particles are still very active
and have little polymer yield. A narrower residence
time distribution is found for the horizontal stirred
bed reactor (HSBR) as a result of the 4 CSTRs in
series for the powder flow. One major advantage of
the HSBR over the VSBR is the reduced fraction of
catalyst particles with very short or very long resi-
dence times in the reactor. Catalyst particles with long
residence times in the reactor have been significantly
deactivated and are not productive. A summary of the
mean catalyst residence times for operation under
base case conditions is shown in Table 4.
It is interesting to note that the residence time
distribution of the HSBR is not as narrow as one
~ VSBR
HSBR 1
FBR
weight, however, the HSBR has a higher mean resi-
dence time (as given by the sum of the mean residence
times of each stage) than the VSBR as a result of the
RTD differences.
The residence time distribution of the fluidized-bed
modeled by n CSTRs in series. At short residence
times, the residence time distribution curve of the
FBR lies in between the VSBR and the HSBR. How-
ever, at longer residence times, the FBR residence
time distribution exhibits a long tail. These results are
easily explained by inspection of Fig. 12. In Fig. 12,
the residence time distribution of three catalyst par-
ticles sizes (10, 33.4, 75 #m) are shown. As a result of
40000 50000 particle size selection, small catalyst particles are seen
to remain inside the reactor for extremely long peri-
ods of time while most of the larger ones leave the
reactor very soon. The residence time distribution for
the mean catalyst radius is seen to be narrower than
the overall residence time distribution. The overall
residence time distribution of the FBR is complex and
can be seen as a combination of the individual resi-
dence time distributions of the different catalyst par-
ticles from the feed.
Figure 13 compares the residence time distribution
for a single-loop reactor as the recycle ratio is
changed. For low recycle ratios the residence time
distribution is oscillatory in nature and presents
a time lag due to the first pass of material through the
tubular section. Peaks of material leave the reactor
after each circulation time. As the recycle ratio is
increased the oscillations disappear and the residence
time distribution tends toward that of a CSTR. Fig-
ure 14 shows the effect of recycle ratio on two-loop
reactors in series. As in the case of a single reactor the
RTD is time delayed and oscillatory for low recycle
ratios. Complex peaks in the RTD result from non-
synchronized interactions between the peaks of each
 Multistage polymerization of olefins--I 4875
1.8e-4 single reactor. As the recycle ratio is increased the
-- Total RTD
residence time distribution of two continuous-stirred
1.6e-4 /,\ tank reactors in series is obtained. Note that even
1.4e-4 though the residence time distributions of one loop at
high and low recycle ratios are completely different,
1,2e-4

1.0e-4
~ 8.0-5
/1' the residence time distributions of the two-loop pro-
cess are very similar, particularly at longer residence
times. For the range of simulation parameters studied,
it would appear that two loops in series can be simply
modeled as two CSTRs with little error.
6.0-5

4.0-5 5.3. Production and catalyst yield

2,0e-5
Increasing the feed rate of catalyst increases the
production rate (ton/yr) of all reactors mainly because
0.0e+0 - i r i i i i i of two factors: (a) at higher catalyst feed rates (reduced
5000 10000 15000 20000 2 5 0 0 0 3 0 0 0 0 35000 40000 mean residence times) deactivation effects are pro-
Residence Time ( s )
gressively less important and catalyst particles
retain their activity; and (b) higher catalyst concen-
Fig. 12. Catalyst residence time distribution for the FBR
base case (log mean catalyst radius = 33.4/~m). trations are available for polymerization inside of
the reactor. On the other hand, reduced mean resi-
dence times result in lower catalyst mean yields
(cf. Figs 15 and 16). For the VSBR, for example,
1.2e-3 the mean residence time drops from 2.096 to 1.312 h
....... ~Sh RecydeR a ~ o
- - LowRecyclRatio= 5 by increasing the feed rate from 0.2 to 0.4 g/s.
1.0e-3 Production rate was calculated by assuming normal
operation at 0.95 service factor. Although catalyst
8.00-4 feed rate was varied over a wide range of flow rates
(0.05-1.6 g/s), practical process operational issues
6.0e-4
obviously restrict this. This sensitivity may be differ-
ent for each type of process. In addition, if catalyst
~3 yield is insufficient, residue content may be too high in
4.0e-4
the end product.
As a consequence of the higher mean residence time
2.0~4
of the HSBR over the VSBR, a production 'boost' is
noted. This yield enhancement, however, is a function
0.0e+0 I [ i i of catalyst deactivation rate and mean residence time.
2500 5000 7500 10000
Time(See)
When catalyst feed rate is changed from 0.05 to 1.6 g/s
the relative production rate of the HSBR over the
Fig. 13. Base case catalyst residence time distribution for VSBR increases from 1.175 to 1.255.
one-loop reactor.

