Computers and Chemical Engineering 28 (2004) 2219–2231

Scalable multi-objective optimization of industrial purified

terephthalic acid (PTA) oxidation process
Shengjing Mu∗ , Hongye Su, Tao Jia, Yong Gu, Jian Chu
National Laboratory of Industrial Control Technology, Institute of Advanced Process Control,
Zhejiang University, Yuquan Campus, Hangzhou 310027, PR China

Received 5 July 2003; received in revised form 15 March 2004; accepted 24 March 2004

Available online 6 May 2004

Abstract

In the present study, a scalable multi-objective optimization strategy of industrial purified terephthalic acid (PTA) oxidation process is
proposed to improve the industrial operation efficiency. The model is based on the fundamental oxidation mechanism and historical industrial
data, which is structured into two series ideal continuously stirred tank reactor (CSTR) models. Generally, the optimal objective of industrial
operation is to produce more and polish the quality of the production with minimizing the consumption of both energy and materials. In the PTA
oxidation process, the most important undesired intermediate product generated and accompanied with the product is 4-carboxy-benzaldehyde
(4-CBA), and its content is usually regarded as a criterion to judge the quality of the product. The yield of PTA oxidation process is represented
by the inlet rate of the reactor, which is also one of the decision variables in the model. In order to be better applied in different industrial
operation cases, a four level scalable operation strategy is proposed in the steady multi-objective optimization problem. In each operation
cases, different combinations of decision variables are presented according to the industrial practice. The steady multi-objective optimization
algorithm applied in this study is based on evolutionary algorithm for its natural characteristics, which is proposed by the authors and named
as neighborhood and archived genetic algorithm (NAGA).
© 2004 Elsevier Ltd. All rights reserved.

Keywords: Multi-objective optimization; Scalable operation; Purified terephthalic acid (PTA) oxidation process; Neighborhood and archived genetic
algorithm (NAGA)

1. Introduction lems were usually solved using a single scalar objective

Process industries aim at maximizing their production
while simultaneously improving product qualities. Unfortu-
nately, the two requirements are often conflicted or incon-
sistent. It is useful and necessary to find the trade-off com-
promises to balance the two objectives. The trade-off solu-
tions in the multi-objective optimization problem are often
not unique, but a solution set, which is named as Pareto
set. However, the Pareto set is extremely useful in indus-
trial operation since it narrows down the choices and helps
to guide a decision-maker in selecting a desired operating
point (called the preferred solution) from among the (re-
stricted) set of Pareto optimal points, rather than from a
much larger number of possibilities (Yuen, Gupta, & Ray,
2000). In earlier years, multi-objective optimization prob-
∗ Corresponding author. Tel.: +86-571-87952369; fax: +86-87952279.
E-mail address: sjmu@iipc.zju.edu.cn (S. Mu).
function, which was a weighted-average of the several ob-
jectives (‘scalarization’ of the vector objective function). It
leads to the solution obtained depends largely on the val-
ues assigned to the weighting factors used, which is done
quite arbitrarily. An even more important disadvantage of the
scalarization of the several objectives is that the algorithm
may miss some optimal solutions, which can never be found,
regardless of the weighting factors chosen. This happens if
the non-convexity of the objective function gives rise to a
duality gap, which is popular in practical industrial problem.
In many multi-objective optimization methods, evolution-
ary algorithms are most popular because they deal simul-
taneously with a set of possible solutions and find several
members of the Pareto solutions in a single run of the algo-
rithm. Additionally, evolutionary algorithms are less suscep-
tible to the shape or continuity of the Pareto front (Coello,
2001). Fonseca and Fleming (1994) and Coello (2001)
presented comprehensive reviews on the development of

0098-1354/$ – see front matter © 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compchemeng.2004.03.007
2220 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231

the evolutionary multi-objective optimization, respectively.

