1. Introduction
Phthalic anhydride (PA) is used widely in industry for the production of a
large variety of products. It is used as chemical intermediates in the production of
plastics from vinyl chloride, and for the production of polyester resins, plasticizers,
dyes, insect repellants, etc. PA is produced by the gasphase catalytic oxidation of o
xylene or naphthalene, or a mixture of both. Mixed oxide catalysts, mainly consisting
of V
2
O
5
and TiO
2
and packed in several zones in a multitubular reactor, are used for
oxidation. The gas leaving the reactor is cooled in one set of switch condensers. The
PA solidifies on the finned tubes. The solidified PA is melted and collected from
these during the heating cycle, during which the exit gas from the reactor is sent to the
other set of cooled switch condensers. The treated gas is then either scrubbed with
water, or catalytically or thermally incinerated (Ullmann, 1992).
The oxidation of oxylene to PA has been studied by several workers
(Wainwright and Hoffman, 1977; Chandrasekharan and Calderbank, 1979; Skrzypek
et al., 1985) over the years. The earlier workers used the redox model to explain the
oxidation process. Studies conducted by Wainwright and Hoffman (1977) showed
that the redox model could not explain fully all the available experimental data. For
example, it failed to explain the maximum observed by Calderbank (1977) in the rate
of disappearance of oxylene with the increase in the feed concentration of oxylene.
Skrzypek et al. (1985) used the LangmuirHinshelwoodHougenWatson (LHHW)
model to overcome this limitation. In the present study, the latter is used for modeling
PA reactors, which are then optimized using multiple objectives.
Evolutionary techniques, such as genetic algorithm (GA), have been used
successfully to solve single and multiobjective optimization problems for over a
decade. GA generates a pool of solutions and with the help of probabilistic operators,
2
reproduction, crossover and mutation, finds the global optima. Several workers have
developed different adaptations of GA to improve its computational efficiency,
enabling its use for solving complex optimization problems. Deb (2001) and co
workers developed two versions of the nondominated sorting genetic algorithm,
NSGAI and the elitist NSGAII, to solve problems with two or more objective
functions. A set of nondominated (equally good) optimal solutions, referred to as
Pareto sets, with a good spread of solutions, is generated using these techniques.
Kasat and Gupta (2003) incorporated the concept of the variablelength jumping gene
(JG; McKlintock, 1987) in the binarycoded NSGAII and found an eightfold
reduction in the computational time required for convergence for a computationally
intensive optimization problem, namely, the multiobjective optimization of an
industrial fluidizedbed catalytic cracking unit (FCCU). Bhat (2004) found that the
fixedlength JG adaptation, NSGAIIaJG, of the binarycoded NSGAII led to even
faster convergence of the results. Several parallel studies (Simoes and Costa, 1999a,
1999b; Man et al., 2004; Chan et al., 2005a, 2005b; Ripon et al., 2007; Guria et al.,
2005; Bhat, 2007; Agarwal and Gupta, 2007a, 2007b) also indicate efficacies of other
JG adaptations of both the binarycoded as well as the realcoded NSGAII.
In the present study, multiobjective optimization of two industrial PA reactors
is carried out using NSGAIIaJG. The second of these problems is particularly
complex, computationally, and a guided NSGAIIaJG had to be developed to obtain
optimal solutions.
3
2. Formulation
2.1. Reaction Scheme and Mathematical Model
Figure 1 shows the reaction network suggested by Skrzypek et al. (1985). The
reaction model developed by these workers is based on the LHHW kinetics. The six
species, oxylene (OX), otolualdehyde (OT), phthalide (P), phthalic anhydride (PA),
maleic anhydride (MA) and oxygen (O
2
), are assumed to be adsorbed on the active
sites of the catalyst, while H
2
O, N
2
, and the combustion products, CO
x
(a mixture of
CO and CO
2
), are assumed not to be adsorbed. The surface reaction between the
appropriate species is assumed to be the rate limiting step. The LHHW rate
expressions for this scheme are given in Appendix 1 (Eqs. A1, A2). The values of the
kinetic parameters and the heats of reaction are given in Table 1, while the parameters
characterizing the adsorption are given in Table 2.
The catalyst considered by Skrzypek et al.
(1985) was V
2
O
5
TiO
2
dispersed
on a nonporous carborundum support. The steady state mass and heat balance
equations involving the (external) catalyst surface and the bulk gas are given in
Appendix 1 (Eqs. A3 A11). The temperature of the entire catalyst particle is
assumed to be uniform since the Prater No. is usually low (Elnashaie and Elshishini,
1993). The following assumptions have been used to develop the model for the
kinetics:
a) The reactor operates under steady state conditions;
b) Radial dispersion of mass and heat are negligible;
c) Axial dispersion of mass and heat are negligible;
d) The gas mixture follows the ideal gas law.
The derivations of all the equations are given in Appendix 2.
4
Figure 1: Reaction scheme proposed by Skrzypek et al. (1985). Reaction numbers
indicated on the arrows
(MA)
(PA)
(P)
(OT) (OX)
Phthalic Anhydride oXylene oTolualdehyde Phthalide
1 4 5
6
7
Maleic Anhydride
CO
x
2
3
8
5
Table 1: Kinetic parameters and heats of reaction (Elanshaie and Elshishini, 1993) for
the scheme of Skrzypek et al. (1985)
Reaction, i
E
i
kJ mol
1
10
15
k
io
mol (m
3
bed)
1
h
1
(MPa)
2
(H
i
)
kJ mol
1
1 108.36 130 456.05
2 96.65 1.7 1503.7
3 85.35 0.7 3998.8
4 85.35 3.8 414.2
5 93.72 18.0 368.19
6 108.78 84.0 1238.5
7 96.23 28.0 782.4
8 117.72 0.00699 2760.0
6
Table 2: Parameters (Elnashaie and Elshishini, 1993) characterizing the adsorption for