45000

...... High Recycle Ratio -- VSBR

Low Recycle Ratio = 5 40O00
\ ......... HSBR
1.6e-4 -- - - - 2 Loops - High Recycle
FBR
35000
\
\\
\
30000 \
1.2e-4 \
\
25000

\,,
8.0~5 -~ z000o
v

4.0e-5
/ ~. 15000

10000

500O
i
/

0.0e+0 0 i i i i i m._ .__~

0 5000 10000 15000 20000 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Time (~) Catalyst Feed Rate ( g / s )

Fig. 14. Base case catalyst residence time distribution for Fig. 15. Effect of catalyst feed rate on mean catalyst yield of
two-loop reactors in series, the product.
4876
800000
~ VSBR
HSBR
2 Loops - High Recycle
FBR
600000 /////
///
///////
"
-~ 400000
/ .....
1 200000 ///
,/
.......
.... . . . .
0 -g----"-7 r r r r
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Catalyst Feed Rate ( g / s )
Fig. 16. Effect of catalyst feed rate on polymer production
rate.
Figures 15 and 16 illustrate the advantage of the
liquid pool loop process (two loops at high recycle).
The extremely high monomer concentrations give this
process the highest production rates (assuming the
same catalyst intrinsic activity). Among the gas-phase
reactors the HSBR has the highest production rate, as
a result of its higher mean residence time at identical
total reactor volumes. It is interesting to note (cf.
Fig. 15) that at low catalyst flow rates (high mean
residence times) the FBR performs worse than the
VSBR. As the catalyst flow rate is increased (de-
creased mean residence times) the FBR production
surpasses the VSBR. Similar effects of catalyst flow
rate on the product yield are found. This result is due
to particle selection effects in the FBR. Under the
conditions of the base case, particle selection hurts the
FBR performance by withdrawing the large catalyst
particles from the reactor prematurely, thus reducing
overall polymer yield. However, as the catalyst feed
rate is increased and the mean residence time of the
catalyst decreases, the particles are not able to grow as
large in size. Thus, particle selection effects do not
appear to suppress production as significantly as at
the lower feed rates. This effect is extremely interesting
since many models of the fluidized bed assume either
a continuous-stirred tank (Choi and Ray, 1985a;
McAuley, 1991; Talbot, 1990) or several stirred tanks
in series for the powder phase. Thus, particle selection
effects must be considered.
The influence of the outlet solids content on the
production and yield of two-loop reactors in series
was found to be as expected. Higher production and
yields are obtained with higher solids level. Of course,
there is a practical limit to the solids content as
dictated by process operation and safety.
5.4. Polymer properties
5.4.1. Yield distribution. Figure 17 shows the dis-
tribution of yields obtained by each of the continuous
processes studied. These curves are based on catalyst
J. J. ZACCAet al.
1.4e-4
I ~ VSBR
1.2e-4 f"
HSBR
FBR
2 Loops - High Recycle
J i
1.0e-4
,," 8.0e-5 J
'~ 6.0e-5
4.0e-5
2.0e-5
I ~ .... ~'x\
\
\
\
\
\
1.6 O.Oc+O ---r r r~ -
10000 20000 30000 413000 50000
Yield(g/g)
Fig. 17. Catalyst yield distribution for base case.
weight basis which is the natural method for calcu-
lation of yield. Note also that all curves tend to the
limiting yield as a result of catalyst deactivation which
is obtained at infinite residence times.
Again the main difference between the VSBR and
the HSBR is the increased weight fraction of catalyst
particles that exit the VSBR with low yields. The
narrow yield distribution of the HSBR reflects its
residence time distribution. For the FBR, particle
selection effects cause the smaller catalyst particles to
remain in the reactor for long residence times and
therefore reach values very close to the maximum
yield. The yield distribution of the FBR, therefore, is
sharply increasing close to the maximum yield, for the
base case simulation parameters. In the case of two-
loop reactors (high recycle) the maximum yield is
larger because of higher monomer concentration and
the distribution is broader.
The effect of recycle ratio on the yield distribution
of a single-loop reactor and two-loop reactors in
series is shown in Figs 18 and 19. For low recycle
ratios the oscillatory nature of the RTD is reflected in
the yield distribution. At high recycle ratios the yield
distribution of a CSTR is obtained. The yield distribu-
tion of two loops in series at low recycle shows the
same interaction pattern as the residence time distri-
bution curve. It is interesting to note that practically
no particles leave the two-loop reactors process with
yields less than about 7000 g/g for the low recycle
case.
By varying the feed rate of catalyst to the VSBR
and hence changing the mean residence time of the
catalyst, the shape of the yield distribution changes
dramatically (cf. Fig. 20). For high catalyst flow rates
(very low residence times) catalyst deactivation is not
very significant and, therefore, the catalyst weight
yield distribution tends to approach the exponential
decay shape of the residence time distribution curve.
[When deactivation is not considered at all (not
shown) the yield distribution curve actually mimics
 Multistage polymerization of olefins--I 4877
1.64 1.6e-4
-- Low Raeyele Ratio = 5 !-- qcat = 0.05 g/s ; ~ = 5.979 hr
....... High R~eyele Ratio .... qeat = 0.Hi g/s ; ~= 3.471 hr [ I
1.4e-4 1.4e-4 - - - - qcat = 0.20 g/s ; ,w= 2.096 hr [ I
\ r .... q.,=0,0,, .... ,,,2~p /
1.2e-4 1.2e-4

