Journal of Industrial and Engineering Chemistry 33 (2016) 298306

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Dynamic simulation of liquid polymerization reactors in Sheripol

process for polypropylene
Shin Hyuk Kim a, Seung Won Baek a, Jae Cheol Lee b, Woo Jin Lee c,
Seong Uk Hong a,**, Min Oh a,*
a
Department of Chemical Engineering, Hanbat National University, 125 Dongseo-daero, Yuseong-gu, Daejeon 305-719, South Korea
b
Schneider-Electric Co., Ltd., 13F, Jei Platz, 186, Digital 1st, Geumcheon-gu, Seoul, South Korea
c
Hanwha Corporation, 117 Yeosusandan 3-ro, Yeosu-si, Jeollanam-do, South Korea

A R T I C L E I N F O A B S T R A C T

Article history: This work executed mathematical modelling and dynamic simulation of a polyolen process with pre-
Received 19 August 2015 polymerization and two loop reactors. Transient changes occurring within the reactors were simulated
Received in revised form 13 October 2015 based on a one-dimensional plug ow assumption. Temperature control in the reactors is germane to the
Accepted 14 October 2015
realization of the desired products because of the exothermic reactions, and this was accounted for using
Available online 23 October 2015
cooling jackets. The gPROMS package was utilized as a software platform for modelling and simulation.
The results identied the physicochemical changes in each reactor. Molecular weight and
Keywords:
polydispersity were predicted. Simulation results were validated with commercial data and agree well.
Polymerization
Polypropylene
2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Ziegler Natta reserved.
Loop reactor
Simulation

Introduction
Mathematical modelling and simulation of the polypropylene
reactors covered in this project has been carried out previously
with most of these works focused on liquid-polymerization
reactors [13]. These researchers modeled loop reactors as a
continuous stirred tank reactor (CSTR), and this approximation of
loop reactors works fairly well in regimes with high recycle ratios.
In practice, loop reactors can exhibit outlet polymer concentrations
that differ signicantly from concentrations inside the reactor as
explained by Ferrero and Chiovetta (1990) [46].
Discrepancy in the CSTR assumption has been elucidated
through their prediction of end-use polymer properties via steady-
state as well as dynamic simulations [7,8]. Development of
computer and mathematical analysis tools has enabled the
simulation and analysis of loop reactors on a multi-dimensional
scale. Zacca and Ray [9] predicted physical changes occurring
within a loop reactor using a one-dimensional model; but this
work could not reect molecular weight (MW), which decides the
property of a polymer made from the prediction of physical
* Corresponding author. Tel.: +82 42 821 1535; fax: +82 42 8211593.
** Corresponding author. Tel.: +82 42 821 1536.
E-mail addresses: suhong@hanbat.ac.kr (S.U. Hong),
minoh@hanbat.ac.kr (M. Oh).
changes and is the most important property for deciding polymer
characteristics. Many researchers propose the method of most
probable distribution (MPD) to overcome this difculty [10,11];
however, the MPD method, which is an expression of MW based
on statistics, cannot reect the variables of mathematical models
so that it is not acceptable for dynamic simulation expression. A
reactor based on the commercial process data designed and
simulated was investigated in 2007 and 2010 [12,13]. Although
they found that the technology of polymer simulation could be
used for real process design, they maintained the CSTR assumption.
Olen polymerization normally requires catalysts. The composi-
tion and structure of the catalyst used directly affects polymer
properties and characteristics [14,15]; therefore, catalyst selection is
an important factor. Despite the broad spectrum of high mileage
catalyst systems that have been available in recent times, use of
ZieglerNatta catalysts has dominated propylene production
processes. The 1970s witnessed probing research into reaction
mechanisms involving ZieglerNatta catalysts [2,1618]. This
culminated in the suggestion of a kinetic mechanism that involves
a consideration of the elementary reaction with a catalyst [19]. Since
then, many researchers have developed the universal kinetics of
polypropylene synthesis on the basis of Hutchinsons idea.
A review of previous works reveals the absence of a multiscale
model that adequately accounts for a realistic reactor mode and
rigorous mathematical description of MW distribution. Most
works employ the plug ow assumption and account for MW

http://dx.doi.org/10.1016/j.jiec.2015.10.017
1226-086X/ 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
 S.H. Kim et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 298306 299