the kinetic scheme of Skrzypek et al. (1985)
Component, j
( )
ads
j
H
kJ mol
1
K
io
(MPa)
1
oxylene (OX) 27.70 0.987
otolualdehyde (T) 30.96 1.905
maleic anhydride (MA) 24.27 5.724
phthalide (P) 16.74 3.760
phthalic anhydride (PA) 24.31 3.819
oxygen (O
2
) 0.00 0.199
7
The properties of the individual components, like the viscosity, thermal
conductivity and the specific heat of the vapor phase are estimated using the equations
given in Daubert and Danner (1989). These properties are estimated using the group
contribution method (Poling et al., 2001) for OT and P. The binary diffusion
coefficients are computed using the Wilke and Lee equation (Poling et al., 2001). The
effective diffusion coefficients for any component, i, in the gas mixture are computed
using the Wilke equation (Elnashaie and Elshishini, 1993). The mass transfer
coefficient, k
g,i
, of component, i, through the gas film surrounding the catalyst
particle, and the film heat transfer coefficient, h, are computed using the equations
proposed by Wakao and Kaguei (1982) and Wakao et al. (1978), respectively. The
properties of the gas mixture, e.g., viscosity (Wilke equation in Poling et al., 2001),
thermal conductivity (Wassiljewa equation in Poling et al., 2001), and the specific
heat, are computed using the component values and the compositions. The detailed
correlations used can be supplied on request.
Eqs. A1A23 in the Appendix comprise a complete set of coupled equations.
Some of these (for the gas phase) are ordinary differential equations of the initial
value kind (ODEIVP), while those for the catalyst particles are nonlinear algebraic
equations. These need to be solved simultaneously. The concentrations of all the
species and the temperature are known at z = 0. These are used to compute the
concentrations and the temperature at the catalyst surface at that axial location, using
the modified Powell hybrid algorithm (program DNEQNF in the IMSL library). The
effectiveness factors of all the reactions are assumed to be unity at this stage (this is
required since several concentrations are zero at the entry point), and the ODEIVPs
are integrated using Gears method (code DIVPAG in the IMSL library). This gives
the concentrations and the temperature at location, dz. The gas phase values at dz (or
8
any general z
i
) are used to compute the concentrations and temperature at the solid
surface at that axial location, the effectiveness factors of the reactions are then
evaluated and the ODEIVPs further integrated for a small interval, dz. This is
continued till the end of the reactor.
2.2. Multiobjective Optimization
Two industrial reactor systems are optimized in this study. These problems are
now described.
2.2.1. Reactor System1
Reactor System1 has been suggested by Sato et al. (1981). In this system, o
xylene is oxidized using air. The reactor operates at atmospheric pressure, and
consists of several identical parallel tubes. Some amount of recycled process gas and
steam are also mixed with the (original) feed so as to reduce the concentration of
oxygen in the feed to the reactor to about 10 % volume by volume. This ensures that
the hot spot is within the safe limit of about 510
o
C (Reuter et al., 2004; the auto
ignition temperature of PA is 580
o
C; Ullmann, 1992). A severe decrease in the PA
yield (due to formation of CO
x
) and in the operating life of the catalyst also result
above about 500
o
C (Reuter et al., 2004). The use of recycle and steam permits the use
of as high a concentration of the original feed as 85 g oxylene/m
3
air at NTP. The
exothermic heat of reaction is removed by a eutectic mixture of molten sodium and
potassium nitrates and nitrites (KirkOthmer, 1982) flowing cocurrently outside the
tubes (referred to as the shell side). Because of the symmetry involved, a single tube
is studied.
Sato et al. (1981) reported the use of several zones (layers) of the catalyst, in
between which there is no catalyst and the process gas just exchanges heat with the
9
jacket fluid and cools down. One of these configurations, using two layers of lengths,
L
1
and L
2
(see Figure 2a), has been used in the present study. This configuration has
been selected since the high activity catalyst of Skrzypek et al. (1985) is being used.
Details of the reactor are given in Table 3.
For the optimization of Reactor System1, we assume a fixed value of the
mass flux, G, inside the tube. One important objective function is the total amount of
catalyst used. The yield, X
PA
, of PA is a natural choice of the second objective. Since
the latter is related to the amount of steam produced, no additional objective on the
steam production need be considered. The decision variables are taken as
u [R
gas
, H
2
O
in
, T
F,in
, T
c,in
, m, D
p
, L
1
, L
2
]
T
(1)
In Eq. 1, R
gas
and H
2
O
in
are the volumes of recycle gas (assumed to be pure nitrogen
after postreactor treatment) and steam added (at actual conditions) per m
3
of air at
NTP in the incoming mixture (called original feed) of oxylene and air, T
F,in
and T
c,in
are the inlet temperatures of the process gas (after mixing of the original feed with the
recycle stream and steam) and coolant, mis the kg of coolant per kg of the process
gas, and D
p
is the diameter of the catalyst particles.
A reasonable twoobjective optimization problem for Reactor System1 is
written mathematically as:
Max I
1
(u) X
PA
(2a)
Min I
2
(u) L
1
+ L
2
L
cat
(2b)
subject to:
constraints:
T
max
= 510
o
C (2c)
L
cat
3 m (2d)
10
Figure 2: Reactor Systems  (a) 1 and (b) 2
S
4
S
3
S
2
S
1
L
1
L
2
L
3
L
4
L
5
L
9
L
1
L
2
Coolant
(a) (b)
11
Table 3: Details of the Reactor Systems 1 and 2
Parameter Value Reference
(a) Reactor System1
Tube length, L 3 m Sato et al. (1981)
Tube diameter, D 20 mm Sato et al. (1981)
OX concentration in the
(original) feed
85 g (m
3
air at
NTP)
1
Sato et al. (1981)
Mass flux, G 19,455 kg m
2
h
1