Nomenclature Compared with the previously famous methods, such
cO2 the O2 content (%) as Non-dominated Sorting Genetic Algorithm (NSGA)
c1 –c5 the exit concentrations of five chemical (Srinivas & Deb, 1994), Niched Pareto Genetic Algorithm
species (mol kg−1 ) HAc (NPGA) (Horn, Nafpliotis, & Goldberg, 1994), Pareto
c1,0 –c5,0 the feed concentrations of five chemical Archive Evolutionary Strategy (PAES) (Knowles & Corne,
species (mol kg−1 ) HAc 2000) and Strength Pareto Evolutionary Algorithm (SPEA)
c4-CBA the concentration of 4-CBA in the crude (Zitzler & Thiele, 1999), the method this work employed,
TA (ppm) (by mass) Neighborhood and Archived Genetic Algorithm (NAGA)
[Co] catalyst concentration (ppm) (by mass) offers several advantages (Mu, Su, Wang, & Chu, 2003b):
d the neighborhood size in NAGA • Low computation complexity.
Ei active energy (kJ mol−1 ) • Insensitive of the efficiency to the method parameters.
f 1, f 2 minimization objective • Uniform distribution on the Pareto front.
f1 –f4 the functions of the concentration of
Many studies have been reported in the literature on
catalyst
the multi-objective optimization strategies applied in in-
FFeed feed to reactor (kg h−1 )
dustrial process modeling, optimal design and operation.
FPX p-xylene to feed mixing tank (kg h−1 )
Bhaskar (2000) provided a review for the applications
F1 –F6 plant factor
of multi-objective optimization in chemical engineering.
kc the first crystallizer reaction rate constants
Santos and Dourado (1999) utilized multi-objective opti-
(min−1 )
mization genetic algorithm to solve optimal pulping process
ki,0 the coefficients of reaction rate constants
scheduling problem with high order constraints that was
kr the oxidation reactor reaction rate constants
usually hard to handle by traditional methods. Wang and
(min−1 )
Sheu (2000) applied multi-objective optimization method
k1 –k4 the reaction rate constants of the four
in handling parameter estimation problems of fermentation
reactions (min−1 )
processes. The objectives are the mean least-squares error
k10 –k40 oxidation reaction rate constant of the measured values and the calculated values of differ-
(min−1 ) ent batch and fed-batch observations. Shi and Yao (2001)
Kc the normal value of the concentration solved MILP and MINLP problem in process synthesis with
of 4-CBA (ppm) (by mass) multi-objective optimization strategy. In order to maximize
Kf the normal value of the feed flow (kg h−1 ) simultaneously the purity of the extract and productivity
Kmax maximum number of generations in NAGA of the unit in optimization simulated moving bed, Zhang
LR level of reactor (%) et al. (2003) used multi-objective optimization algorithm
rj the reaction rates of the four main to obtain the Pareto optimal solution of the two conflict
reactions (min−1 ) objectives, which presented the best operating condition for
TC first crystallizer temperature (◦ C) process optimization. Recently, Gupta and Ray and their
TR reactor temperature (◦ C) colleagues have applied the multi-objective optimization
VOC vent O2 content from the first genetic algorithm in different industrial processes, such as
crystallizer (vol.%) membrane separation modules (Yuan et al., 2000), industrial
VOR vent O2 content from the reactor (vol.%) wiped-film pet reactor (Bhaskar, Gupta, & Ray, 2000a,b,
VA the volume of the history archive in NAGA 2001), industrial hydrogen plants (Rajesh, Gupta, Rangaiah,
w1 , w2 the coefficients of the profit to per & Ray, 2001), fluid catalytic cracking unit (Kasat, Kunzru,
unit 4-CBA concentration decrement and Saraf, & Gupta, 2002), industrial styrene reactor (Yee,
per unit the feed rate increment Ray, & Rangaiah, 2003), etc. Most of these studies involve
WWC reactor condenser to water withdraw minimizing the concentration of the side products and/or
(kg h−1 ) maximizing the concentration of the principal products.
WWD total water withdrawal (kg h−1 ) In PTA oxidation process, the concentration of 4-CBA
in the crude TA is usually regarded as main qualification
Greek letters to value the quality of the product, crude TA. 4-CBA is the
ε the constant of co-crystallization effect main intermediate product and its content should be con-
τ the residence time of the oxidation trolled below a limit to ensure some other properties, like
reaction tank (min) optical density and 4-carboxy-p-terphenyl (4-CTr) concen-
τc the first crystallizer residence time (min) tration of the crude TA, to lie within certain specifications.
τr the oxidation reactor residence time (min) Additional, 4-CBA is prone to co-crystallization with TA
and contaminates crude TA (Mu, Su, Gu, & Chu, 2003a).
On the other hand, increasing the production will get effect
 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231
instantly to increase the economic benefit of the operation.
Thus, the optimization of design and operation of PTA
oxidation process requires multiple objective functions and
constraints. In our earlier optimization study of the PTA ox-
idation process, six process variables are employed simulta-
neously, viz. catalyst concentration, total water withdrawal,