= 1.0e-4 = 1.0e-4

~ 8.0e-5 ~ 8.0e-5

g
6.0e-5 6.0e-5

4.0e-5 4.0e-5

2.0e-5 2.0e-5

00e+0 0.0e+0
0 1O1300 20000 30000 40000 50000 60000 0 5000 10000 15000 20000 25000
Catalyst Yield ( g / g ) Ca a yst Yield I g / g )

Fig. 18. Catalyst yield distribution for a single loop reactor Fig. 20. Effect of catalyst feed rate on mean catalyst yield of
(base case). the VSBR.

are related to the presence of a second stable site. In

4e-5 -- 2 Loops, Low Recycle Ratio = 5 [
..... 2 Loops, High R~eycle Ratio this case the mean residence time of the catalyst is
1
longer than the deactivation time constant of the first
site, which causes a positive increasing slope to the
3e-5
curve. However, the mean residence time is shorter
than the deactivation times for the second site causing
the downward trend at high yields. Thus, this curve
2e-5 represents a hybrid of the two extreme cases. Perhaps
other kinetic schemes with more than two sites can
lead to other exotic distributions.

le-5
Oe+O !"
10000 20000 30000 40000
Catalyst Yield ( g / g )
Fig. 19. Catalyst yield distribution for two-loop reactors in
series (base case).
the residence time distribution curve scaled for yield.]
For very low catalyst feed rates (high residence times)
catalyst deactivation effects dominate and a large
proportion of the catalyst leaves the reactor with little
remaining activity. The shape of the yield distribution
curve then tends to approach infinity at the maximum
catalyst yield. For intermediate feed rates, transitional
curves are found.
The results of Fig. 20 are explained as follows. The
shape of the yield distribution curve for the VSBR is
dependent on the relative relationship between cata-
lyst deactivation and mean catalyst residence time in
the process. When the catalyst mean residence time is
shorter than the time constant for deactivation, the
curve is a decay type that asymptotically approaches
the maximum yield. When the catalyst mean residence
time is greater than the decay times, the curve is
positive exponential and tends to infinity at the max-
imum yield. Transitional curves showing a maximum
5.4.2. Porosity distribution. Porosity distributions
(weight of polymer basis) at base case conditions are
related to the yield distributions and shown in Fig. 21.
Since the productivities of the loop reactor are the
50000 60000 highest, polymer from this reactor has the lowest
porosity. This can be important for the addition of an
ethylene-propylene copolymer phase for impact
copolymer as well as the effect on monomer diffusion
limitation, monomer devolitization and additive addi-
tion in downstream units. Note that the selection
factor for the FBR leads to a sharp peak at the lowest
porosity. Figures 22 and 23 show the effect of the
recycle ratio on the porosity distributions of a single-
loop reactor and two-loop reactors in series, respec-
tively. Again the oscillatory nature of the residence
time distribution is apparent at low recycles. In the
case of two loops in series the damped oscillations
might not even be detected experimentally.
5.4.3. Particle size distribution. Steady-state weight
particle size distributions for the base case of the
VSBR, HSBR, FBR and two loops (high recycle) are
shown in Fig. 24. On a polymer wcight basis the PSDs
for the VSBR and HSBR are very similar. This is
because the weight contribution of the particles leav-
ing the VSBR at small times is not very significant.
Particle size selection effects in the FBR tend to nar-
row the particle size distribution compared to the
VSBR and HSBR gas-phase reactors, and reduces the
4878 J. J. ZACCA et al.

20 3.0e-3
-ff
I I - VSBR -- VSBR
]] ....... HSBR /,, ......... HSBR
t'~ ] ~ FBR
2.5e-3

151 f'. o= 2.0e-3

~ 1.5e-3

~" 1.0e-3

//\ \,

0 ~ i i
5,0e-4

O.Oe+O
J
0.15 0.20 0.25 0.30 0~35 0.40 0.45 0.50 ) 5OO 1000 1500 2000 2500 3000
Particle Porosity ( void fraction ) Particle Radius ( microns )

Fig. 21. Particle porosity distribution for base case. Fig. 24. Weight particle size distribution for base case.