(b) Reactor System2
Tube length, L 3.5 m 
Tube diameter, D 25 mm 
Size of the catalyst particle, D
p
3 mm 
Mass flux, G 19,455 kg m
2
h
1

(c) Details of the Catalyst (both systems)
Surface area, a
s
1000 m
2
kg
1
Skrzypek et al. (1985)
Shape Spherical 
Bulk density,
b
980 kg m
3
Skrzypek et al. (1985)
Void fraction of bed,
b
0.42 Leva (1959)
(d) Heat transfer coefficient
Overall heat transfer coefficient, U 110 W m
2
K
1
Elnashaie and
Elshishini (1993)
12
Bounds on the decision variables:
1 R
gas
3.6 m
3
/(m
3
of air at NTP) (2e)
0 H
2
O
in
1.8 m
3
/(m
3
of air at NTP) (2f)
147
o
C T
F,in
247
o
C (2g)
347
o
C T
c,in
447
o
C (2h)
1 m 25 kg coolant/kg process gas (2i)
0.002 D
p
0.008 m (2j)
0.01 L
1
1.5 m (2k)
0.4 L
2
2.4 m (2l)
The lower limit on the feed input temperature is set as 147
o
C because the boiling
point of oxylene is 144
o
C. According to the Coastal Chemical Company
(http://www.coastalchem.com), heat transfer salts can be used for a wide range of
temperatures. The eutectic mixture of sodium and potassium nitrates and nitrites has a
low melting point of 142
o
C and can be used up to temperatures as high as 538
o
C.
With plain carbon steel, the heat transfer salts can be operated up to 454
o
C
(http://www.coastalchem.com). Hence the upper bound on the coolant temperature is
set as 447
o
C (the coolant temperatures are observed to lie below 454
o
C with this
choice).
The constraints in Eq. 2 are taken care of by the use of penalty functions. We
do not wish to have solutions with yields of PA below 1.1, since these indicate
incomplete oxidation of oxylene. Similarly, we need to use penalties if the randomly
generated values of L
1
and L
2
lead to a violation of Eq. 2d, or if the maximum
temperature of the process gas exceeds 510
o
C. The modified problem can be rewritten
as:
13
Max I
1
(u) = X
PA
+
2 2
cat PA
1 2 3
L X
w 1 w 1 w
1.2 3.0
( (
+ +
( (
(3a)
Min I
2
(u) = L
cat
+
2 2
cat PA
1 2 3
L X
w 1 w 1 w
1.2 3.0
( (
+ +
( (
(3b)
subject to:
Eqs. 2e 2l (3c)
The weightages, w
1
w
3
, are assigned as follows:
If X
PA
1.1, w
1
= 1000, else w
1
= 0 (4a)
If L
cat
3m, w
2
= 0, else w
2
= 1000 (4b)
If T
max
510
o
C, w
3
= 0, else w
3
= 1000 (4c)
This problem can now be solved for Reactor System1.
2.2.2. Reactor System2
The second industrial reactor (similar to a unit in India) involves nine
layers/zones of catalyst (Fig. 2b), and there is no mixing of recycle gas or steam at the
feed end. The catalyst of Skrzypek et al. (1985) is used. The diameter of the catalyst
particle is assumed constant at 3 mm, a typical industrial value. Details of this reactor
configuration are given in Table 3.
A meaningful twoobjective optimization problem for this system can be
written as:
Max I
1
(u) = X
PA
(5a)
Min I
2
(u) = L
cat
9
i
i 1
L
=
(5b)
subject to:
constraints:
T
max
= 510
o
C (5c)
14
Total length of reactor tube = 3.5 m (5d)
L
i
0.01 m; i = 1, 2, . . . , 9 (5e)
Bounds on decision variables:
65 c
in
85 g OX/m
3
of air at NTP (5f)
147
o
C T
F,in
297
o
C (5g)
337
o
C T
c,in
447
o
C (5h)
1 m 25 kg coolant/kg process gas (5i)
0.2 S
i
0.45 m; i = 1, 2, . . ., 7 (5j)
0.1 S
8
0.45 m (5k)
none on L
i
(5l)
The upper bound on the feed temperature has been increased from 247
o
C for
the first reactor system to 297
o
C since several optimal solutions for the second reactor
system occurred at the upper bound of 247
o
C. An extra constraint has been put on the
minimum length of each catalyst zone. Again, in order to ensure nearcomplete
conversion of oxylene, and to take care of the constraints, the objective functions are
reformulated using penalty functions as:
Max I
1
(u) = X
PA
+
2 2
cat PA
1 2 3
L X
w 1 w 1 w
1.2 3.6
( (
+ +
( (
(6a)
Min I
2
(u) = L
cat
+
2 2
cat PA
1 2 3
L X
w 1 w 1 w
1.2 3.6
( (
+ +
( (
(6b)
subject to:
8 8
9 i i
i 1 i
L 3.5 L S 0
=
 
=

\
(6c)
Eqs. 5e 5l (6d)
The weightages in the penalty terms are given by
If X
PA
1.1, w
1
= 500; else w
1
= 0 (7a)
15
If L
9
0 m, w
2
= 3000; else w
2
= 0 (7b)
If T
max
510
o
C in bed i; i = 1, 2, . . ., 9; w
3
= 0; else w
3
= 3000 + 250(i1)
(7c)
If L
i
0.01 m; i = 1, 2, . . ., 9; w
3
= 0; else w
3
= 300 (7d)
The decision variables for this problem would be
u = [c
in
, T
F,in
, T
c,in
, m, L
1
, L
2
, . . . , L
8
, S
1
, S
2
, , S
8
]
T
(8)
In Eq. 8, c
in
is the mass of OX per m
3
of air at NTP, and S
1
S
8
are the spacing
between the catalyst layers (Fig. 2b). L
9
is computed from the total length of the
catalyst tube.
We found that the code for the standard NSGAIIaJG did not converge to
optimal (Pareto) solutions for this problem. This was because of the extreme
sensitivity of the gas phase temperature to values of L
i
. A guided NSGAIIaJG
procedure had to be developed to avoid this problem. This is now described.
The number of decision variables for this problem is reduced from twenty in
Eq. 8 to the following twelve:
u = [c
in
, T
F,in
, T
c,in
, m, S
1
, S
2
, , S
8
]
T
(9)
Upper estimates, L
1,estimate
, L
2,estimate
, . . . , L
8,estimate
, of the lengths of the first
eight catalyst zones are provided to the code. After the mapping of any chromosome,
the code calls the subroutine for reactor simulation, which integrates the model
equations. The integration for any catalyst zone, i, is stopped as soon as the
temperature goes past the limiting value of 510
o
C. This gives improved values, L
i
, of
the lengths of the catalyst zones (the values of S
i
to be used for this chromosome are
the same as generated in the NSGAIIaJG code). It is to be noted that the Gear
subroutine used comes out of the integration after every specified value of z
i
to store
the results, and so these improved values of L
i
would violate the temperature
16
constraint. The correct estimates of L
i
to be used for final simulation should, thus, be
L
i
 z
i
(L
9
is computed as the balance of the total length of the reactor tube). These,
values, along with the twelve values of the decision variables (Eq. 9) are again sent to
the subroutine for reactor simulation, and the values of the modified objective
functions in Eq. 6 obtained. The guided NSGAIIaJG works well and gives us the
desired Pareto solutions rapidly, with values of X
PA
of around 1.1 kg PA produced/kg
OX consumed. The above procedure helps search for solutions in the decision
variable space where the values of X
PA
are high while keeping the temperature of the
gas phase within its upper bound. These solutions are missed by the original
algorithm, at least for the several attempts made us. The reason for the success of the
guided algorithm is that X
PA
increases with the gas phase temperature, and we need to
have the highest possible temperature while having intermediate cooling.
This problem can now be solved for Reactor System2.
17
3. Results and Discussions
3.1. Model Development
The model is first checked for its validity. Elnashaie and Elshishini (1993)
have provided plots of the gas phase temperature and the conversion of oxylene as a
function of the axial location in a reactor tube, using the kinetic expressions
developed by Skrzypek et al.
(1985) It was observed that three additional model
parameters were needed to obtain good agreement between model predictions and the
plots of Elnashaie and Elshishini (1993). These are multiplying factors, TP
1
TP
3
, for
the viscosity, specific heat and the thermal conductivity of the gas mixture:
mix
=
mix, correl
TP
1
(9a)
C
p,mix
= C
p,mix,correl
TP
2
(9b)
mix
=
mix,correl
TP
3
(9c)
In Eq. 9, subscripts mix and mix,correl indicate mixture properties to be used, and
values estimated by the correlations (as described earlier). SGAIIaJG has been used
to obtain the three multiplying parameters that minimize the sum of square errors
between one set of results (for the feed mole fraction of OX of 0.0092) of Elnashaie
and Elshishini (1993) and model predicted values. Figure 3 shows the agreement of
the tuned model with this set of data to be quite good. The tuned model was also
found to predict results for two other values of the mole fraction of oxylene in the
feed (0.0042 and 0.0027), even though the latter were not used for tuning (see Fig. 3).
This lends credence to the fact that the model is trustworthy. The tuned values of the
three multiplying factors are given in Table 4.
18
Axial position (m)
0.0 0.1 0.2 0.3 0.4
C
o
n
v
e
r
s
i
o
n
o
f
o