vent O2 concentration from the reactor and from the first
crystallizer, reactor temperature and first crystallizer tem-
perature (Mu et al., 2003a). All of these variables can easily
be changed in the industrial PTA oxidation process. But it
is only from the view of academic that all six decision vari-
ables included in the formulation of optimization problem
with the same priority. It is proved that this strategy is not
appropriate in industrial practical optimal operation. In fact,
the operators usually have some ideas that different opera-
tion variables have different preference or priority to be se-
lected. In most cases, they prefer to operate only one or part
of the candidate decision variable set, instead of adjusting
all available decision variables simultaneously. It presses us
to further research on the development of different opera-
tion stages to fit for the practical requirement. In this paper,
a scalable problem with four level operation cases for PTA
oxidation process optimization is proposed and the detailed
study results of the further insight are presented.
2. Process description
Fig. 1 presents the oxidation reaction mechanism com-
monly be considered (Cao, Alberto, & Massimo, 1994a;
Cao, Massimo, & Massimom, 1994b). The oxidation re-
action sequence of p-xylene (PX) generates three inter-
mediates, p-tolualdehyde (TALD), p-toluic acid (P-T) and
4-carboxy-benzaldehyde (4-CBA).
The schematic diagram of PTA oxidation process is shown
in Fig. 2. p-xylene, acetic acid solvent, promoter (hydro-
bromic acid), catalyst (cobalt acetate and manganese acetate)
and the recycle mother liquid are continuously metered into
feed mixed tank. The mixed stream pumps the reactor, and
the air is fed to the reactor through four-inlets. The oxidation
reaction is conduced in two stages, first stage being the agi-
tated oxidation reactor, while the second stage is the agitated
first crystallizer. Exothermic heat of reaction is removed by
condensing the boiling reaction solvent. A portion of this
condensate is withdrawn to control the water concentration
in the reactor, and the remainder is refluxed to the reactor.
Autoxidation of p-xylene in acetic acid solvent with cobalt
acetate, manganese acetate, and hydrobromic acid as catal-
CHO
CH3 COOH COOH COOH
O2 O2 O2 O2
CH3 CHO
CH3 CH3 COOH
TALD TA
PX P-T 4-CBA
Fig. 1. The oxidation reaction process mechanism of PX.
2221
ysis proceeds by the following overall reaction to afford
terephthalic acid in 98% molar yield, in which 97–98% re-
action is occurred in the oxidation reactor and the rest reac-
tion is finished in the first crystallizer. The combined molar
yield of the intermediates (4-carboxy-benzaldehyde, p-toluic
acid and p-tolualdehyde) from the first crystallizer is about
0.2%. The detailed discussion about the oxidation reaction
theory and mechanism of p-xylene was referred to Cao et al.
(1994a,b) or Wang (2001).
The concentration of 4-CBA is related with oxidation pro-
cess closely. Therefore, the variables affect the oxidation
process as well as the concentration of 4-CBA. In the oxida-
tion reactor, the key variables to affect the reaction are the
residence time of reaction, the ratio of PX to acetic acid, the
ingredient and concentration of catalyst, reaction tempera-
ture and pressure, the partial pressure of oxygen and water
content in the reactor (Wang, 2001; Mu et al., 2003a).
3. Modeling of the PTA oxidation process
The reaction scheme consists of four main sequential ox-
idation reactions as shown in Fig. 1, along with several
combustion side reactions, which the final products are wa-
ter, carbon monoxide and carbon dioxide. The model of the
present study is based on two sequential reactors, which is
illustrated as the oxidation reactor and the first crystallizer
in Fig. 2. Both reactors are agitated sufficiently and are re-
garded as ideal continuously stirred tank reactor (CSTR).
Thus, the main reaction model of the oxidation process can
be described as follows (Wang, 2001):
c1,0 − c1 + τr1 = 0, c2,0 − c2 + τ(r2 − r1 ) = 0,
c3,0 − c3 + τ(r3 − r2 ) = 0, c4,0 − c4 + τ(r4 − r3 ) = 0,
c5,0 − c5 − τr4 = 0 (1)
where ci,0 and ci (i = 1, 2, . . . , 5) are the feed and exit con-
centration of PX, TLAD, P-T, 4-CBA and TA, respectively.
τ denotes the residence time of the tank (reactor/first crys-
tallizer). rj (j = 1, 2, . . . , 4) are the reaction rates of the
four main reactions, which are formulated as follows (Wang,
2001):
fj
rj = −kj
4 cj , j = 1, . . . , 4 (2)
1 ki c i +ε
where k1 , k2 , k3 , k4 are the reaction rate constants of the
four reactions, which are regards as the functions of reac-
tion temperature and the concentration of the vent oxygen in
the reactor. f1 , f2 , f3 , f4 are the functions of the concentra-
tion of catalyst. These detailed formulations and parameter
values are given in Appendix A.
The reaction model simulates both the reaction process
in oxidation reactor and the first crystallizer, which each of
them followed Eq. (1). The output of the oxidation reactor
is the input of the first crystallizer. That is, the composition
2222 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231