Nomenclature

A area of tube, m2
A co-catalyst
Atran heat transfer area, m2
ci concentration of component i, mol m3
C* active catalyst
Cd inactive catalyst
Cp heat capacity, J kg1 K1
Dz dispersion coefcient, m2 s1 Fig. 1. Block diagram of the loop reactor structure.
E activation energy, J mol1
H2 hydrogen Table 1
k reaction constant, m3 mol1 s1 or s1 Design parameters of polymerization reactor.
k0 frequency factor, m3 mol1 s1 or s1 Parameter Pre-polymerization Polymerization
Kz heat dispersion coefcient, J m1 s1 K1 reactor loop reactor
m mass, kg Length of reactor 45 m 190 m
m mass ow rate, kg s1 Diameter of tube 0.168 m 0.6 m
Diameter of jacket 0.273 m 0.8 m
M monomer Recycle ratio 75 153.3
Mn number average molecular weight, g mol1 Flowrate of cooling water 11.11 kg s1 222.22 kg s1
Mw weight average molecular weight, g mol1
MW molecular weight, g mol1
and changes occurring in the one-dimensional model of the loop
MWm molecular weight of monomer, g mol1
reactors instead of a widespread statistical approach. The
MWn molecular weight of polymer chain n, g mol1 polymerization loop reactor in the Spheripol process, being
PPi active polypropylene of chain i comprised of three reactors (pre-polymerization reactor, two loop
PPi inactive polypropylene of chain i reactors), was employed as a target process. The simulation was
q heat of transfer with cooling jacket, J s1 carried out and validated with data from an existing commercial
R ideal gas constant, J mol1 K1 plant. The gPROMS package was utilized as a software platform for
Se energy source term of polymerization, J m3 s1 modelling and simulation [20].
Sm,i mass source term of component i, mol m3 s1
T temperature, K Model description and mathematical modelling
u velocity, m s1
Description of reactors
V volume of reactor
The polymer reactor (Fig. 1) is a thin-walled tubular reactor
Greek notations surrounded by external cooling jackets for heat exchange to induce
r density, kg m3 the growth of macromolecules because of the temperature
req density by thermal dynamic, kg m3 sensitivity of the polymerization reaction. Sufcient circulation
@ partial is also required in the loop reactor because of its susceptibility to
Si active mis-insertion polymer space alteration.
A summary of some important design parameters of the pre-
Indices polymerization and loop reactors is shown in Table 1. Very high
d deactivation recycle ratios and cooling water rates are required in the loop
reactors to avoid thermal runaways compared with those required
in initiation
in the pre-polymerization reactor.
n number of polymer chain
p propagation
Mathematical modelling of reactors
s secondary insertion
str chain transfer after mis-insertion The loop reactor has been modeled as a one-dimensional plug
t cooling jacket tube Simulation time index ow reactor, and the resulting changes in concentration and heat
tr,A transfer to co-catalyst of reaction are represented as source terms in the following
tr,H transfer to hydrogen mathematical formulations. Continuity assumption underscores
tr,M transfer to monomer the mathematical models presented below.
z dimension index
Reactor
Mass balance
via statistics, while rigorous mathematical modelling of MW is
often seen to be accompanied by the CSTR approximation based @ci @c u @ @c
 i Dz i Sm;i (1)
on high recycle ratios. This unravels the necessity of dynamic @t @z @z @z
simulation based on a rigorous mathematical model for the
@r @ru
performance, analysis, and optimization of the process.  (2)
@t @z
In this work, rigorous mathematical modelling involving the
polymerization mechanism and balance equations for all chemical where ci is the concentration of component i, u is the velocity, Dz
species is used in predicting the properties of each polymer chain is the dispersion coefcient, Sm,i is the mass source term of
300 S.H. Kim et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 298306

component i and u is calculated from momentum balance equation Table 2

ZieglerNatta reaction mechanism for PP polymerization.
in reactor model. Sm,i is calculated by reaction mechanism using
the Arrhenius equation and reaction constant. Initiation kin
C  Mxrarr;PP1
Momentum balance
Propagation kp
ru req u (3) PP1 Mxrarr;PP2
..
.
kp
PPi Mxrarr;PPi1