x
y
l
e
n
e
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
Axial position (m)
0.0 0.1 0.2 0.3 0.4
G
a
s
t
e
m
p
e
r
a
t
u
r
e
(
o
C
)
355
360
365
370
375
380
Figure 3: Results of model tuning. Results of Elnashaie and Elshishini (1993) for
input mole fractions of OX of : 0.0092, +: 0.0042 and : 0.0027, respectively;
: Results using the model tuned on data for 0.0092
19
Table 4: Details for tuning the model
Parameter Value
(a) Reactor details (Elnashaie and Elshishini, 1993)
Tube diameter 0.026 m
Tube length 0.365 m
mole fractions of oxylene in feed 0.0092, 0.0042, 0.0027
Mass flux, G 18,080 kg m
2
h
1
Feed/(constant) coolant temperature 360
o
C/360
o
C
Catalyst Skrzypek et al.
(1985)
(b) Values of the tuned multiplying factors
TP
1
0.986
TP
2
0.982
TP
3
0.984
20
3.2. Optimization
The original and the guided NSGAIIaJG codes are used to solve the two
twoobjective optimization problems in Eqs. 2 and 6. The codes are first checked
using standard tests (Kasat and Gupta, 2003) to ensure that they are free of errors. MS
Powerstation Version 4.0 is used to solve the problems using a Pentium4 PC (3.4
GHz, 1.0 GB RAM). The CPU times taken to solve the problems are 34.75 hrs (for
450 generations) and 39.77 hrs (for 45 generations), respectively. The two objectives
are found to be conflicting in nature and lead to Paretooptimal solutions.
3.2.1. Reactor System1
The computational parameters required in NSGAIIaJG are first determined
by trialanderror so as to give the best solutions. The final values of these parameters
are given in Table 5. It is observed that a fairly high value of the mutation probability
is needed to generate a wellspread Pareto set. Fig. 4a shows the optimal solutions for
Reactor System1. If we go from any one point to any other, say, from B to A, we
observe that X
PA
improves (increases) while L
cat
worsens (increases). Thus, the
solutions comprise a Pareto front. Point A corresponds to the highest value (1.173 kg
PA/kg OX) of X
PA
. Point A (X
PA
= 1.173, L
cat
= 2.508 m) is superior to the industrial
values reported by Sato et al. (1981) (X
PA
= 1.149, L
cat
= 2.5 m). This indicates the
usefulness of our optimization study. Figs. 4b i show the associated decision
variables. A considerable amount of scatter is observed in four of the plots for the
decision variables. This is characteristic of almost all reallife industrial problems and
has been encountered in our earlier studies (Kasat and Gupta, 2003; Agarwal and
Gupta, 2007b).
21
Table 5: Computational parameters used in NSGAIIaJG and guided NSGAIIaJG
for Reactor Systems1 and 2, respectively
Parameter
Reactor
System1
Reactor
System2
Number of decision variables 8 12
Population size 100 100
Chromosome length 160 240
Crossover probability 0.95 0.95
Mutation probability 0.048 0.025
Jumping gene probability 0.5 0.5
Fixed length for jumping gene 5 4
L
1,estimate
 1 m
L
2,estimate
L
8,estimate
 0.2 m
z
i
 L
i,estimate
/2000
22
Figure 4(A) (Fig. 4 continued)
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
R
e
c
y
c
l
e
g
a
s
(
m
3
/
m
3
a
i
r
a
t
N
T
P
)
1.5
2.0
2.5
3.0
3.5
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
S
t
e
a
m
i
n
p
u
t
(
m
3
/
m
3
a
i
r
a
t
N
T
P
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
(a)
(b)
(c)
(d)
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
G
a
s
i
n
p
u
t
t
e
m
p
e
r
a
t
u
r
e
(
o
C
)
160
180
200
220
240
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
C
o
o
l
a
n
t
f
l
o
w
r
a
t
e
(
k
g
/
k
g
f
e
e
d
)
5
10
15
20
25
(e)
(f)
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
C
o
o
l
a
n
t
i
n
p
u
t
t
e
m
p
e
r
a
t
u
r
e
(
o
C
)
360
380
400
420
440
B
A
C
A
C
23
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
C
a
t
a
l
y
s
t
d
i
a
m
e
t
e
r
(
m
)
0.002
0.004
0.006
0.008
(h)
(g)
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
L
1
(
m
)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
(i)
Yield of PA
1.11 1.12 1.13 1.14 1.15 1.16 1.17 1.18
L
2
(
m
)
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
Figure 4(B)
Figure 4: Pareto optimal set and decision variables for Reactor System1
24
Interestingly, the optimal value of L
1
remains almost unchanged (Fig. 4h), and the
increase in X
PA
is associated almost solely with the increase of L
2
.
In Fig. 4a, point B corresponds to X
PA
of 1.151 while point A, to an X
PA
of
1.173. The values of the decision variables for these two points are given in Table 6.
Figure 5 shows the profiles of the temperature, OX conversion and the various mole
fractions for these two points. It is interesting to note that an intermediate zone having
no catalyst is required in these reactors for cooling of the gas, so that its temperature
does not go above the limiting value of 510
o
C. A decision maker can use these results
to decide the preferred solution/operating point, using his or her intuition.
It is interesting to compare the results for two adjacent points, A and C, in
Figs. 4a and d. These points are associated with almost the same values of X
PA
and
L
cat
. The values of the decision variables for these points are given in Table 6. We
observe that the values of the feed temperature, coolant flow rate and the steam input
(and so the concentration of oxygen) are quite different for these points. The relative
insensitivity of X
PA
and L
cat
to these decision variables is responsible for the scatter.
More meaningful and useful results without such scatter can be generated by
parameterizing the decision variables, as done by Sareen and Gupta (1995) for an
industrial nylon6 reactor.
25
Table 6: Values of the decision variables corresponding to points A, B and C in Figs.
4a and d
Value/Decision Variable Point A Point B Point C
X
PA
1.151 1.173 1.152
Recycle gas [m
3
/(m
3
air at NTP)] 3.134 3.183 3.051
Steam input [m
3
/(m
3
air at NTP)] 0.974 1.014 0.687
Feed/coolant temperature (
o
C)
224.51/
445.21
223.57/
446.31
201.41/
445.22
Coolant flow rate (kg/kg process
gas)
4.2 4.879 4.67
Catalyst diameter (m) 0.0075 0.0075 0.0076
Catalyst lengths, L
1
/L
2
(m) 0.57/1.001 0.571/1.937 0.571/0.989
26
(a)
Axial position (m)
0.0 0.5 1.0 1.5 2.0 2.5 3.0
T
e
m
p
e
r
a
t
u
r
e
(
o
C
)
200
250
300
350
400
450
500
550
Gas
Coolant
(b)
Axial position (m)
0.0 0.5 1.0 1.5 2.0 2.5 3.0
T
e
m
p
e
r
a
t
u
r
e
(
o
C
)
200
250
300
350
400
450
500
550
Gas
Coolant
Axial position (m)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
C
o
n
v
e
r
s
i
o
n
o
f
o