10

I -- Low Recycle Ratio = 5

......... High Recycle Ratio fraction of large size particles. For two-loop reactors
in series the PSD is broader and larger particle sizes
can be obtained.
Particle size distributions may be measured on
a polymer weight basis by mechanical sieving
6 or a particle number basis by scanning electron
microscopy. A comparison of the number and weight
basis particle size distributions shows that these
distributions are not the same. The weight basis al-
g.
ways gives a higher mean size than the number basis
(cf. Fig. 25).
2 For a single-loop reactor the number particle size
distribution (cf. Fig. 26) indicates that with lower
recycle ratios narrower particle size distributions are
0 obtained and no particles will leave the reactor with
0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 short residence times. This is not true of the loop at
Polymer particle Porosity ( void fraction )
high recycle ratios. On a polymer weight basis, how-
ever, Fig. 27 shows that the particle size distributions
Fig. 22. Particle porosity distribution for single-loop reactor.
of the loop at low and high recycle ratios are practic-
ally indistinguishable from each other. For two loops
,"~"~. [ -- Low Recyde Ratio ='~q in series, the particle size distributions at low and high
........ High Recycle Ratio
recycle ratios are even closer.
8 The effect of varying the spread of the catalyst
particle size distribution on the polymer particle size
distribution of the VSBR has the obvious effect of
6 broadening the polymer particle size distribution
(Fig. 28). No changes in production or yield are noted
for the loop, VSBR and HSBR since diffusion was not
considered. Slightly higher weight average particle
sizes are obtained for the catalyst with larger spread
parameters since the log normal average size was
2 preserved, not the catalyst weight average size.
Particle size selection effects cause the external par-
ticle size distribution of the FBR to be different than
0 the internal particle size distribution as illustrated in
0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 Fig. 29. Size selection causes the external particle size
Polyr~r particle Porosity ( void fraction ) distribution to produce larger particles than the inter-
nal distribution. The particle size distribution from
Fig. 23. Particle porosity distribution for two loops in series. the FBR is also narrower than the other reactors.
 Multistage polymerization of olefins--I 4879

- - VSBR- Wright Flzcdon 4.0c-3

2.0e-3 ....... VSBR - N u m l ~ r Fraeti<m -- ~== 0.25j
..O- 2 Loq~- l-lighR~yde - Ntna~rFriction 3.5e-3 .... o" a= 0.10
--II.-- 2 Loops- High R ~ y d e - Weight Fraction --- O'c= 0.50

3.0e-3
1.5e-3
g
'~ 2.5e-3
u.
== 2.0e-3
1.0e-3
1.5e-3 . : ~ ~ ~

1.0e-3 t
5.0e-4

5.0e-4 1

O.Oe+O
.~'"~ - _-
0 500 1000 1500 2000 2500 3000 3500 4000
500 1000 1500 2000 25C0 3000 particle Radius ( microns )
Particle Radius( microns )

Fig. 28. Effect of catalyst particle size distribution on poly-

Fig. 25. Comparison of number and weight particle size mer particle size distribution of the VSBR (log mean catalyst
distribution for base case. radius = 33.4 #m).

1.6e-3
-- LowRceydRatio= 5 3.0e-3
1.40-3

1.2e-3 2.5e-3

1.0o-3
~ 2.0-3
8.0o-4
1.5-3

z 4.00-46"00-41" "a
1.0-3

2.0e-4
5.0e-4
O.Oe+O i i

0 500 1000 1500 2000 2500 0.0e+0 """'/ F

Particle Radius ( microns ) 500 1000 1500 2000
Particle RaclkL~ ( microns)
Fig. 26. Number particle size distribution for a single-loop
reactor (base case). Fig. 29. Comparison of the internal and external particle
size distribution of the for the FBR (base case).
1.4e-3

1.2e-3
Varying the spread of the catalyst particle size dis-
tribution has a pronounced effect on the production
1.0e-3
of the FBR (cf. Table 5). For the same log mean
catalyst particle size, the production and yield from
8.0e-4
g the FBR is considerably higher for the narrow cata-
lyst particle size distribution than the broad size
6.0e-4 distribution. By inspection of Table 5, it is seen
g. that the mean yield of the polymer inside of the
4.0e-4 reactor is larger than in the product stream for the
broad catalyst distributions. However, as the catalyst
2.0e-4
size distribution becomes narrower, the outlet catalyst
yield exceeds the internal yield and the performance of
O.Oe+O
the unit surpasses the VSBR. Simulations for three
0 500 1000 1500 2000 2500 3000
sizes of monodispersed catalysts were also performed
P a ~ c l e Radius (microns)
and reveal the outlet mean yield was always higher
Fig. 27. Polymer weight particle size distribution for a single- than the internal yield and productivities were always
loop reactor (base case). higher than cases for broader catalyst particle size
4880 J. J. ZACCAet al.
Table 5. Summary of results for the FBR

