18th European Symposium on Computer Aided Process Engineering ESCAPE 18

Bertrand Braunschweig and Xavier Joulia (Editors)

2008 Elsevier B.V./Ltd. All rights reserved.

Modeling of Polyvinyl Acetate Polymerization

Process for Control Purposes
Teodora Mitevaa, Rodrigo Alvarezb, Nadja Hvalaa, Dolores Kukanjac
a

Joef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia

UPC, Enginyeria Qumica , Avda. Diagonal 647, Pab. G-2, E-08028 Barcelona, Spain
c
MITOL, Seana, Partiyanska cesta 78, SI 6210, Slovenia
b

Abstract
The research work presented in this paper considers the polymerization process in
MITOL factory in Seana (Slovenia). The challenge is to increase the production rate,
while keeping quality parameters at the desired values. For this purpose a model based
on differential and algebraic equations (DAE) has been already constructed7. The model
is intended to take over the role of a soft sensor, being able to provide estimates of the
given process outputs. In this paper we derive an extended version of the model in order
to reach fully predictive capabilities. By using modeling from first principles (energy
balance), the dynamics of the temperature is derived as a function of the concentrations
of reacting chemicals. The preliminary simulation results based on real plant data,
derived in gPROMS environment, are presented.
Keywords: vinyl acetate, control, modeling, gPROMS

1. Introduction
Emulsion polymerization of vinyl acetate is quite a complex chemical process. Efforts
have been made to determine the mechanisms of the reaction. Initial estimations of the
number of particles and conversion, based upon the Smith and Ewarts polymerization
model were written by O Donnel and Mesrobian1. Dunn and Taylor2 went further and
developed many of the theories commonly accepted nowadays. In the literature it is also
possible to find a good number of comprehensive models of the vinyl acetate
polymerization reaction, gathering the different theories and mechanisms proposed. In
1992, Urquiola et al.3,4,5 wrote a series of papers about the polymerization of vinyl
acetate using a polymerizable surfactant.
The presented work addressis modeling of a polymerization process in a chemical
factory Mitol in Seana, Slovenia. The problem we have is to design optimal control
actions required to reach the final product with specified quality parameters in as short
time as possible. The motivation arises from the fact that current batch control is done
by following a recipe derived from experience. The large quantities of raw materials and
equipment resources involved in the batch prevent us from performing experiments
directly on the plant. Therefore we need a good predictive model of the polymerization
reaction. The model of Aller et al.6,7 was designed to provide estimates of four outputs:
conversion, particles size, solids content and viscosity, having the temperature and
initial amounts and flow rates of the monomer and initiator as model inputs. The
problem appeared that having the temperature as a model input does not allow us to
fully optimize the polymerization process and to observe the changes of the
temperature, and consequently the process outputs, by supplementing different amounts

T. Miteva

of monomer and initiator. The sufficient amount of initiator was also difficult to be
predicted. In our work we extend the proposed model with energy balance equations
and in this way simulate the temperature in the reactor as an additional model variable.
In this way the necessary control actions for shortening the batch duration could be
studied.

2. Process description
The modeled reaction is polymerization of vinyl acetate using potassium persulfate
(KPS) as initiator and polyvinyl alcohol as protective colloid. The production process is
semi batch polymerization. Initial amounts of initiator and monomer are added into the
system as well as the whole amount of the polyvinyl alcohol. The reactor is closed and
the heating starts. When the temperature of the reactor reaches approximately 70C, the
operator stops the hot water through the heating jacket (Figure 1). The exothermic
reaction and the heat of the remaining water filling the heating coat continue to rise the
temperature over the set point. After the reactor temperature reaches a certain level, the
remaining monomer starts to be pumped into the reactor with a continuous flow of 370
kg/h.