Fig. 2. Skeleton drawing of PTA oxidation process.

of five components of the oxidation reactor outlet flow is
the composition of the first crystallizer feed flow.
In the oxidation reaction, the significant influencing fac-
tors in the oxidation process are the residence time of tank,
the ratio of PX to acetic acid, the ingredient and the con-
centration of catalyst, reaction temperature and pressure, the
partial pressure of oxygen and water content in the reactor.
After the comparison of these factors and practical process
variables, 10 process variables are selected as input variables
of the model, which are shown in Table 1.
Among the 10 process variables selected by mechanism
analysis in Table 1, the sensitivity analysis of each variable
is performed to obtain the quantitative relationship with the
concentration of 4-CBA by utilizing the mechanistic model.
The third column in Table 1 gives the signs and values of
the change of 4-CBA content with 1% increase in each pro-
cess variables from their reference values, i.e., reactor tem-
perature increases 1% from 188 ◦ C causes 4-CBA content
decrease 149 ppm from 2702 ppm. It is shown in Table 1
that reactor condenser to water withdraw, WWC, is so small
to be negligible compared with other variables. As a matter
of fact, it is also confirmed by the plant operators that the
control valve of WWC is fixed in most cases.
The reactor liquid level LR is close to 90% of the reactor
nominal height and the upper of liquid level is full of foam
and vapor, which is hard to be regulated. Therefore, for the
sake of brevity, LR is excluded from the decision variable
set of the optimal operation.
In the PTA oxidation process, many other factors also
affect the reaction but hard to be recurrence at laboratory

Table 1
The all variables of the process model
No. Variables/units Sensitivity value (ppm) Range Reference value