Effect fP (h) f (h) W~,t (g) Y (g/g) Yo (g/g) rp.cut(#m) Capacity

(t/yr)
Catalyst PSD
Narrow (goat= 0.1) 1.787 2.254 1623.0 10,494 13,238 967.5 79,322
Base case (trcat =0.25 ) 2.122 2.064 1485.8 11,453 11,150 833.4 66,806
Wide (O'cat = 0 . 5 ) 2.844 1.821 1310.9 13,009 8318 594.1 49,841
Monodisperse (rear= 16.7/zm) 1.819 2.699 1943.5 8,763 13,009 499.8 77,948
M o n o d i s p e r s e (teat = 33.4 vm) 1.712 2.725 1962.2 8,678 13,819 1000.1 82,799
Monodisperse (r~,t=66.8/~m) 1.630 2.780 2001.9 8,508 14,514 2008.1 86,966
Catalyst flow rate
qc,t= 0.05 g/s 6.438 5.783 1040.9 16,351 14,699 890.8 22,019
qcat=0.2 g/s (base case) 2.122 2.064 1485.8 11,453 11,150 833.4 66,806
qcat= 1.6 g/s 0.512 0.595 3427.6 4966.8 5769.8 701.3 276,574
Selection parameter (b)
b = 0.007054 #m- 1 (base case) 2.122 2.064 1485.8 11,453 1,150 833.4 66,806
b = 0.003527 #m -1 2.000 2.118 1524.7 11,076 1,837 894.2 70,926
b =0.001764/~m -1 1.987 2.131 1534.2 11,090 1,908 947.6 71,348

distributions. Monodispersed catalysts with larger 5e-3

sizes led to higher production rates. Simulations with
........ o = 0 . I 0
the largest catalyst size (66.8#m radius) reveal the - - - - a = = 0.50
FBR production rate exceeded that of the HSBR 4e-3

reactor.
The above results are explained by understanding .g
the role of size selection in the FBR. Consider a mono- ,.~ 3e-3

dispersed catalyst polymerizing in an FBR. Since size

selection implies larger polymer particles are preferen-
tially removed from the reactor, the catalyst particles ~ 2e-3

do not leave the reactor until they have grown suffi-

ciently in size and yield. Thus, the mean catalyst yield
in the product leaving the reactor is always higher
than inside the reactor. To maintain the proper vol-
ume of powder in the reactor, the concentration of
catalyst in the reactor is then higher than that of
a CSTR. Thus, size selection aids the FBR by provid-
ing a 'boost' in production. Larger catalyst particles
lead to larger 'boosts' in production since the selection
factor is sensitive to the size of the polymer particles
[cf. eq. (46)] which are proportional to catalyst size
according to eq. (75). Increased cutting diameters and
outlet yields cause production levels to increase with
catalyst radius.
By broadening the particle size distribution of
the catalyst, size selection begins to suppress the
productivity of the FBR. This is because larger poly-
mer particles no longer imply high yield catalyst
particles. Large polymer particles may also be gener-
ated from large catalyst particles with low yield.
It would then seem reasonable that utilization of
large catalyst particles with narrow particle size
distribution would be beneficial to the productivity
of the FBR (Fig. 30). However, practical issues
limit the maximum catalyst size that can be employed
in the reactor. The potential for particle overheating
greatly increases with catalyst size, for example
(Hutchinson and Ray, 1987), and monomer diffusion
limitations also become more significant (Hutchinson,
1990).
/
le-3
//
0e+0 J J J ~ ~ p I I
500 1000 1500 2000 2500 3000 3500 4000
Particle Radius ( microns )
Fig. 30. Effect of catalyst particle size distribution on the
polymer weight particle size distribution of the FBR (log
mean catalyst radius = 33.4 #m).
Since size selection appears to have significant im-
plications on the performance of the FBR, simulations
were performed by varying the sensitivity of selection
by changing the selection parameter 'b'. The effect of
changing 'b' on the residence time distribution of the
FBR is shown in Fig. 31. As particle size selection
becomes less sensitive, more particles leave the reactor
with shorter residence times. Under no size selection
the residence time distribution approaches the CSTR
case. The effects of size selection on the production of
the FBR are shown in Fig. 32. We find an optimal
value of b for which the production of the FBR is
maximized, given the base case conditions and cata-
lyst size distribution. At high values of the selection
parameter b, particle selection effects tend to decrease
production due to the withdrawal of large particles
with low polymer yield. At very low values of b some
fraction of the particles will leave the reactor with
 Multistage polymerization of olefins--I 4881
1.4e-4
--'" b=7.054x I04Coasec~se) I
i

1.8e-3 I .... ]
----- b = 3 , 5 2 7 x 10 d /
1.20-4 ...... b = 1.7635x 10 .3 ] 1.6e-3 - - - Largepor~ty changes(fl = 8 109x]O~) j
- - b=0
1.40-3
1.0e-4
:'k\ .~ 1.2e-3

~ 8.0e-5 ~ ,.oe-3

6.0e-5 ~ 8.0e-4
/ f
,~ a, 6.00-4
4.0e-5
4.00-4
It
2.00-5 I / / ~ 2.0e-4

/ ~ o.oo+o ! "*'#
-
I i i

O, Oo+O i j i 0 50O 1000 1500 2000 2500

0 5000 10000 15000 20000 25000 PartideSi~ (micmns)
ResidenceTime(s)
Fig. 33. Effectof porosity changes on the particle size distri-
Fig. 31. Effectof size selection parameter'b'on the residence bution of the VSBR reactor.
time distribution of a fluidized-bed reactor.