Figure 1. Scheme of polymerization reactor in MITOL

The monomer flow rate is controlled by a PID controller acting on the pump. In the
beginning of the reaction, the temperature can reach 82C. From now on, for the product
quality reasons, it is necessary to keep the temperature between 75-80C. Temperature
control is performed by manually adding a small amount of initiator every time the
temperature decreases. The temperature of the added monomer is the outhdoors
temperature. When all the monomer is added into the system, a larger amount of
initiator is added in order to terminate the reaction. The temperature is then allowed to
increase up to 90C. The reaction is considered as finished when the temperature starts
to decrease again. The heat in the reactor is released in three ways:
Direct cooling in the reactor.
Losses to the surroundings
Heating the incoming flow rate of the monomer until the average
temperature in the reactor.
The main variables affecting the duration of the reaction are: the temperature, initial
amount of monomer, flow rate of the monomer and the addition of the initiator.
The quality of the product is defined by the following parameters: conversion into
polymer, particle size distribution, viscosity and solid content.

Modeling of Polyvinyl Acetate Polymerization Process for Control Purposses

3. Temperature model
The model of the polymerization process of vinyl acetate was developed using
gPROMS modeling tool. The current model is based on previous work of Aller et al.6,7,
where the monomer flow rate, initiator addition and the temperature were taken as
inputs into the system. The temperature was not estimated by the model. In order to
observe the changing of its profile as a result of the change of the initiator addition we
took out the temperature as an input, but rather estimate it from the energy balance
model. This enables us to controlling it by adding a sufficient amount of initiator.
The most influential factors attributing to reaction rate are the decomposition of the
initiator and the temperature in the reactor.
The mass of the initiator in the reactor (I) is increased by the flow addition of initiator
(Ie) and decreased by its thermal decomposition9,10. To obtain the concentration of the
initiator (Iw) in the aqueous phase we divide by the volume of water (Vw).

dI
dt

Ie

kd I w Vw

(1)

To account for higher rate of decomposition of KPS at higher temperature we use the
following function

Kd

8.4

T Tstart
40

1.6

T Tstart
40

(2)

where Kd is the initiator decomposition rate constant, TR is the reactor temperature and
Tstart is the temperature when an appreciable decomposition is observed.
Reaction heat capacity (KR) accounts for the heat capacity of the still present monomer
and converted monomer (polymer) in the reactor. It is calculated by the specific heat
capacities (Cpmon, Cppol) of the monomer (M), having into account its molecular weight
(MWm) and the converted monomer (Mconv).

KR

MMWmCpmon M convMWmCp pol

(3)

The flow through the condenser is estimated by the flow coming in and out of it (QFC),
its heat capacities (CpCout) and temperature of the reflux going through the condenser
(TCout, TCin). The is vaporization heat.

Qcond

(QFC (CpCout (TCout TCin ))) QFC

0.00281T 2 Cout

0.32738 TCout

(4)

408 .178

(5)

We also take into account the heating through the heating jacket. This is considered in
the first part of the modeling the temperature profile when the jacket is heated. In that
first part we do not have heat looses and also there is no flow though the condenser,
therefore we have the following equation for the energy balance:

KR

dTR
dt

TR

dK R
dt

Qm MWm Cp monTmon

H r rpol

H jacket

(6)

Where on one side of the equation is the reaction heat capacity multiplied by the
changes in the temperature in the reactor and vice versa. On the other side of the

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equation is the monomer enthalpy, the reaction heat and the heating in the jacket. The
heating through the jacket is given by:

H jacket

0.00018 (T T jacket ) K R

(8)

where the changes in the temperature in the jacket is:

dT jacket dt (0.00018 K R 4.18 * 1000 )(T

T jacket )

(8)

The energy balance for the part of the model when no heating is needed anymore, does
not include heating through the jacket and takes into account heat losses (Qloss) and flow
through the condenser (Qcond). The equation has the following form:

KR

dTR
dt

Qloss

TR

dK R
dt

Qm MWm CpmonTmon

H r rpol Qcond Qloss

0.9502 (T Text )

(9)

(10)