x
y
l
e
n
e
0.0
0.2
0.4
0.6
0.8
1.0
(c)
Axial position (m)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
C
o
n
v
e
r
s
i
o
n
o
f
o

x
y
l
e
n
e
0.0
0.2
0.4
0.6
0.8
1.0
(d)
Axial position (m)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
M
o
l
e
f
r
a
c
t
i
o
n
0.000
0.001
0.002
0.003
0.004
0.005
0.006
(e)
(f)
Axial position (m)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
M
o
l
e
f
r
a
c
t
i
o
n
0.000
0.001
0.002
0.003
0.004
0.005
0.006
OX
CO
x
PA
OX
PA
CO
x
Figure 5(A) (Fig. 5 continued)
27
Axial position (m)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
M
o
l
e
f
r
a
c
t
i
o
n
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
(g)
Axial position (m)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
M
o
l
e
f
r
a
c
t
i
o
n
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
(h)
OT
MA
P
OT
MA
P
Figure 5(B)
Figure 5: Profiles corresponding to point A (a, c, e and g) and point B (b, d, f and h),
in Figure 4a
28
3.2.2. Reactor System2
The computational parameters required in the guided NSGAIIaJG for this
problem are first determined by trialanderror so as to give the best solutions. The
final values of these parameters are given in Table 5. Fig. 6 shows how the optimal
solutions evolve over the generations for Reactor System2. Converged Pareto
solutions are observed at the end of about 45 generations. A very sharp increase in L
cat
is observed in the converged Pareto set after X
PA
of about 1.166. A decision maker
may like to select this point as the preferred solution (operating point) since the
catalyst length almost doubles beyond this point to give a further increase of X
PA
from
about 1.166 to 1.1708.
Fig. 7a shows the Paretooptimal solution for Reactor System2. One of the
objective functions improves at the cost of the other along the Pareto front. Figs. 7b
m show the associated decision variables. Figs. 7n v show the lengths of the nine
catalytic zones. It is observed that even though there is a considerable amount of
scatter in Figs. 7b u, the increase in X
PA
in Fig. 7a depends mainly on L
9
. A similar
inference was deduced for Reactor System1 too, where the increase of the length of
the last zone of the catalyst was associated with an increase of X
PA
. The values of the
decision variables and the lengths of the catalyst zones are given in Table 7 for points
A and B of Fig. 7a.
Figure 8 shows the profiles of the temperature, conversion and the mole
fractions of the several species corresponding to these two points. It is interesting to
note that the longer ninth catalyst zone (Fig. 7v) leads to a higher increase in the yield
of PA for point B (in Fig. 7a)
29
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Gen = 1
Gen = 2
Gen = 3 Gen = 4
Gen = 5
Gen = 10
Figure 6(A) (Figure 6 continued)
30
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
Gen = 15
Gen = 20
Gen = 25 Gen = 30
Gen = 35 Gen = 40
Figure 6(B) (Figure 6 continued)
31
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Gen = 45
Figure 6(C)
Figure 6: Evolution of the Pareto set over the generations for Reactor System2
32
Figure 7(A) (Fig. 7 continued)
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
Yield of PA
1.10 1.12 1.14 1.16 1.18
O

x
y
l
e
n
e
f
e
e
d
c
o
n
c
e
n
t
r
a
t
i
o
n
(
g
O
X
/
m
3
a
i
r
a
t
N
T
P
)
65
70
75
80
85
Yield of PA
1.10 1.12 1.14 1.16 1.18
G
a
s
i
n
p
u
t
t
e
m
p
e
r
a
t
u
r
e
(
o
C
)
160
180
200
220
240
260
280
Yield of PA
1.10 1.12 1.14 1.16 1.18
C
o
o
l
a
n
t
i
n
p
u
t
t
e
m
p
e
r
a
t
u
r
e
(
o
C
)
340
360
380
400
420
440
Yield of PA
1.10 1.12 1.14 1.16 1.18
C
o
o
l
a
n
t
f
l
o
w
r
a
t
e
(
k
g
/
k
g
p
r
o
c
e
s
s
g
a
s
)
5
10
15
20
25
Yield of PA
1.10 1.12 1.14 1.16 1.18
S
1
(
m
)
0.20
0.25
0.30
0.35
0.40
0.45
(a)
(b)
(c)
(d)
(e)
(f)
A
B
33
Yield of PA
1.10 1.12 1.14 1.16 1.18
S
2
(
m
)
0.20
0.25
0.30
0.35
0.40
0.45
Yield of PA
1.10 1.12 1.14 1.16 1.18
S
3
(
m
)
0.20
0.25
0.30
0.35
0.40
0.45
Yield of PA
1.10 1.12 1.14 1.16 1.18
S
4
(
m
)
0.20
0.25
0.30
0.35
0.40
0.45
Yield of PA
1.10 1.12 1.14 1.16 1.18
S
5
(
m
)
0.20
0.25
0.30
0.35
0.40
0.45
Yield of PA
1.10 1.12 1.14 1.16 1.18
S
6
(
m
)
0.20
0.25
0.30
0.35
0.40
0.45
Yield of PA
1.10 1.12 1.14 1.16 1.18
S
7
(
m
)
0.20
0.25
0.30
0.35
0.40
0.45
(g)
(h)
(i)
(j)
(k)
(l)
Figure 7(B) (Fig. 7 continued)
34
Yield of PA
1.10 1.12 1.14 1.16 1.18
S
8
(
m
)
0.1
0.2
0.3
0.4
Yield of PA
1.10 1.12 1.14 1.16 1.18
L
1
(
m
)
0.1
0.2
0.3
0.4
0.5
Yield of PA
1.10 1.12 1.14 1.16 1.18
L
2
(
m
)
0.01
0.02
0.03
0.04
0.05
Yield of PA
1.10 1.12 1.14 1.16 1.18
L
3
(
m
)
0.01
0.02
0.03
0.04
0.05
Yield of PA
1.10 1.12 1.14 1.16 1.18
L
4
(
m
)
0.00
0.01
0.02
0.03
0.04
0.05
Yield of PA
1.10 1.12 1.14 1.16 1.18
L
5
(
m
)
0.01
0.02
0.03
0.04
0.05
(m)
(n)
(o)
(p)
(q)
(r)
Figure 7(C) (Fig. 7 continued)
35
Yield of PA
1.10 1.12 1.14 1.16 1.18
L
6
(
m
)
0.01
0.02
0.03
0.04
0.05
Yield of PA
1.10 1.12 1.14 1.16 1.18
L
7
(
m
)
0.01
0.02
0.03
0.04
0.05
Yield of PA
1.10 1.12 1.14 1.16 1.18
L
8
(
m
)
0.02
0.04
0.06
0.08
0.10
Yield of PA
1.08 1.10 1.12 1.14 1.16 1.18
L
9
(
m
)
0.0
0.2
0.4
0.6
0.8
1.0
(s)
(t)
(u)
(v)
Figure 7(D)
Figure 7: Pareto optimal set and corresponding results for the decision (and other)
variables for Reactor System2
36
Table 7: Values of the decision (and some other) variables corresponding to point A
and B in Fig. 7a.
Variable Point A Point B Variable Point A Point B
X
PA
1.166 1.1708 S
7
(m) 0.357 0.208
Concentration of OX
(g OX/m
3
of air at NTP)
72.814 80.648 S
8
(m) 0.435 0.275
Gas input temperature (
o
C) 274.52 285.5 L
1
(m) 0.291 0.243
Coolant input temperature
(
o
C)
388.01 387.6 L
2
(m) 0.012 0.010
Coolant flow rate (kg/kg
process gas)
6.087 12.022 L
3
(m) 0.011 0.011
S
1
(m) 0.356 0.356 L
4
(m) 0.011 0.012
S
2
(m) 0.363 0.367 L
5
(m) 0.016 0.015
S
3
(m) 0.345 0.348 L
6
(m) 0.011 0.011
S
4
(m) 0.436 0.343 L
7
(m) 0.019 0.019
S
5
(m) 0.245 0.206 L
8
(m) 0.027 0.024
S
6
(m) 0.369 0.263 L
9
(m) 0.205 0.798
37
Axial position (m)
0 1 2 3
T
e
m
p
e
r
a
t
u
r
e
(
o
C
)
250
300
350
400
450
500
550
Gas
Coolant
Axial position (m)
0 1 2 3
T
e
m
p
e
r
a
t
u
r
e
(
o
C
)
250
300
350
400
450
500
550
Gas
Coolant
Axial position (m)
0 1 2 3
C
o
n
v
e
r
s
i
o
n
o
f
o