5.5. Effect of varyin 9 the kinetic parameters

1.07
To study the effects of changing the kinetic rate
constants has on the behavior of the processes
1.06 studied, simulations were performed by varying the
rate of site transformation reaction. Results are shown
1.05
for the VSBR in Fig. 34. Changing the site trans-
1.04 formation rate (by possibly operating at higher co-
catalyst concentrations) has a similar effect as chang-
1.03
,,:.. ing catalyst feed rate on the yield distribution. There is
1.02 a maximum yield based on catalyst deactivation and
it can be quite low for rapid catalyst deactivation.
1.01 Often, researchers use a one site plus simple first-
order decay to model their catalyst system. Metal-
1.00
locene catalysts may also be modeled in this manner.
0.99 Simulations were performed with the VSBR using
a one-site model fit to the data of Di Drusco and
0.98 i I [ I I I
Rinaldi (1984) and shown in Table 6 (see also Fig. 35).
0 1 2 3 4 5 6 7
Small differences are noted in the overall yield and
Size Selection P a r a m e t e r "b" x 10 3
production rates of the reactor compared to the two-
Fig. 32. Effect of size selection parameter 'b' on the relative site model of Fig. 34. However, there is no maximum
production of the FBR with respect to the VSBR. in the yield distribution curve because of the absence
of the second stable site.

short residence times and low polymer yield and the 5.6. Statistical properties of the distributions
FBR production reaches the levels of the VSBR. Statistics for the base case are shown in Table 7. It
Table 5 also illustrates the fact that for nonwell is important to recognize that different bases (catalyst
mixed reactors the mean residence time on a polymer weight, number of particles, weight of polymer) show
weight basis differs from the one calculated on a different results. It is important to choose the proper
catalyst weight basis. This is an important difference basis for calculation purposes. For instance, average
to keep in mind whenever average residence times of yield is more naturally calculated on weight of cata-
a reactor are calculated. lyst basis while average particle size is usually ex-
Additionally, in this paper we consider varying the pressed on a polymer weight basis. The standard
rate at which polymer particle porosity changes with deviation is the variable of choice to evaluate the
polymer yield. By varying this sensitivity it can be spread of the different distributions. Due to particle
seen that changes in porosity can have a significant size selection phenomena in case of the fluidized-bed
effect on the particle size distribution as shown in reactor, number-based statistical properties differ
Fig. 33. Often, however, researchers neglect these cha- from catalyst-weight-based statistical properties.
nges and attempt to correlate polymer yield with Among the gas-phase reactors the HSBR is the one
weight mean polymer particle size. The results of with the highest catalyst weight average yield since its
Fig. 33 indicate this may not be a valid measurement average residence time is the highest at base case
unless the changes in polymer porosity are small. conditions. The HSBR is the reactor with the smallest
4882
porosity a n d yield distribution spreads because of its
n a r r o w residence time d i s t r i b u t i o n relative to the
o t h e r gas-phase reactors. However, as a consequence
of size selection the F B R possesses the n a r r o w e s t
J.J. ZACCAet al.
particle size distribution a m o n g all reactors, yet its
yield distribution is broad. Low recycle ratios n a r r o w
the distributions with respect to the well mixed case
for the loop reactor. F u r t h e r n a r r o w i n g takes place
with the a d d i t i o n of one more reactor in series.

2.0e-4
i 1~ lqR= 1.193x 10~ (1 is)
kit2= 2.385 x 10 4 (1 Is) 6. CONCLUDING REMARKS
[ kal2= 4.770 x 10 4 (1 Is) In this paper, we have developed a general framework
1.6e-4 [/ k~I~= 2.385 x 10.3 ( 1/ s)
for p o p u l a t i o n balance modeling of solid-catalyzed
//' olefin processes using a comprehensive multisite
1.2e-4 kinetic model a n d including catalyst particle size
z

~ 8.0e-5 2.0e-4
-- No Deactwation
--- kal = 9.055 x 10"~sq
......... kdl = 1.811 x 104 S"l
4.0e-5 ---- kal = 3.622 x 10"+s"t
1.5e-4
I
II
0.0e+0
5000 10000 15000 20000 25000 30000 35000 40000
1.0e-4
i
t
Yield ( g/g ) 1
/
I ,;
Fig. 34. Effect of site transformation reaction on catalyst
yield distribution for the VSBR.
// /,,,"
5,0e-5 // J/

Table 6. Kinetic parameters used for the one site model

Kinetic parameter Value O.Oe+O ~

0 5000 10000 15000 20000 25000 30000 35000 40000
kill (l/mol/s) 269.1
Weld(g/g)
kd~ (l/s) 1.811 10 -4
0.40
To'0t 10 Fig. 35. Effect of catalyst deactivation rate on catalyst yield
distribution: one-site model for VSBR.

