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Modeling and Simulation of Batch Poly Methyl Methacrylate Production

Reactor with Enhanced Controling System

Conference Paper · February 2014

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 th
The 8 International Chemical Engineering Congress & Exhibition (IChEC 2014)
Kish, Iran, 24-27 February, 2014

Modeling and Simulation of Batch Poly Methyl Methacrylate

Production Reactor with Enhanced Controling System

M.Mofarahi, M.A.Makarem, M.Delalat, P.Jowkar

Chemical Engineering Department, Persian Gulf University, Bushehr, Iran
mofarahi@pgu.ac.ir

Abstract
In this study, batch stirred poly methyl methacrylate production reactor is modeled. Governing
equations are solved using finite difference method by a program written by MATLAB; in order to
set the reactor temperature, heating system with variable power and a thermal jacket containing
cooling fluid (water) with variable flow rate are considered. Overall heat transfer coefficient is
considered to be a function of the cooling fluid volumetric flow and the flow regime; therefore,
more accurate estimations of reactor condition is be obtained, and gel effect can be controlled
more efficiently. Also, by addition of nanoparticles to cooling fluid at different volume fractions,
not only less amount of coolant is needed, but also the controlling system is perform more flexible,
especially when the temperature increases suddenly due to gel effect. Because of dependency of
overall heat transfer coefficient to the cooling fluid flow rate and its regime, it increases suddenly
when regime changes from laminar to turbulent; by the controlling system provided here, sharp
temperature increases can be controled faster.

Keywords: Poly Methyl Methacrylate, Batch Stirred Reactor, Numerical Simulation, Control
System, Nanofluid.

Introduction
Polymers are chemical compounds with increasing applications in different industries. They
have special properties such as high resistance to tension, and as the result, are used currently
in medical prosthesis, military and etc. Poly Methyl Methacrylate (PMMA) is the polymer of
the monomer Methyl Methacrylate (MMA) and its polymerization reaction and its process are
very common and important in chemical industries; therefore accurate modeling of this
process is needed. In this process batch or CSTR reactors can be used isothermally or non-
isothermally. There have been many studies in this field of research such as works done by
Cueteanu [1], Rafizadeh [2], and more recent by Moreno [3].
Gel effect is a very important phenomenon that occurs in MMA free radical polymerization
process. Due to this phenomenon, at monomer conversion of about 40% to 60%, the reaction
rate increases suddenly, which changes the product properties [4]. Several models have been
presented for this polymerization reactions; for examplele Curteanu et al. [1] have modeled
MMA polymerization reactor including gel effect. This model is in good agreement with
experimental data, but there is no information about the temperature controlling system. Also,
Simulation of Poly Methyl Methacrylate Production Reactor

Soroush et al. [5] have modeled the reactor and have used a thermal jacket to control the
temperature but the overall heat transfer coefficient has been considered to be constant. Since
the cooling fluid flow rate in the jacket is not constant and flow regime may change, it may
not be suitable to take this coefficient constant.
Temperature control is the key element in polymerization Process. Nanofluids for their high
thermal conductivity can be used as cooling fluid in thermal jacket [6]. There are several
common nano particle used for heat transfer enhancement such as metals of metal oxides [7].
In this study, batch stirred MMA polymerization reactor is modeled and accurate temperature
control system is presented. In this modeling, the overall heat transfer coefficient varies with
cooling fluid flowrate. Also, nanofluid is used as cooling fluid in reactor jacket which
includes water as base fluid and Al as added nanoparticle; the effect of nanoparticle volume
fraction is studied. The results shown that this work presnted controlling system by nanofluids
can control the reactor behavior more effectively, especifically when gel effect occures. Using
the mentioned new changes in the process model and operational conditions, this very sesitive
process can be handeled easier and the product specifications will be enhanced enormously.

Problem Formulation
In this study, a batch stirred reactor with the volume of 100 L is considered. The kinetic model
in this study is based on the following polymerization reactions [1]:
I 
K
2R
d
, R  M  P , P  M  P
Ki
, P  P  D  D
1 (1)
n
KP
n1 n m
Ktd
n m

The two first reactiones are intiation, the third one is propegation, and the last one is the
termination reaction. By neglecting the valume changes during the reactions, in presence of
gel effect, the rate constants can be defined as follows:
C C
Kt  Kt0 , KP  KP0 (2)
C  t Kt 0  C  P KP0 
Where C and conversion factor, x, is defined by:
1 x M
C , x  1 (3)
A  B(1  x) M0
Where M is monomer concentration. In this study the subscript zero represent the variables at
their initial states. Other variables used in this model are defined as:
 t0
t  exp( Et /( RTr )) ,  P   P0 exp( E /( RTr )) , A  C1  C2 (Tr  Tgp ) 2 (4)
I0 P

Finally, the following set of non-linear differential equations are obtained:

dM
 2 fK d I  K P M
dI d
,  K d I ,  2 fK d I  K t 2
dt dt dt
dTr (H )k P 0 MV dT j  cf P UAh (5)
 ,  Fcf (Tcf  T j )   (Tr  T j )
dt C p ,r m dt m0 C p ,cf m0 C p ,cf m0