m ruA (4)
Chain transfer to hydrogen ktr;H
PPi H2 xrarr;PP i C 
where r, req are density and density by thermal dynamic, Chain transfer to monomer ktr;M
respectively. Momentum balance is considered continuity equa- PPi Mxrarr;PP i C 
tion under some assumption. Chain transfer to co-catalyst ktr;A
PPi Axrarr;PP i C 
Energy balance Deactivation reactions kd
PPi xrarr;PP i C d
Spontaneous deactivation
@T @T @ @T q kd
C  xrarr;C d
rC p  urC p  K Se (5)
@t @z @z z @z v
where Cp is the heat capacity, Kz is the heat dispersion coefcient, Se Table 3
is the energy source term of polymerization, q is the heat of transfer ZieglerNatta reaction constant for PP polymerization.
with cooling jacket, T is the temperature in reactor and V is the
Reaction constant k0 E
volume of reactor. T is dynamically changed by energy source and
4 3 1 1
heat transfer. kin: Initiation 4.97  10 m mol s 50,000 J mol1
kp: Propagation 4.97  104 m3 mol1 s1 50,000 J mol1
Molecular weight
ktr,H: Transfer to hydrogen 4.4  103 m3 mol1 s1 50,000 J mol1
MW n nMW m (6) ktr,M: Transfer to monomer 6.16 m3 mol1 s1 50,000 J mol1
ktr,A: Transfer to co-catalyst 7.04  101 m3 mol1 s1 50,000 J mol1
P kd: Deactivation 7.92  103 s1 50,000 J mol1
nMW n
Mn P (7)
n
where Cp,t is the heat capacity, Tt is the temperature and Vt is the
P
nMW n MW n volume of cooling jacket. Tt is also dynamically changed by heat
Mw P (8) transfer.
nMW n
Heat transfer with reactor
where MWn is the molecular weight of polymer chain n, MWm is
the molecular weight of monomer, Mw is the weight average q UAtran TT t (13)
molecular weight and Mn is the number average molecular weight.
where U is the overall heat transfer coefcient and Atran is the heat
Cooling jacket transfer area (Table 2).
Mass balance
Description of reaction kinetics in polymerization
@rt @r ut
 t (9)
@t @z
A detailed mechanism for the radical polymerization reaction
where rt is the density and ut is the velocity in cooling jacket tube. employing ZieglerNatta catalysts in the loop reactors is shown
There variable value is from momentum balance in cooling jacket in Table 2. This involves initiation, propagation, transfer, and
model. deactivation steps. Rate constants of the various steps can be
Momentum balance determined using the Arrhenius equation.
rtut rt;eq ut (10)  
E
k k0 exp  (14)
RT
mt rt ut At (11)

Energy balance where k reaction constant, k0 is the frequency factor and E is the
activation energy.
@T t @T t q The activation energies E and frequency factors k0 of the
rt C p;t  ut rt C p;t  (12)
@t @z V t reaction steps in Table 3 are shown in Table 4 [10].

Table 4
Material balance of simulation result.

Stream number 101 102 103 104 105 106 107 108 109
Description Catalysts Propylene R1outlet Propylene R2outlet Propylene R3outlet Top Bottom
Fraction kg h1 kg h1 kg h1 kg h1 kg h1 kg h1 kg h1 kg h1 kg h1

Catalysts 12.35
Hydrogen 0.07 0.07 1.13 0.64
Propylene 1719.64 1396.02 27,391.29 12,240.54 15,681.14 17,586.29 15,208.35 2377.94
Propane 180.29 180.49 2871.72 3075.53 1644.02 4734.58 4053.75 680.88
Polymer 335.77 16,860.42 27,181.42 27,181.42
Total 12.35 1900 1912.35 30,264.14 32,176.49 17,325.8 49,502.29 19,262.1 30,240.19
T (8C) 10 10 20.3 45 70.1 45 70.2 70 70
P (bar) 40 35 35 35 35 35 35 18.4 2
r (kg m3) 512 578 512 714 512 725
 S.H. Kim et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 298306 301

Fig. 2. Schematic diagram of liquid polymerization reactors.

Usually, heat of reaction only occurs in the propagation step Result and discussion
when catalysts are employed. In the case of PP, a value of
8.635  104 J mol1 is evolved. Dynamic behavior of reactors

Description of loop reactor section in Spheripol process
A detailed ow chart is represented in Fig. 2. R1R3 represent
the three reactors employed in the process. The pre-polymeriza-
tion reactor is designated R1 and the two loop reactors are denoted
by R2 and R3.
Liquid polymerization of polypropylene begins with the pre-
polymerization step. Pre-polymerization occurs in a reactor with a
height of about 45 m and a diameter of 0.168 m. Better control of
operating conditions can be achieved in the pre-polymerization
reactor compared with the main polymerization step. The rst loop
reactor functions to grow the pre-polymerization product. The rst