Model parameters were taken from the literature8 (Cppol, Cpmon, Cpout) or estimated based
on real plant data (Tstart, Tstart ) so that a satisfactory agreement between the process
and the model was obtained. The values of model parameters are given in Table I.
Table I Variables estimated from the literature and expiriments
Parameter
Value
Tstart [K]
330
MWm [gmol-1]
86.09
Cppol [kJ kg-1]
1.77x10-2
-1
Cpmon [kJ kg ]
1.77x10-2
Cpout [kJ kg]
1.17
Text [K]
283.15

4. Results
Model simulations were performed based on real plant data. The monomer flow rate
was taken from the actual measurements, while the addition of initiator was calculated
from the weight change of the initiator dozing tank (Figure 2).
100

0.004

90

0.0035

80

0.003

70

0.0025

60

0.002

50

0.0015

40

0.001

30

0.0005

20
0

10000

20000

30000

40000

50000

T Reactor C
flow rate init testing mol/s

0
60000

Fig 2Initiator addition and Temperature Profile in time, data taken from real plant
With the presented model we are able to get relatively good estimates of the reactor
temperature. From Figure 3 it can be seen that the estimated profile follows the

Modeling of Polyvinyl Acetate Polymerization Process for Control Purposses

dynamics of the real one. Not so good estimates are obtained at the beginning and at the
end of the batch. At the beginning of the batch, the most influential temperature
parameter is the heating of the reactor through the heating jacket. So most probably, the
corresponding model parameters still need to be estimated more precisely. The
agreement of the model is also not good in the last part of the estimated profile. This
part is when the whole amount of monomer is added in the reactor and a larger amount
of initiator is put to finish the reaction. There are two possible reasons that the
performance of the model in this part is not so good, i.e., (i) the heat losses were
overestimated, (ii) the final addition of initiator was bigger than calculated. For the
latter we have to take into account that the amount of initiator is obtained from the
weight change of the dozing tank, so there might be some disparity of the final addition
because of its larger amount. In the estimated temperature profile there is also a small
delay in the increasing and decreasing of the temperature. The most probable reasons
for that are the value of the initiator decomposition rate constant, heat losses and, most
probably, the amount of initiator addition. The obtained model still needs fine tuning of
parameter values and close inspection of the initiator addition.

Figure 3 Temperature profile and estimated profile

Process outputs were also estimated with the model. Simulations were done for four
batches. Table 1 shows the validation of the model against real plant data. For the
viscosity and the solids content, laboratory analyses were performed at the end of the
reaction. These measurements are normally performed after mixing several batches and
therefore no individual data is available. Expected output results for the conversion are
over than 99%. The range for the solids content is 44 46, the viscosity has to be over
than 34000.
Table II Output Variables real data and estimated data
Batch
Conversion (%)
Solids Content
Viscosity
No.
(%)
(Brookfield 200C,
50rpm), (mPas)
Real
Modeled Real
Modeled Real
Modeled
Data
Data
Data
Data
Data
data
1192
99.95
99.96
46.4
47.2
37520
36166
1214
99.90
99.97
45.9
46.81
31200
35880
1253
99.13
99.95
46.9
47.70
34000
36876
1256
99.37
99.86
46.4
47.16
30160
35261
From the table we see that some of the model outputs are overestimated, but are still in
the quality range of the product. Also for two of the batches (1214 and 1256) the

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viscosity, as measured in the plant, is less than it should be. This output variable is in its
range in the modeled process.

5. Conclusion
A model for polymerization process of vinyl acetate has been developed. The model
extends the work of Aller et al.7 in terms of energy balance. The improved model has
two inputs flow rate of monomer and flow rate of initiator addition. The outputs of the
presented model are four particle size diameter, solids content, viscosity and
conversion. Having the temperature as an additional state variable we are able to
estimate more precisely the sufficient amount of initiator which should be added into
the system every time the temperature drops off. The model has been validated on a new
set of real data taken from the polymerization plant. The work continues with fine
tuning of model parameters, developing optimal control strategies for monomer and
initiator addition, and implementing them in chemical factory in Seana, Slovenia.

6. Acknowledgment
The support of the European Commission in the context of the 6th Framework
Programme (PRISM, Contract No. MRTN-CT-2004-512233) is greatly acknowledged.

References
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