Table 7. Summary of results for the base case simulations

VSBR HSBR FBR 1 loop 1 loop 2 loops 2 loops

(high rec) (low rec) (high rec) (low rec)

Mean residence time (h) 2.096 2.317 2.064 1.016 0.979 1.711 1.630
Production (t/h) 67,620 83,500 66,806 119,000 120,600 173,900 174,124
N* avg mean yield (g/g) 11,270 13,940 13,925 19,860 20,120 29,020 29,060
N yield STD* (g/g) 5791 3269 6256.2 12,760 11,490 11,300 10,082
W: avg mean yield (g/g) 14,240 14,700 13,324 28,060 26,680 33,420 32,501
W yield STD (g/g) 4516 2922 5520.8 11,350 11,030 9722 9212
Cat s avg mean yield (g/g) 11,270 13,940 11,170 19,860 20,120 29,020 29,060
Cat yield STD (g/g) 5791 3269 6277.6 12,760 11,490 11,300 10,082
N avg mean porosity 0.386 0.36 0.363 0.328 0.323 0.265 0.264
N porosity STD 0.053 0.028 0.053 0.091 0.079 0.069 0.0591
W avg mean porosity 0.358 0.353 0.386 0.271 0.279 0.239 0.243
W porosity STD 0.039 0.025 0.051 0.07 0.069 0.053 0.0505
Cat avg mean porosity 0.386 0.36 0.367 0.328 0.323 0.265 0.264
Cat avg porosity STD 0.053 0.028 0.047 0.091 0.079 0.069 0.0591
N avg radius (/~m) 774 858 836.5 896.4 917.1 1035 1040
N radius STD (/~m) 259.5 227.5 158.4 315.7 285.9 295.7 285.9
W avg radius (/~m) 1029 1050 914.2 1238 1212 1304 1294
W radius STD (#m) 285.2 273.1 151.3 353.7 346.8 350.2 345.0

*N = Particle number based.