Fig. 3. Monomer concentration prole with time and space: (a) pre-polymerization reactor, (b) 1st loop reactor, (c) 2nd loop reactor.
302 S.H. Kim et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 298306

loop reactor is 50 times larger than the pre-polymerization reactor,
allowing for a longer residence time while being quite difcult to
control. The existence of active catalysts and live polymer from the
rst loop reactor is exploited by a second loop reactor, which is
similar in size and operating conditions to the rst. The only
notable difference between them is the amount of control action
required to maintain temperature at set-point. A rapid tempera-
ture rise occurs in the second loop reactor compared with the rst.
The monomer concentration in the reactors decreased exponen-
tially and attained a steady-state value after about 10,000 s (Fig. 3).
The zenith and nadir of the graph correspond to concentrations of
11,064.69 mol m3 and 10,081.42 mol m3 respectively. The mono-
mer concentration in the rst loop reactor took 26,000 s to decrease
from 11,065.25 to 6511.77 mol m3 at a temperature of 343.15 K.
The rate of polymerization is rapid after about 10,000 s as illustrated
in Fig. 3(b), while a constant temperature was maintained in the
reactor by the recycle stream. The longer duration taken for the
process to reach steady state can be accounted for by two reasons:
rst, the temperature difference between the inux and operating
condition and, second, the reactor size. In the second loop
reactor, the feed concentration of the monomer decreased from
11,065.41 mol m3 to 6143.68 mol m3. There is a striking similari-
ty between the concentration proles of Fig. 3(b) and (c). Reactions
in the second loop reactor take longer (27,000 s) to reach steady state
because of the difculty in contact between the active polymer and
the active sites of the catalysts.
A decrease in monomer concentration results in generation
of the desired products. A plot of polymer concentration in the

Fig. 4. Polymer concentration prole of live polymer and dead polymer with time at reactor exit: (a) pre-polymerization reactor, (b) 1st loop reactor, (c) 2nd loop reactor.
 S.H. Kim et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 298306 303

Fig. 5. Temperature prole with time at reactor exit: (a) pre-polymerization reactor, (b) 1st loop reactor, (c) 2nd loop reactor.

pre-polymerization reactor (Fig. 4(a)) shows that a maximum
concentration of 3.81 mol m3 is achieved at equilibrium with
living polymers accounting for about 90%. The results of the
generation of polymer in the rst loop reactor with emphasis
placed on the percentage of living and dead polymer (Fig. 4(b))
show that dead polymer accounts for about 80% of the total
polymer produced. From this percentage of dead polymer
obtained, it can be deduced that the decisive point of polymer
growth is the rst loop reactor. The second loop reactor leads to a
7% increase in dead polymer with a 34% decrease in live polymer as
illustrated in Fig. 4(c).
Temperature change in the pre-polymerization reactor is
shown in Fig. 5(a). The temperature increased by 293.25 K because
of the exothermic polymerization reaction. A cooling jacket was
used to maintain normalcy by providing adequate amelioration of
detrimental temperature effects because increasing temperature is
catastrophic to the process. Temperature in the rst loop reactor
increased from about 316 K and was maintained at 343.25 K after
10,000 s of operation with the aid of the PI controller because of the
high heat of reaction (Fig. 5(b)). Temperature rose at a faster rate in
the second loop reactor compared with the rst, taking about
9100 s to reach the operating temperature (Fig. 5(c)), because the
two reactors operate in series.
Polymerization reactors are susceptible to dynamic shock from
the heat of reaction. This temperature sensitivity requires a control
action. The controller was assumed to be applicable to a owrate
10 times larger than the designed owrate. The control action is
illustrated in Fig. 6. An actuating signal allowing for an abrupt
change in owrate to 870 kg s1 was issued by the controller at
about 10,000 s when the temperature exceeded 343.15 K
(Fig. 6(a)). A stable operating temperature was maintained with
a cooling water owrate of 228 kg s1. In the case of the second
304 S.H. Kim et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 298306

Fig. 6. Controlled rate of inow in cooling jacket: (a) 1st loop reactor, (b) 2nd loop reactor.