Inputs
1 First crystallizer temperature, TC (◦ C) −264.4139 [180, 188] 184.177
2 Reactor temperature, TR (◦ C) −149.1769 [185, 195] 188.005
3 Liquid level of reactor, LR (%) −90.6290 [88, 92] 88.994
4 Catalyst concentration, [Co] (ppm) −71.2165 [300, 380] 341.07
5 p-xylene to feed mixing tank, FPX (kg h−1 ) 49.9323 [26000, 34000] 26243.57
6 Feed to reactor, FFeed (kg h−1 ) 49.3565 [130000, 170000] 143008.71
7 Total water withdrawal, WWD (kg h−1 ) −8.5567 [25000, 45000] 38939.270
8 Vent O2 content from the reactor, VOR (%) −0.6565 [3, 6] 4.075
9 Vent O2 content from the first crystallizer, VOC (%) 0.3075 [3, 6] 4.867
10 Reactor condenser to water withdraw, WWC (kg h−1 ) −0.1392 [500, 1000] 673.23
Output
11 4-CBA concentration in the crude TA, c4-CBA (ppm) [2000, 3500] 2702
 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231
Table 2
The plant factors regressing results by the normal operating data
F1
F2
F3
F4
F5
F6
condition, thereby make it difficult to be described in the
mathematical model. For instance, the design of feed inlet
of air flow, the existence of foam in the vapor phase, the
effect of crystallized product to the main oxidation reac-
tion, the occurrence of subsidiary reaction and its product,
the effects of other process parameters from the second
crystallizer to the dryer sampling outlet, etc. To correct
the deviation between the laboratory condition and indus-
trial condition, six plant factors are set in the mathematical
model. They correct the oxidation reactor reaction rate
constants, kr , the residence time, τr , the feed concentration
of PX, and the first crystallizer reaction rate constants, kc ,
the residence time, τ c and the final discharge concentration
of 4-CBA, respectively. The plant factors are regressed by
modified Levenberg–Marquardt algorithm with six sets of
normal operating data. The results of plant factor regression
are given in Table 2. The model with regressed plant factors
was proved to be satisfactory accuracy for industrial online
prediction (Mu, Su, Liu, Gu, & Chu, 2003c).
4. Formulation of the optimization problem
In order to raise the yield of PTA oxidation unit, the feed
flow rate should be increased. But for the reactor liquid level
is almost fixed, the increasing of the feed rate leads to a
decreasing of the residence time, which, in turn, causes the
reaction insufficiency and the exorbitant of the 4-CBA con-
centration. Thus, it is necessary to regulate the new set points
of corresponding to process variables to maintain the ideal
range of 4-CBA content while the feed flow rate increased
as for as possible. Similarly, lowering the concentration of
4-CBA to increase the quality of product without adjust-
ing any process variables corresponded results in low yield
and low profit. Therefore, the suitable trade-off solutions for
both two optimal objectives should be considered.
Based on the analysis in above section, two process vari-
ables, the reactor liquid level and the flow rate of reactor
condenser to water withdraw are removed from decision
variable set. Furthermore, because the ratio of PX to the
solvent (HAc) is fixed, the flow of PX to feed mixed tank,
FPX is approximately proportion to the feed to reactor,
FFeed . The feed to reactor is regarded as an optimization
objective at the same time it is an input variable in the
model of predicts 4-CBA content in crude TA.
Accordingly, the rest six process variables are selected
as the decision variables for optimization in this study.
2223
They are catalyst ([Co2+ ] is the principal component) con-
centration ([Co]), total water withdrawal (WWD), vent O2
1.5911 concentration from the reactor (VOR ) and from the first
0.8701 crystallizer (VOC ), reactor temperature (TR ) and the first
0.9838
0.1215
crystallizer temperature (TC ). All of these variables can be
1.2705 easily and independent changed in industrial PTA oxidation
0.3529 process operation, and therefore used to obtain the optimal
operating conditions.
Because 4-CBA is the main contamination in the crude
TA, lowering its concentration as possible as to guarantee
some other properties, like optical density and 4-CTr con-
centration of the crude TA to lie within certain specifications
and decrease the crude TA loss is the basic requirement in
the industrial operation Meanwhile, maximizing flow rate of
the feed leads to maximizing yield, which improves the oper-
ating profit. Thus, the two objectives, namely, minimization
of the concentration of 4-CBA in the crude TA and maxi-
mization of the feed flow rate of the reactor are formulated
mathematically as following for study
minimize c4-CBA (FFeed , [Co], WWD, VOR ,
VOC , TR , TC )
maximize FFeed (3)
−1
subject to FFeed ≥ 130 000 kg h ,
c4-CBA ≤ 3500 ppm
The decision variables that lead to an increase of the pro-
ductivity of the process might produce a simultaneous
undesirable increase of the concentration of 4-CBA in
crude TA. Similarly, decision variables that cause a mini-
mization of the concentration of 4-CBA in crude TA might
cause lower yield. If we are to study only a single ob-
jective function, e.g., the profit, one would have to assign
appropriate weight factors to several important objectives
while incorporating them into a single economic objec-
tive function. This would be quite difficult to do if we
wish to assign a cost to the decrement of concentration
of 4-CBA. Moreover, the costs or coefficients usually are
not constant and variant with market and other unmeasured
factors.
Obviously, the employing of multi-objective functions, as
in the present study, is a superior and more detailed op-
tion than just minimizing the cost or maximizing the profit.
The algorithm provides a set of equally good solutions to
a plant engineer from which he can select the preferred
solution, using his specified intuition (Kasat et al., 2002).
