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Product and Process Modelling: A Case Study Approach

7.5. POLYMERISATION REACTOR

The methyl methacrylate (MMA) polymerisation takes place in a CSTR (see
Figure 27), using azo-iso-butyronitrile (AIBN) as initiator and toluene as solvent. The reaction is exothermic, and a cooling jacket is used to remove the heat
of reaction (Silva et al. 2001).
The reaction mechanism of MMA free radical polymerisation consists of the
following steps:
Initiation:
k

0
I !
2R
kI
R M !
P1

Propagation:
kp

Pi M ! Pi1
Monomer transfer:
kfm

Pi M ! Pi Di
Addition termination:
ktc

Pi Pj ! Dij
Disproportionation termination:
ktd

Pi Pj ! Di Dj
where I, P, M, R and D refer to initiator, polymer, monomer, radicals and dead
polymer respectively.

[(Figure_7)TD$IG]

FIGURE 27 Polymerisation reactor.

Chapter | 7

Models for Dynamic Applications

207

7.5.1. Modelling Objective

The objective here is to develop a dynamic model so that the transient responses
of the compositions and the temperatures during the operation of the polymerisation reactor can be studied; existence of multiple solutions can be identified;
and closed-loop simulations performed by adding an appropriate control model.

7.5.2. Model Description

7.5.2.1 Model Assumptions
*
*
*
*
*
*

*
*

The contents of the reactor are perfectly mixed.

Constant density and heat capacity of the reaction mixture.
Density and heat capacity of the cooling fluid stay constant.
Uniform cooling of fluid temperature.
The reactions only happen inside the reactor.
There is no gel effect (the conversion of monomer is low, and the proportion
of solvent in the reaction mixture is very high).
Constant volume of the reactor.
Polymerisation reactions occur according to the free radical mechanism.

7.5.2.2 Model Description

Based on the above assumptions, the mathematical model of the MMA polymerisation is given below.
Mass balance:


dCm
F C min  Cm
 k p k f m C m P0
V
dt


F I C I in  FCI
dC I
kI C I
V
dt

42

43

dD0
FD0
0:5ktc ktd P20 kf m C m P0 
dt
V

44



dD1
FD1
M m k p k f m C m P0 
dt
V

45

 F T in  T
dT DH kp Cm
UA 

T  Tj
P0 
dt
rC P V
V
rCP

46





dT j F CW T W0  T j
UA

T  Tj
rW CPW V 0
V0
dt

47

Energy balance:

208

Product and Process Modelling: A Case Study Approach

Defined (constitutive) relations:

s
2f * C I kI
P0
ktd ktc

k r Ar e

E = T
r R

48

r p; f m ; I; td; tc

49

Defined polymer average molecular weight (Pm):

Pm D1 =D0

50

The percentage monomer conversion (X):

X C min  Cm =Cmin *100

51

7.5.3. Model Analysis

The above mathematical model consists of a total of 14 equations out of which 6
are ODEs and 8 are algebraic equations (AEs). The 6 state (dependent) variables
for the 6 ODEs are: Cm, CI, T, D0, D1, Tj. The 8 algebraic (unknown) variables
for the 8 AEs are: k, P0, Pm, X (note that k is a vector of 5 variables). The rest of
the variables must be specified. Table 22 lists the variables that need to be
specified together with their specified values. Table 23 shows the incidence
matrix, which is not ordered in a lower tridiagonal form but it can easily be seen
that the algebraic equations have a lower tridiagonal form.
Based on the incidence matrix given in Table 23, the calculation procedure is
as follows: at any time, t, the values of the state (dependent) variables are known

TABLE 22 List of Specified Variables and their Given Values

F = 1.0 m3/h
FI = 0.0032 m3/h
FCW = 0.1588 m3/h
Cmin = 6.4678 kgmol/m3
CIin = 8.0 kgmol/m3
Tin = 350 K
TW0 = 293.2 K
U = 720 kJ/(hkm2)
A = 2.0 m2
V = 0.1 m3
V0 = 0.02 m3
r = 866 kg/m3
rW = 1000 kg/m3
Cp =2.0 kJ/(kgK)
CpW = 4.2 kJ/(kgK)

Mm = 100.12 kg/kgmol
f* = 0.58
R = 8.314 kJ/kgmol K)
-DH = 57800 kJ/kgmol
Ep = 1.8283  104 kJ/kgmol
EI = 1.2877  105 kJ/kgmol
Efm = 7.4478  104 kJ/kgmol
Etc = 2.9442  103 kJ/kgmol
Etd = 2.9442  103 kJ/kgmol
Ap = 1.77  109 m3/(kgmoh)
AI = 3.792  1018 1/h
Afm = 1.0067  1015 m3/(kgmoh)
Atc = 3.8283  1010 m3/(kgmoh)
Atd = 3.1457  1011 m3/(kgmoh)