x
y
l
e
n
e
0.0
0.2
0.4
0.6
0.8
1.0
Axial position (m)
0 1 2 3
C
o
n
v
e
r
s
i
o
n
o
f
o

x
y
l
e
n
e
0.0
0.2
0.4
0.6
0.8
1.0
Axial position (m)
0 1 2 3
M
o
l
e
f
r
a
c
t
i
o
n
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
Axial position (m)
0 1 2 3
M
o
l
e
f
r
a
c
t
i
o
n
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
(a) (b)
(c) (d)
(e) (f)
OX
PA
CO
x
OX
PA
CO
x
Figure 8(A) (Fig. 8 continued)
38
Axial position (m)
0 1 2 3
M
o
l
e
f
r
a
c
t
i
o
n
0.0000
0.0005
0.0010
0.0015
0.0020
0.0025
Axial position (m)
0 1 2 3
M
o
l
e
f
r
a
c
t
i
o
n
0.0000
0.0005
0.0010
0.0015
0.0020
0.0025
(g) (h)
OT
OT
P
MA
P
MA
Figure 8(B)
Figure 8: Profiles corresponding to point A (a, c, e and g) and point B (b, d, f and h),
in Figure 7a
39
Figure 9 shows the effect of the mutation and crossover probabilities on the
Pareto optimal solution for Reactor System2. Multiobjective optimization of this
system is computationally time consuming. Hence, the right set of values of the
parameters is needed for the guided NSGAIIaJG to obtain a smooth Paretooptimal
solution in the least number of generations. The Pareto solutions obtained for the
reference values of mutation and crossover probabilities give better solutions, at least
in the high PA yield region.
The effect of varying the number of catalyst zones in Reactor System2 is
shown in Figure 10. It is observed that seven zones of catalyst can give almost the
same high yields of PA, as do nine zones. However, the total catalyst length is lower
in the lower PA yield region, where the preferred solution may be located. Figure 11
shows the effect of the total length of the reactor tube for a seven catalyst zone
Reactor System2. It is observed that slightly larger values of L
cat
are indicated when
shorter reactor length of 3 m is taken, than when a 3.5 m tube is used.
It will be interesting to carry out multiobjective optimization of this reactor
with the number of catalyst zones and the length of the reactor tube as decision
variables. The former would require varying lengths of the chromosomes in the
population, depending on the number of catalyst zones. The codes of the various
adaptations of NSGAIIJG do not permit this at present, and is being attempted
currently.
40
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
p
c
= 0.95
p
m
= 0.025 (ref)
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
p
c
= 0.95
p
m
= 0.04
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
p
c
= 0.95
p
m
= 0.01
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
p
c
= 0.95
p
m
= 0.025 (ref)
Yeild of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.4
0.6
0.8
1.0
1.2
p
c
= 0.90
p
m
= 0.025
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.2
0.4
0.6
0.8
1.0
1.2
p
c
= 0.98
p
m
= 0.025
(a) (d)
(b) (e)
(c) (f)
Figure 9: Paretooptimal solutions for different mutation and crossover probabilities
for Reactor System2 at the 45
th
generation
41
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.2
0.4
0.6
0.8
1.0
1.2
Figure 10: Paretooptimal solutions for Reactor System2 with different number of
catalyst zones; : 9 catalyst zones (ref) and : 7catalyst zones.
42
Yield of PA
1.10 1.12 1.14 1.16 1.18
T
o
t
a
l
c
a
t
a
l
y
s
t
l
e
n
g
t
h
(
m
)
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Figure 11: Paretooptimal solutions for Reactor System2 with 7 catalyst zones and
two different lengths of the reactor tube: : L = 3.5 m and : L = 3.0 m
43
4. Conclusion
Multiobjective optimization problems have been solved for two industrial
phthalic anhydride units using a general reactor model. Adaptations to NSGAIIaJG
have been developed so as to obtain converged solutions more rapidly than possible
otherwise. It is observed that the productivity of PA can be easily enhanced by a
proper choice of decision variables.
44
5. Appendix
5.1. Appendix 1
Complete set of equations for oxidation of oxylene to phthalic anhydride
(adapted from Elnashaie and Elshishini, 1993)
(a) LHHW rate expressions for the i
th
reaction in Fig. 1:
1 1
=
v OX
r k Y
3 3
=
v OX
r k Y
4 4
=
v OT
r k Y
5 5
=
v P
r k Y
6 6
=
v OX
r k Y
7 7
=
v OT
r k Y
8 8
=
v PA
r k Y (A1)
Here
2
2 2
2
1
=
(
+ + + + + +
(
O
v
OX OX OT OT MA MA P P PA PA O O
t
Y
K Y K Y K Y K Y K Y K Y
P
i
i io
g
E
k k exp
R T
 