Thus, the two objective functions are conflicting in nature
and would, most likely, lead to a Pareto set of optimal
solutions.
The above formulation of multi-objective optimization
problem has taken all possible decision variables into ac-
count. It is under the assumption from the academic views
that all six decision variables had the same priority and can
be adjusted in the process simultaneously. From the indus-
trial practice view, however, it is unpractical and unneces-
2224 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231
sary to manipulate all decision variables at one time when
a little offset emergence of an optimal operating position.
In most cases of industrial operating, only one or a few
process variables are operated to maintain the plant stable
and high efficient. Generally, there exists an operating rule
warehouse for different kinds of operating conditions. For
variant operational cases, the choice of operating variables
or their combinations is diverse. The reasons to build the
candidate decision variables set sequence for different op-
erational conditions are manifold, such as considering op-
erating stability and security, operating cost, operating ef-
ficiency, available region of operating variable, etc. In the
PTA oxidation process optimization, a four combination se-
quences of decision variables is proposed by considering
the specific industrial practical plant. The four combination
sequences are given as follows:
1. [Co].
2. [Co] and WWD.
3. [Co], WWD, VOR and VOC .
4. [Co], WWF, VOR , VOC , TR and TC .
The practical operation on the plant follows the four level
of decision variable combination sequence above. That is,
adjusting [Co] is the first choose in most cases, and then
adjusting WWD, VOR and VOC , TR and TC in sequence if
necessary. WWD is selected as the supplementary operating
variable when the adjustment of [Co] cannot derive satisfac-
tory outcome. Similarly, if the change of [Co] and WWD
is not profitable in their available operating bounds, VOR
and VOC will be introduced as the new resort. Finally, if all
of the above four decision variables cannot bring satisfac-
tory operating profit, TR and TC will be appended to the
decision variables set to realize the optimal operation. The
choice of the four combination sequence is according to the
operating stability and security, operating cost, operating ef-
ficiency, operating available region, etc., the detailed dis-
cussion of which will be given in the follow sections. The
bounds and reference values of the decision variables are
given in Table 1.
Moreover, with the addition of every new decision vari-
able, the characteristic and the Pareto front of the optimiza-
tion problem will be changed. Therefore, using different
number of decision variables in different optimization for-
mulations will help to develop the further insight into the
relationship between the new added decision variable and
the quality variable.
Different with general dynamic optimization or real time
optimization (RTO) problem (Nath & Alzein, 2000), the
proposed optimization formulation is a steady optimization
problem, which implies that the obtained optimal solution is
regards as the optimal set point for process controller rather
than the optimal path from current to the optimal operating
condition. So in this paper, more attention is paid on the
effects of additional decision variables on the process rather
than on the inter-relation between the decision variables and
how the optimal solution is implemented.
According the four combinations of decision variable, the
four operating cases associated for multi-objective optimiza-
tion problem are presented. In all cases, the other variables
that being not included are assumed to be fixed at their ref-
erence values in Table 1. The first cases are given by the
following.
4.1. Operating case I
minimize c4-CBA (FFeed , [Co])
(4)
maximize FFeed
The second objective function FFeed is also one of the deci-
sion variables in the first objective function c4-CBA . So in this
case there is only one decision variable, [Co]. The reason
we choose [Co] as the first choice is that the concentration
of catalyst is the most commonly tunable decision/operating
variable in the industrial PTA oxidation process. It is inde-
pendent from other variables, which means the adjustment
of [Co] causes little effect to other process variables, such
as the reactor temperature, the total water withdrawal, etc.
Its available operating bound is from 300 to 380 ppm, i.e.,
about ±13%. Considering [Co] has high sensitivity value,
which make the regulation of [Co] can obtain the effective
and quick responsive. Furthermore, it is easy to change the
set point by changing the opening of the catalyst feed flow
valve in the practical operation.
4.2. Operating case II
minimize c4-CBA (FFeed , [Co], WWD)
(5)
maximize FFeed
The adjustment of total water withdrawal flow rate of the
reactor is both to control water content in the reactor and
regulate the reactor temperature. Too large a value of WWD
decreases the concentration of water in the oxidation reac-
tor, which causes an increase the temperature of the reactor
(Wang, 2001), which, in turn, leads to a promotion of the
oxidation progress and a decrease of the concentration of
4-CBA, vice versa. Moreover, the pressure and the temper-
ature of the reactor are in cascade control, i.e. changing the
temperature of the reactor will change the pressure of the
reactor, with that affects the flow rate of the vent gas. Thus,
adjusting WWD will affect more process variables than that
of [Co]. These effects may counteract the operation profit,
or may cause the plant running in instability condition. So,
operating WWD as the decision variable is only adopted
as the second means when the adjustment of [Co] cannot