Chapter | 7

209

Models for Dynamic Applications

TABLE 23 Incidence Matrix (note that Eq 49 is actually five equations for the
vector k). The shaded Cells Indicate the ODEs and their Corresponding
Dependent Variables
Eq\Variable

Eq. 49
Eq. 48
Eq. 42
Eq. 43
Eq. 44
Eq. 45
Eq. 46
Eq. 47
Eq. 50
Eq. 51

*
*
*
*
*
*
*

P0

Cm

CI

D0

DI

Tj

Pm

*
*
*

*
*
*

*
*
*

*
*
*
*
*
*

*
*
*

and so the AEs (Eq. 49 and then 48) are solved. Using these variables and the
known variables, the right-hand sides (RHSs) of ODES (Eqs. 4247) are determined, and based on these, new values of the dependent variables are obtained.
Equations 50-51 are used to calculate the polymer average molecular weight and
the percentage conversion at any time.

7.5.4. Numerical Solution

The model equations have been solved through ICAS-MoT (Sales-Cruz, 2006).
The calculated steady-state values for the state variables are given in Table 24. It
can be noted that this reactor has multiple steady states, which can be obtained

TABLE 24 Calculated Steady-State Values for the MMA Polymerisation

Reactor

Cm, kgmol/m
CI, kgmol/m3
T, K
D0, kgmol/m3
D1, kgmol/m3
T j, K
X, %
PM, kg/kgmol

State 1

State 2

State 3

5.9651
0.0249
351.41
0.0020
50.329
332.99
7.8
25000

5.8897
0.0247
353.40
0.0025
57.881
334.34
8.9
23000

2.3636
1.7661  10-04
436.20
0.4213
410.91
390.93
63.5
975

210

Product and Process Modelling: A Case Study Approach

[(Figure_8a)TD$IG]

FIGURE 28a Transient response of CI (y-axis) versus time (x-axis).

[(Figure_8b)TD$IG]

FIGURE 28b Transient response of Cm (y-axis) versus time (x-axis).

by starting the dynamic simulation runs from different initial conditions but
keeping all the known variables at the listed values of Table 22. This is an
example of output multiplicity. The transient responses for the 6 state variables
are shown in Figures 28a-f. These results are obtained for the following initial
conditions of the state variables: Cm = 0 ; CI = 0.5 ;T = 200 ; D0 = 0 ; D1 = 0; Tj
=0. This corresponds to steady state 1 in Table 24.

Chapter | 7

Models for Dynamic Applications

[(Figure_8c)TD$IG]

FIGURE 28c Transient response of D0 (y-axis) versus time (x-axis).

[(Figure_8d)TD$IG]

FIGURE 28d Transient response of DI (y-axis) versus time (x-axis).

[(Figure_8)TD$IG]

FIGURE 28e Transient response of T (y-axis) versus time (x-axis).

211

212

Product and Process Modelling: A Case Study Approach

[(Figure_8f)TD$IG]

FIGURE 28f Transient response of Tj (y-axis) versus time (x-axis).

The model equations as implemented in ICAS-MoT are given in Appendix 1

(see chapter-7-5-poly-reactor.mot file).
Discussion: Try to obtain all the three steady states and evaluate their
stability through calculating the eigenvalues. Add the gel-effect to evaluate
the changes in the transient responses. A more detailed polymerisation reactor
model is given by Lopez-Arenas et al. (2006) try to implement this model.

REFERENCES
Cooper, H., 2007. Fuel cells, the hydrogen economy and you. Chemical Engineering Progress.,
3443.
Fogler, S. H., 2005. Elements of Chemical Reaction Engineering, 4th Edition, Prentice Hall, USA.
Ingram, C.D., Cameron, I.T., Hangos, K.M., 2004. Chemical Engineering Science 59, 21712187.
Lopez-Arenas, T., Sales-Cruz, M., Gani, R., 2006. Chemical Engineering Research and Design 84,
911931.
Luss, D. and Amundson, N. R., 1968, Stability of Batch Catalytic Fluidized Beds, AIChE Journal,
14 (2), 211221.
Morales-Rodriguez, R., 2009. Computer-Aided Multi-scale Modelling for Chemical ProductProcess Design, PhD-thesis. Lyngby, Denmark: Technical University of Denmark.
Sales-Cruz, M., 2006. Development of a computer aided modelling system for bio and chemical
process and product design, PhD-thesis. Lyngby, Denmark: Technical University of Denmark.
Sundmacher, K., Schultz, T., Zhou, S., Scott, K., Ginkel, M., Gilles, G., 2001. Chemical Engineering
Science 56, 333341.
Xu, C., Follmann, P.M., Biegler, L.T., Jhon, M.S., 2005. Computers and Chemical Engineering 29,
18491860.