t STD = Standard deviation.
; W = Polymer weight based.
SCat = Catalyst weight based.
 Multistage polymerization of olefins--I
distributions and monomer diffusion. Catalyst resi-
dence time was used as the internal coordinate and
the internal and external distributions may be differ-
ent. The modeling framework may be applied to
a process consisting of a train of reactors in series. The
steady-state modeling of multistage processes for
propylene polymerization has been shown.
It is shown that common industrial processes for
propylene polymerization can produce a product with
a wide distribution of polymer properties. Processes
with narrow residence time distributions produce
a product with narrow property distributions. Signifi-
cant differences among the processes were noted.
With no diffusion resistances considered, catalyst par-
ticle size distribution does not affect the production
and yield of the VSBR, HSBR or loop. However,
catalyst particle size distribution does have a signifi-
cant effect on the performance of the FBR. To im-
prove the performance of the FBR it would appear
advantageous to use a very narrow catalyst particle
size distribution. For monodispersed catalysts, larger
particle sizes lead to higher productivities in the FBR
compared to smaller particles. Larger polymer par-
ticles are often desired for better fluidization, minimiz-
ing fines carryover and product handling. However,
larger catalyst particles may be more prone to over-
heating and sticking in the reactor. Issues such as
catalyst feed position, removal of fines, the presence of
a disengagement zone will clearly have an effect on the
performance of the fluidized bed. For the simulations
presented here, some conditions for maximizing pro-
duction in the FBR were noted. Further optimization
with the modeling work presented here is easily pos-
sible.
From the results of this study, it is clear that the size
selection features of the FBR greatly affects its perfor-
mance. Thus, there is value in considering the rational
design of size selection functions. Some loop processes
have settling legs which can favor larger particles; the
VSBR is an expanded bed and by adjustment of the
withdrawal tube one can achieve some degree of size
selection. A recent patent by Mitsubishi Chemical
Industries describes the use of external size selection
equipment to return smaller particles to the reactor
(Takashima et al., 1985). The modeling approach de-
veloped here can be used as a tool to simulate and
design practical size selection equipment in order to
improve process performance.
It should be noted that simulation studies shown
here are for reactors at steady-state model where
processes are usually maintained. However, many
processes are designed for the production of multiple
grades during a set cycle time. Minimizing the amount
of 'offspec' product produced during the transition
to a different molecular weight or comonomer com-
position is important and the subject of several
articles (Debling et al., 1994; McAuley and Mac-
Gregor, 1992). It is interesting to note that population
balance modeling can be used to study the effect of
changing grades on the complete distribution of prod-
ucts produced in the reactor environment. Grade
4883
transition studies may be done by extending the
modeling work here.
In addition to the obvious role of catalyst deactiva-
tion, a secondary effect is to dilute the differences
between the natural residence time distributions of
the different processes. We find the largest differ-
ences amongst the processes for cases where the resi-
dence time of the process is shortest (little catalyst
deactivation).
Besides the properties calculated in this work, other
important properties can also be generated from the
residence time distribution. Polymer architecture
properties such as composition and molecular weight
distributions can be predicted. This will be addressed
in a future publication (Zacca et al., 1996}.
Residence time distributions can have a pro-
nounced effect on the properties of multi-layered
products produced in a series of reactors. In each
reactor, a completely different polymer product may
be formed by changing the composition of the reactor
fluid, temperature and pressure adding to the pre-
viously formed polymer. In a subsequent paper of this
series, we look at the case of impact polypropylene
produced by several commercial processes (Debling
et al., 1996a). It is seen that the residence time distri-
bution of the process leads to varying amounts of
copolymer in the final product. This has implications
for polymer particle sticking, diffusion, composition
distributions and can affect product quality. Also, as
a result of site transformation effects, catalyst particles
that remain in the homopolymer stage for long peri-
ods of time are essentially in the Ti 2 + state. Thus,
when they enter the copolymer reactor, they produce
a more ethylene-rich copolymer.
Acknowled(4ements The authors are indebted to the Na-
tional Science Foundation, the Industrial Sponsors of the
University of Wisconsin Polymerization Reaction Engineer-
ing Laboratory (UWPREL), O.P.P. Petroqu[mica S. A. and
Conselho Nacional de Desenvolvimento Cientlfico e Tec-
nol6gico (CNPq) for their financial support of this research.
NOTATION
b size selection parameter, 1//~m
(7 vector of normalized catalyst site concen-
trations, dimensionless
C~ normalized concentration of dead sites,
dimensionless
~'p normalized concentration of potential
sites, dimensionless
/)k normalized concentration of dead chains
of length n at site k, dimensionless
loop axial dispersion coefficient, cm2/s
f generic distribution representation,
1/property
[H2] concentration of hydrogen at the sites,
gmol/l
k~ apparent rate constant for activation of
site type k, 1/s
kcllj
k rate constant for chain transfer at site
type k, 1/mol/s
4884 J. J. ZACCAet al.
k~j apparent rate constant for deactivation e~i. minimum catalyst porosity, dimensionless
of site type k, 1/s 2 eigenvalue of matrix K
k~o, rate constant for initiation of site type k, /~. normalized zeroeth moment of polymer
l/mol/s chains ending in monomer i at site k,
k~,~ rate constant for propagation of mono- dimensionless
mer i at a chain ending with monomer /]ko normalized zeroeth moment of all poly-
j on site type k, 1/mol/s mer chains at site k, dimensionless
k~,' apparent rate constant for site trans- mathematical constant (3.14159 ... )
formation from type k to 1, 1/s PR, Peat, reactor, catalyst, polymer and liquid-
K matrix of apparent kinetic rate constants, Pp, Pt phase densities, respectively, g/cm 3
1/s a distribution normalized standard devi-
L loop tube length, cm ation
[Mi]b concentration of monomer i in the bulk acat catalyst particle size distribution spread
fluid, gmol/1 parameter,/~m
[Mi]~ sorbed concentration of monomer i at ~O size selection factor, dimensionless
the catalyst sites, gmol/l z catalyst residence time in reactor, s
MWl molecular weight of monomer i, g/gmol .~tot,.~, ~p total, catalyst and polymer weight mean
MWT, molecular weight of Titanium, g/gmol residence times, respectively, s
Nsites number of sites ~ effectiveness factor for monomer i,
Nmon number of monomers (dimensionless)
P matrix of right-hand eigenvectors of K
Pe Peclet number, dimensionless Acronyms
normalized concentration of sites of type CSTR continuous-stirred tank reactor
k and chain length n ending in monomer FBR fluidized-bed reactor
j, dimensionless HSBR horizontal-stirred bed reactor
normalized concentration of vacant sites PSD particle size distribution
of type k, dimensionless RTD residence time distribution
q, qeat, qp total, catalyst and polymer mass flow VSBR vertical stirred bed reactor
rates, respectively, g/s
QO loop volumetric discharge rate, cma/s Superscripts and subscripts
QRec loop volumetric recycle rate, cm3/s n number fraction of particles
rcat catalyst radius, #m p weight fraction of polymer
rp particle radius,/~m tot total mass fraction
rp, c u t particle cutting radius, #m w weight fraction of catalyst
r, rate of change of property with time, F reactor feed
property/s O outlet of reactor
Rec loop recycle ratio, dimensionless R inside the reactor
kinetic rate of mass consumption of catalyst radius
Feat
monomer i, g/g/s rp particle radius
A obs
Rpi observed rate of mass consumption of y polymer yield
monomer i, g/g/s e particle porosity
t chronological time, s catalyst residence time
loop tubular velocity, cm/s mean value
v~ reactor volume, cm 3 mol fraction with respect to the total
x~i fraction of titanium atoms that are cata- amount of catalyst
lyst sites, dimensionless
Ws solids weight fraction, dimensionless
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