achieve the required operating target.
4.3. Operating case III
minimize c4-CBA (FFeed , [Co], WWD, VOR , VOC )
(6)
maximize FFeed
 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231
The values of vent O2 concentration from the reactor and
from the first crystallizer are controlled by air feed flow
from air compressor, which involves the main operating cost.
Moreover, partial similar to the effect of WWD, changing
VOR and VOC (adjusting the air flow rate) will affect the
temperature and the liquid level of both the oxidation reac-
tor and the first crystallizer. Too high a value of VOR and
VOC (oxygen concentration in the off-gas) will deteriorate
processing safety and increase operating cost, and too low a
value of VOR (low air flow rate) result in the first stage oxida-
tion reaction insufficient and high concentration of 4-CBA.
The second stage oxidation reaction in the first crystallizer,
however, is different to the case of the oxidation reactor in
that 4-CBA content of the outlet of oxidation reactor is a
disturb variable to the first crystallizer. Furthermore, the ox-
idation reaction occurred at the first crystallizer only occu-
pies 2–3% ratio of the whole oxidation reaction. The ratio
of air flow rate to the first crystallizer is 2% of the whole re-
quirement of air flow rate of the oxidation reaction, thereby
the effect of VOC on the concentration of 4-CBA is much
less than that of VOR .
In the first crystallizer, the O2 content of the released
off-gas is taken as an observer to the change of 4-CBA
content from the oxidation reactor when its air flow rate
is constant. That is, the decreasing of VOC usually implies
the increasing of the concentration of 4-CBA after the first
oxidation stage, which will cause high 4-CBA content in the
final product. But it is not definitely the same effect on the
product after the second oxidation stage.
4.4. Operating case IV (Eq. (3))
The reactor temperature is controlled by adjusting the
pressure of the tank. Generally, temperature is the most sen-
sitive factor to the chemical reaction. Changing the reactor
temperature directly will involve almost all factors of the
reaction and the reactor sharply, which causes the process
instability, even being accident. Compared with operating
cost and efficiency, the operating stability and security is
more important to be considered in the industrial operation.
Moreover, the operating regions of TR and TC are the least
among all decision variables. So, adjusting the temperatures
of both the reactor and the first crystallizer is only adopted
as the final resort when all other four decision variables are
inefficient, even its effect is quite prominent compared with
other variables.
Because NAGA only deals minimization objective (Mu
et al., 2003b), the maximization of FFeed can be replaced by
the minimization of a function f 2, where f 2 = 1/(FFeed +
1), without the transformation changing the location of the
optima. In order to normalize the objective functions, the
function f 1 is transform to f 1 = c4-CBA /Kc and the function
f 2 may be simplified as f 2 = Kf /FFeed if FFeed = 0,
where Kc and Kf are the reference operating value of the
concentration of 4-CBA and the feed flow, respectively, in
Table 1.
2225
Table 3
Algorithm parameters used in this study
Volume of the archive 500
Maximum generation 2000
Probability of crossover 0.8
Probability of mutation 0.02
Population size 50
Neighborhood size 0.0005
Range of mutation 12
5. Results and discussion
The solution of the multi-objective optimization prob-
lem described in the above section is obtained using the
neighborhood and archived genetic algorithm (NAGA: see
Appendix B for a summary). Table 3 gives the parameters
of NAGA applied in this study.
The computer code was written in Matlab 5.3 to obtain
the results of the multi-objective optimization problems.
The code was tested by several typical and challeng-
ing multi-objective optimization problems (Mu et al.,
2003b). The computational time required for solving the
multi-objective optimization problem is about 100 min on a
Pentium 4 (1.7 GHz) personal computer.
The number of decision variables of multi-objective opti-
mization problem is scalable in PTA oxidation process. The
diverse operation alternatives are fit for different operating
conditions and targets. In addition, the scalability of different
number of process operation variable is beneficial to obtain
the sensitivity analysis of each variable to 4-CBA content.
This conflict between the effects of the decision variables
on the two objective functions, results in the optimum be-
ing a Pareto optimal set rather than a unique solution. A
Pareto set (for the present case of two objective functions)
has the property that when we move from any one point on
the set to another, one objective function improves but the
other worsens. Hence, neither solution dominates an over
the other, and both are equally good. One has to use the ad-
ditional information that is often intuitive (based on experi-
ence) and non-quantifiable in nature, to choose an operating
point (preferred solution) from among the entire Pareto set,
for operation (Rajesh et al., 2001). In other words, it is im-
possible to identify a unique set of operating conditions that
will maximize the feed flow rate and minimize the concen-
tration of 4-CBA simultaneously.
The four level operating cases are used to analyze the ef-
fects of each variable on the objective functions detailed.
Figs. 3–9 give the Pareto optimal solutions and associated
variables for the four cases, respectively. The typical Pareto
solutions are selected to show in the result diagrams for the
sake of clarity. From the observations in Figs. 3–9 we infer
that the multi-objective optimization problem with different
number of decision variables offers the greatest amount of