= 

\
; i = 1, 2, . . . , 8
ads
j
j jo
g
H
K K exp
R T
 
= 

\
; j = OX, OT, P, PA, MA, O
2
(A2)
2 2
=
v OX
r k Y
45
(b) Steady state mass and heat balance equations between the bulk gas and the outer
surface of the impervious catalyst:
( )
1 2 3 6
, , ,
1
+ + +
( =
s
g OX s OX b OX s t
b
r r r r
k a Y Y P
(A3)
( )
1 4 7
, , ,
1
( =
s
g OT s OT b OT s t
b
r r r
k a Y Y P
(A4)
( )
2
, , ,
1
( =
s
g MA s MA b MA s t
b
r
k a Y Y P
(A5)
( )
4 5
, , ,
1
( =
s
g P s P b P s t
b
r r
k a Y Y P
(A6)
( )
5 6 7 8
, , ,
1
+ +
( =
s
g PA s PA b PA s t
b
r r r r
k a Y Y P
(A7)
( )
3 8
, , ,
8
1
+
( =
s
g COx s COx b COx s t
b
r r
k a Y Y P
(A8)
( )
2 2 2
1 2 3 4 5 6 7 8
, , ,
4.5 8.5 3 2 5.5
1
+ + + + + + +
( =
s
g O s O b O s t
b
r r r r r r r r
k a Y Y P
(A9)
( )
2 2 2
1 2 3 4 5 6 7 8
, , ,
3 5 3 2 2
1
+ + + + + + +
( =
s
g H O s H O b H O s t
b
r r r r r r r r
k a Y Y P
(A10)
( )
8
,
1
( )
1
i i s
i
s s
b
H r
ha T T
(A11)
The above coupled equations are solved using the DNEQNF program in the IMSL
library.
(c) Effectiveness factors:
46
The effectiveness factor of each reaction is determined as:
( )
( )
, ,
, ,
,
,
i s s i s
i
i b i b
r T Y
r T Y
= (A12)
while the component effectiveness factors are written as:
( )
( )
1 2 3 6
1 2 3 6
+ + +
=
+ + +
s
OX
b
r r r r
r r r r
( )
( )
1 4 7
1 4 7
=
s
OT
b
r r r
r r r
( )
( )
2
2
s
MA
b
r
r
=
( )
( )
4 5
4 5
s
P
b
r r
r r
( )
( )
5 6 7 8
5 6 7 8
s
PA
b
r r r r
r r r r
+ +
=
+ +
( )
( )
3 8
3 8
s
COx
b
r r
r r
+
=
+
(A13)
(d) Steady state balance for the bulk gas phase:
( )
,
1 1, 2 2, 3 3, 6 6,
 
= + + +

\
OX b
b b b b
F
Y
d
G r r r r
dz M
(A14)
( )
,
1 1, 4 4, 7 7,
 
=

\
OT b
b b b
F
Y
d
G r r r
dz M
(A15)
( )
,
2 2,
 
=

\
MA b
b
F
Y
d
G r
dz M
(A16)
( )
,
4 4, 5 5,
 
=

\
P b
b b
F
Y
d
G r r
dz M
(A17)
47
( )
,
5 5, 6 6, 7 7, 8 8,
 
= + +

\
PA b
b b b b
F
Y
d
G r r r r
dz M
(A18)
( )
,
3 3, 8 8,
8
 
= +

\
COx b
b b
F
Y
d
G r r
dz M
(A19)
( )
2
,
1 1, 2 2, 3 3, 4 4, 5 5, 6 6, 7 7, 8 8,
4.5 8.5 3 2 5.5
 
= + + + + + + +

\
O b
b b b b b b b b
F
Y
d
G r r r r r r r r
dz M
(A20)
( )
2
,
1 1, 2 2, 3 3, 4 4, 5 5, 6 6, 7 7, 8 8,
3 5 3 2 2
 
= + + + + + + +

\
H O b
b b b b b b b b
F
Y
d
G r r r r r r r r
dz M
(A21)
( ) ( ) ( )
8
,
1
4
pF
ref i i i b c
i F
C
d
G T T H r U T T
dz M D
=
(
=
(
(A22)
( ) ( )
(
=
(
pC
c C ref C
C
C
d
m T T DU T T
dz M
(A23)
The above set of equations is solved using the program, DIVPAG in the IMSL library.
The yield of PA, X
PA
, is defined by
X
PA
(kg PA produced)/(kg oxylene consumed)
The concentrations of the two species are used to evaluate the yield.
48
5.2. Appendix 2
Derivations
(a) L H rate expression:
Consider reaction 1:
oXylene + O
2
oTolualdehyde + H
2
O
Step 1: Adsorption of oxylene on the catalyst active site:
OX + l
OXa
OXd
k
k
OXl
where, l is a vacant active site and OXl is an active site with oxylene adsorbed on it,
k
OXa
is the adsorption rate constant and k
OXd
is the desorption rate constant.
The rate equation for this step can be written as:
OXl
OXa OX,s l OXd OXl
dC
k P C k C
dt
= (B1)
where, P
OX,s
is the partial pressure of oxylene just adjacent to the catalyst surface, C
l
is the concentration of the vacant active sites and C
OXl
is the concentration of the
active sites with oxylene adsorbed on them.
Similarly for oxygen:
2
2 2 2 2
O l
O a O ,s l O d O l
dC
k P C k C
dt
= (B2)
where,
2
O ,s
P is the partial pressure of oxygen just adjacent to the catalyst surface and
2
O l
C is the concentration of the active sites with oxygen adsorbed on them.
Step 2: Surface reaction between the adsorbed species (OXl and O
2
l):
OXl + O
2
l
*
1
k
2l + H
2
O
Water formed by the reaction is not adsorbed on the catalyst surface.
49
The surface reaction rate equation can be written as:
2
*
1 1 OXl O l
r k C C = (B3)
The surface reaction between the adsorbed species is taken as the rate limiting step
(Skrzypek et al., 1985).
Hence
2
O l
OXl
dC
dC
0
dt dt
= = .
Thus:
OXa
OXl OX,s l OX OX,s l
OXd
k
C P C K P C
k
= =
2
2 2 2 2
2
O a
O l O ,s l O O ,s l
O d
k
C P C K P C
k
= = (B4)
Similarly for all the other adsorbed species:
OTl OT OT,s l
C K P C =
MAl MA MA,s l
C K P C =
Pl P P,s l
C K P C =
PAl PA PA,s l
C K P C = (B4)
where, K
i
are the adsorption equilibrium constants.
The total number of active sites, C
T
, on the catalyst surface is:
2
T l OXl OTl MAl Pl PAl O l
C C C C C C C C = + + + + + +
Equation (B4) gives:
2 2
T l OX OX,s OT OT,s MA MA,s P P,s PA PA,s O O ,s
C C 1 K P K P K P K P K P K P ( = + + + + + +
(B5)
50
Using equations (B4) and (B5) in equation (B3) gives:
( )
2 2
2 2
* 2
1 OX O T OX,s O ,s
1 2
OX OX,s OT OT,s MA MA,s P P,s PA PA,s O O ,s
k K K C P P
r
1 K P K P K P K P K P K P
=
( + + + + + +
(B6)
Dividing both numerator and denominator by
2
t
P gives:
2
2 2
1 OX,s O ,s
1 2
OX OX,s OT OT,s MA MA,s P P,s PA PA,s O O ,s
t
k Y Y
r
1
K Y K Y K Y K Y K Y K Y
P
=
(
+ + + + + +
(
(B
7)
Rate expressions for the other reactions are derived in the same manner.
(b) Steady state component balance and heat balance for the gas phase:
Assumptions:
i) The reactor operates at steady state conditions.
ii) Radial dispersion of mass and heat are negligible.
iii) Axial dispersion of mass and heat are negligible.
iv) The gaseous components follow ideal gas law.
Component balance in bulk phase:
Component j
IN
Component j
OUT
= Rate of removal of j
( ) ( ) ( ) ( ) ( )
2 2 2 s s
j b j b j
z z z
b b
u u
C R C R R R z
+
   