Fig. 7. Velocity prole with time and space: (a) pre-polymerization reactor, (b) 1st loop reactor, (c) 2nd loop reactor.
 S.H. Kim et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 298306 305

loop reactor (Fig. 6(b)), cooling water was maintained at
1490 kg s1 by the controller. This amount is 1.7 times larger
than that used in the preceding reactor, an indication of the relative
amounts of heat generated. Cooling water temperature varied from
327.2 K at the inlet to 331.15 K at the cooling jacket outlet.
The velocity prole of the pre-polymerization reactor (Fig. 7(a))
shows that the velocity changed from 3.55 m s1 at the onset of
the process to 3.14 m s1 at steady state under the inuence of
concentration and temperature. This corresponds to a volume
owrate of 250.45 m3 h1, which is similar to a owrate of
250 m3 h1 obtained from commercial data. The outlet owrate
obtained from our simulations deviate from the actual value by
less than 0.2%. The recycle ratio is a key factor that enables the
approximation of ow patterns in the loop reactor. In this project,
a recycle ratio of 153.3 was maintained in the rst loop reactor
with circulation velocity decreasing from 9.52 m s1 upon entry to
6.84 m s1 at exit. The exit velocity compares well with an actual
velocity of 6.88 m s1 in the process as shown in Fig. 7(b). The
operating conditions of the two loop reactors are similar in all
respects with slight variations in certain steady-state variables
such as a velocity. In the second loop reactor, a steady state value
of 6.91 m s1 is predicted (Fig. 7(c)) instead of the 6.84 m s1
predicted in the rst loop reactor.
Mn, Mw and PD of the growing polymer increased with time
(Fig. 8). The polymer produced in the pre-polymerization reactor
possesses Mn and Mw of 27,000 g mol1 and 51,000 g mol1
respectively and a PD of 1.98, which lies between the PD of 1.5 and
2.5 of the polymer produced from the existing plant. It is evident

Fig. 8. Average molecular weight and polydispersity prole of produced polymer: (a) pre-polymerization reactor, (b) 1st loop reactor, (c) 2nd loop reactor.
306 S.H. Kim et al. / Journal of Industrial and Engineering Chemistry 33 (2016) 298306
Fig. 9. Comparison and validation of polymer conversion rate for each reactor.
that an increase in polymer growth was achieved in the rst loop
reactor from a quick comparison with the Mn of 205,746 g mol1
and Mw of 398,085 g mol1 of the issuing pre-polymerization
products, which resulted in a PD of 1.93 (Fig. 8(b)). A plot of these
values from the simulation of the Spheripol process is shown in
Fig. 8(c). Inferring from this graphical representation indicate
values of 215,053 g mol1 and 412,558 g mol1 for Mn and Mw
respectively with a PD of 1.92. The PD and MW in the second
reactor remained almost constant. The second loop reactor
increased the yield of polymer as reected in an increase in the
polymer ow rate from 16,860.42 kg h1 to 27,181.42 kg h1
(Table 4) despite the constancy in PD and MW.
Validation of simulation
Simulation results shown in Table 4 predict conversions of
17.56%, 52.4%, and 54.91% in the pre-polymerization, R1, and R2
respectively. Comparing these conversions with conversions
achieved from an existing plant under the same operating
conditions in the bar chart of Fig. 9 below shows absolute errors
of 1.90%, 1.69%, and 3.02% in the pre-polymerization, R1, and R2
respectively. These are errors less than 10% and considered
acceptable for engineering applications.
Conclusion
A plethora of factors such as operating conditions, processing
methods, catalysts, and the choice of reactors inuence the quality
and efciency of polymer processes. This difculty has led to the
development of model based analysis of the Spheripol process for
polyolen production, particularly in consideration of steady and
dynamic state simulation. Deductions and conclusions from the
work carried out are as follows:
First, rigorous mathematical modelling of the reactors, namely
the pre-polymerization reactor, rst loop reactor, and second loop
reactor, was carried out to provide an accurate description of
physicochemical changes by way of conservation equations,
polymerization reaction kinetics, methods of moment, and
population balance. Important process variables such as concen-
tration, density, temperature, and mass ow rate as well as MW
and growth of the polymer chains were considered in the
formulation of the mathematical models.
Second, based on the developed mathematical model, a
dynamic simulation was executed using commercial operating
and design data to identify the dynamic behavior of the process.
The simulation results were compared with commercial data to
verify the accuracy and effectiveness of this research. The
simulation predicted an overall conversion of 54.91% with an
associated error of 3.02%. It is concluded that this study can be
extended for design and operational optimization of polyolen
processes as well as other polymerization process without
considerable modications.
Acknowledgements
This research is funded by the LINC Program of Hanbat National
University (2015) and the authors would like to acknowledge for
the assistance.
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