In this equation set, I is the initiator concentration, 𝝀 is polymer moment generating function
and Tr and Tj are reactor and jacket temperatures, respectively. The overall heat transfer
coefficient is calculated by the following equations:
K  Nu
U
Dh
1
1 D  3 ( f f / 8) Re . Pr
Nu  1.86(Re . Pr) 3  h  , Re  2300 Nu  , Re  2300 (6)
 L  1.07  12.7 f f / 8 (Pr 2 / 3  1)

ff 
1  cf Fcf Dh C p ,cf .
(1.82 log10 Re 1.64) 2 , Re  , Pr 
Ac K cf
In the current work, an enhanced temperature controlling system is defined. For reduction of
temperature a cooling jacket with variable cooling fluid flow is utilized, and for rising the
 th
The 8 International Chemical Engineering Congress & Exhibition (IChEC 2014)
Kish, Iran, 24-27 February, 2014
temperature, a heater with variable power is used. The fluid flow and heater power are
calculated and set as follows:
T T 
2
Fcf  0 , T  Tin  0.5 Fcf  1e 7   set  , T  Tin  0.5 (7)
 0.1 
, T  Tin  0.5
P  2.0 10 2 (Tset  T ) P0 , T  Tin  0.5 (8)
It is possible to use nanofluids instead of ordinary cooling fluids. To calculate the density,
specific heat capacity and thermal conductivity of nanofluids, following equations are used:
 nf  (1   )  w   Al (9)
(1   )( C p ) w   Al
C p , nf  (10)
nf
(k Al  2k w )  2 (k w  k Al )
K nf  Kw (11)
(k Al  2k w )   (k w  k Al )
Where φ is nanoparticle volume fraction, ρ represent density, Cp specific heat capacity and k
values are thermal conductivities.

Results and Discussion

A MATLAB based computer program is used to solve equation set (5) by explicit finite
difference numerical method (Δt= 0.1s). Three operational states are studied here; in the first
state, water is used as cooling fluid and in the second and third state Al-Water nanofluid is
used with nanoparticle volume fractions of 0.1 and 0.2. The initial values for model
parameters are represented in [1] and [8]. In figure 1, monomer conversion is plotted versus
time. As is shown the result of this modeling, at isothermal reactor condition, is in good
agreement with result represented in literature. Also, by using the enhanced temperature
controlling system, the gel effect, shown by sudden increase in the slope of conversion-time
curve, is controlled more effectively. And as well, the addition of nanoparticles enhances the
heat transfer from the reactor to the jacket, and controlling system works better.
Consequently, it reduces the slope of conversion-time curve faster. The reactor temperature
profile is represented in figure 2. The controlling system sets a the reactor temperature to 340
K. Because temperature has direct effect to the polymer properties [4] other temperature
profiles (not just a constant one) can also be defined here. At the beginning, the reactor
temperature drops due to cooling fluid present in thermal jacket. Consequently, the heater
turns on to recover the set point, shown in figure 3.

Figure1. Comparison of the model represented in Figure 2. Reactor and thermal jacket temperature
[1] and this work for φ=0, 0.1 and 0.2 profile for φ= 0, 0.1 and 0.2.
As the reaction continues, the temperature rises, and the cooling system starts to work, shown
in figure 4. When gel effect happens, the cooling fluid flowrate increases, and therefore,
 Simulation of Poly Methyl Methacrylate Production Reactor

changes the flow regime from laminar to turbulent. As the result, the overall heat transfer
coefficient rises sharply, which is occurred twice in the current system. After controlling the
gel effect, the cooling system is turned off. Figure 5 represents the changes of overall heat
transfer coefficient over reaction time. It is obvious that the setting this coefficient as a
constant [5, 8] is not logical at all and leads to inaccuracy in the results. Also the flowrate of
cooling fluid with constant U is far away from the variable U, and real, condition. It is
noticeable that the sharp peaks in figure 5 are due to the changes of the flow regime from
laminar to turbulent. It can be seen that using nanofluid as cooling fluid not only leads to
decrease in its flowrate, but also it reduces the jumps of the regime from laminar to turbulent.

Figure 3. Profile of the heater Figure 4. Cooling fluid flow Figure 5. Profile of overall
power required by control profile for φ=0, 0.1 and 0.2 in heat transfer coefficient
system comparison with constant U. over reaction time

Conclusions
In this study, batch stirred MMA polymerization reactor with gel effect is modeled. A more
accurate temperature control system is applied to control the gel effect. Unlike prior studies,
overall heat transfer coefficient varies with cooling fluid flowrate. Nanofluid is also used as
cooling fluid to enhance the temperature controlling mechanism.

References
[1] S. Curteanu, V. Bulacovschi., C. Lisa, Free Radical Polymerization of Methyl
Methacrylate: Modeling and Simulation by Moment Generating Function, Iranian Polymer
Journal, 7 (1998) 225-233.
[2] M. Rafizadeh, Non-isothermal Modelling of Solution Polymerization of Methyl
Methacrylate for Control Purposes, Iranian Polymer Journal, 10 (2001) 251-263.
[3] S. Terrazas-Moreno, A. Flores-Tlacuahuac, I. Grossmann, Simultaneous design,
scheduling, and optimal control of a methyl-methacrylate continuous polymerization reactor,
AIChE Journal, 54 (2008) 3160-3170.
[4] M. Alger, Polymer Science Dictionary, Elsevier Applied Science, London, 1989.
[5] M. Soroush, C. Kravaris, Optimal design and operation of batch reactors. 2. A case study,
Industrial & Engineering Chemistry Research, 32 (1993) 882-893.
[6] X. Wang, X. Xu, S. Choi, Thermal Conductivity of Nanoparticle–Fluid Mixture, Journal
of Thermophysics and Heat Transfer, 13 (1999) 474-480.
[7] S. Murshed, K. Leong, C. Yang, Thermophysical Properties of Nanofluids, in: K. Sattler
(Ed.), Handbook of Nanophysics-Nanoparticles and Quantum Dots, CRC Press, 2011.
[8] A. Silva-Beard, A. Flores-Tlacuahuac, Effect of Process Design/Operation on the Steady-
State Operability of a Methyl Methacrylate Polymerization Reactor, Industrial & Engineering
Chemistry Research, 38 (1999) 4790-4804.

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