=
 
\ \
(B8)
where,
j,produced
j 3
bed
mol
R
m .s
Dividing throughout by
2
R z and taking limits as z 0 , gives:
( )
j s
j
d C u
R
dz
= (B9)
51
Substituting
j
j s
F
GY
C u
M
= in the above equation gives:
( )
j F
j
d Y / M
G R
dz
= (B10)
Heat Balance in bulk phase:
Heat
IN
Heat
OUT
+ Heat transferred from catalyst = Heat removed by jacket
( )[ ] ( )[ ]
( ) ( ) ( )[ ]
2 2 s s F F
F b ref F b ref
z z z
F b F b
2
j j j c
j
u u Cp Cp
R T T R T T
M M
H r R z U 2 R z T T
+
   
+
 
\ \
=
(B11)
Dividing throughout by
2
R z and taking limits as z 0 , gives:
[ ]
( ) ( )
F
F s ref
F
j j j c
j
Cp
d u T T
M 2U
H r T T
dz R
 

\
=
(B12)
Substituting
j s
C u G = gives:
[ ] ( ) ( )
F
ref j j j c
j F
Cp d 4U
G T T H r T T
dz M D
 
=

\
(B14)
Heat balance for coolant:
Heat
IN
Heat
OUT
+ Heat transferred from bulk phase = 0
[ ] [ ] ( )[ ]
c c ref c c ref c
z z z
mCp T T mCp T T U D z T T 0
+
+ = (B15)
Dividing throughout by z and taking limits as z 0 , gives:
[ ] ( )
( )
c c ref
c
d Cp T T
m U D T T
dz
= (B16)
52
5.3. Appendix 3
Kinetic and Transport properties
(i) Binary Diffusivity: (Poling et al., 2001)
Wilke and Lee equation:
( )
0.5 3 1.5
AB
AB 0.5 2
AB AB D
3.03 0.98/ M 10 T
D
PM
=
(C1)
where,
1
AB
A B
1 1
M 2
M M
(
= +
(
;
A B
AB
2
+
= ;
1/ 3
A B b,i
, 1.18V = (
o
A) ;
( )
( ) ( ) ( )
D B * * *
*
A C E G
exp DT exp FT exp HT
T
= + + + ;
*
AB
kT
T =
;
0.5
AB A B
k k k
 
=

\
;
b
1.15T
k
= and
P Pressure, bars; V
b
molar volume at normal boiling point, cm
3
/gmol; T
b
normal boiling point, K; A = 1.06036, B = 0.1561, C = 0.193, D = 0.47635, E =
1.03587, F = 1.52996, G = 1.76474, H = 3.89411
(ii) Effective Diffusivity: (Elnashaie and Elshishini, 1993)
Wilke Equation:
n
j
eff
j 1 i,mix i ij
j i
Y
1 1
D 1 Y D
=
(C2)
53
(iii) Mass transfer coefficient between catalyst particle and gas phase: (Wakao and
Kaguei, 1982)
*
g,i p 0.6 1/ 3
i eff
i,mix
k D
2.0 1.1Re Sc
D
= + (C3)
where,
p
mix
GD
Re =
and
mix
eff
mix i,mix
Sc
D
(iv) Viscosity of gaseous mixture: (Poling et al., 2001)
n
i i
mix n
i 1
j ij
j 1
Y
Y
=
=
(C4)
where,
2
0.5 0.25
i i
j j
ij 0.5
i
j
M
1
M
M
8 1
M
(
   
(
+
 
 
(
\ \
=
(  
+ ( 

(
\
(v) Thermal Conductivity of gaseous mixture: (Poling et al., 2001)
Wassiljewa equation:
n
i i
mix n
i 1
j ij
j 1
Y
YA
=
=
(C5)
where, A
ij
= 1.0, if i = j
else
( ) ( )
2
0.5 0.25
*
tri trj i j
ij 0.5
i
j
1 / M / M
A
M
8 1
M
(
+
(
=
(  
+ ( 

(
\
;
*
1.0 ;
( ) ( )
( ) ( )
j r ,i r,i
tri
trj
i r, j r , j
exp 0.0464T exp 0.2412T
exp 0.0464T exp 0.2412T
(
=
(
;
1/ 6
3
c,i i
i 4
c,i
T M
210
P
(
=
(
(
and
T
c,i
critical temperature, K; P
c,i
critical pressure, bar
54
(v) Heat transfer coefficient between catalyst particle and bulk phase: (Wakao et al.,
1978)
p 0.6 1/ 3
mix
hD
2.0 1.1Re Pr = +
(C6)
where,
pmix mix
mix
C
Pr
(vi) Specific heat of the gas mixture:
n
pmix i pi
i 1
C YC
=
=
(C7)
(vii) For components like oxylene, maleic anhydride, phthalic anhydride, combustion
products, oxygen, nitrogen and steam, the values of the vapor phase viscosity, thermal
conductivity and specific heat are obtained from Daubert and Danner (1989).
(viii) For otolualdehyde and phthalide, the group contribution method is used for the
property estimations. Specific heat, C
p
; boiling point, T
b
; critical constants, T
c
, P
c
and
V
c
; and acentric factor, , are calculated using the Constantinou and Gani property
functions from the group contributions (Poling et al., 2001). With these values, the
vapor phase viscosity and thermal conductivity of OT and P are estimated using the
Chung et al. method given in Poling et al. (2001). This method was first tested on
components whose viscosity and thermal conductivity were known, viz, PA and OX.
The values were found to be almost the same as that obtained from Daubert and
Danner (1989).
55
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