insights in understanding the effects of each operating vari-
able on the objectives.
2226 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231
Fig. 3. Pareto optimal set of solutions obtained for the simultaneous
optimization of f1 vs. f2 and the original objectives FFeed vs. c4-CBA and
its corresponding decision variable of case I.
Figs. 3, 4, 6 and 8 show the typical Pareto set of optimal
solutions obtained by a single run of NAGA for the case I,
II, III and IV formulated above, respectively. Figs. 3a, 4a,
6a and 8a denote the Pareto set between the two minimum
objectives, f 1 versus f 2, while Figs. 3b, 4b, 6b and 8b stand
for the Pareto set of the two original objectives. The lines
formed by dot in Figs. 3b, 4b, 6b and 8b indicate the Pareto
Fig. 4. Pareto optimal set of solutions obtained for the simultaneous
optimization of f1 vs. f2 and the original objectives FFeed vs. c4-CBA of
case II.
Fig. 5. The decision variables correspond to each of the Pareto optimal
solutions shown in Fig. 4.
optimal fronts that denote the minimum concentration of
4-CBA and the corresponding maximum feed flow rate with
the given operating variable bounds. It is confirmed that the
increasing of the feed flow rate always leads to the raising of
4-CBA content correspondingly. Each point in Figs. 3b, 4b,
6b and 8b is a Pareto optimal solution, which is associated
with a set of decision variables shown in Figs. 3c, 5, 7 and
9, respectively.
In the case I, only [Co] is considered as a decision
variable for optimization problem. Its Pareto optimal so-
lution is reached when [Co] is located at its upper bound
(Fig. 3c). It matches the practical condition that increas-
ing the concentration of catalyst promotes the oxidation
Fig. 6. The Pareto optimal solutions for the two objective functions and
two original objectives of case III.
 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231
Fig. 7. The decision variables correspond to each of the Pareto optimal solutions shown in Fig. 6.
reaction and decreases the concentration of 4-CBA in the
normal condition, thereby giving rise to increase the pro-
cess yield. Considering the case II, both [Co] and WWD
are selected as decision variables, as shown in Fig. 5a and
b. The two decision variables are both approach to their
upper bounds. Furthermore, [Co] is more close to its up-
per bound than that of WWD, which can be explained
that the effect of [Co] on the reaction is greater than that
of WWD.
Figs. 6 and 7 show the Pareto optimal solutions and the
associated decision variables for case III, respectively. It is
Fig. 8. The Pareto optimal solutions for the two objective functions and
two original objectives of case IV.
2227
observed from Fig. 7 that the concentration of catalyst still
lies near its upper bound. The total water withdrawal rate
and the vent O2 concentration from the reactor disperse at
their upper half. Moreover, VOR is farther from the upper
bound than that of WWD, which can also be explained with
above effect. However, the vent O2 concentration from the
first crystallizer converges to its lower half. This is basically
consistent with the sensitivity analysis given in Table 1, i.e.,
the effect of VOC on reaction is opposed to that of [Co],
WWD and VOR .
Compared with the solutions obtained in the former three
cases, case IV has all six available decision variables, which
had been discussed before (Mu et al., 2003a). Fig. 8 gives
its Pareto optimal solutions and the subplots in Fig. 9 are
the corresponding decision variables. Similarly to Fig. 7,
the decision variables, [Co], [WWD] and VOR converge to
their upper bounds whilst VOC converge to its lower bound.
Furthermore, the distributions of WWD and VOR in their
upper bounds are more dispersive than those of TR and TC ,
which is truly identical to the results in Table 1. It was
observed that the effect of WWD, VOR and VOC on the
objective functions were very mild compared with other
three variables, as evidenced by the scatter in their optimal
solutions.
The four scalable cases are formed with different number
of decision variables, which makes the Pareto solutions in
Figs. 3, 4, 6 and 8 are different in nature. For case II pos-
sesses two decision variables while case I has only one, the
Pareto optimal front for case II is more flexible and elas-
tic than that for case I, which causes the profit produced by
case II is greater than that by case I. So do the relationships
among those for cases III and II and for cases IV and III.
In order to obtain the relationships visualized and quantifi-
2228 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231

Fig. 9. The decision variables correspond to each of the Pareto optimal solutions shown in Fig. 8.

cationally, the comparison among the Pareto optimal fronts
of four cases is shown in Fig. 10.
In both two sub-figures of Fig. 10, the point N denotes
the industrial normal operating point, which is below the
obtained four Pareto optimal fronts in the below sub-figure.
The distances between point N and the Pareto optimal front
are combined with horizontal ordinate part and vertical or-
dinate part, which represent the benefit of the decrement of
the objective 4-CBA content and the benefit of the incre-
ment of the objective feed rate, respectively. The coefficients

Fig. 10. The comparison among the Pareto optimal fronts of four cases.
 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231
w1 and w2 denote the profit to per unit 4-CBA concentra-
tion decrement and per unit the feed rate increment. They
are changing with the operating cost and market quotation
rather than be constant values. The total economic profit for
the bi-objective optimization strategy is included with the
two parts
J = w1 × decrement of c4-CBA
+ w2 × increment of FFeed (7)
The points Op1 , Op2 , Op3 and Op4 in the Pareto front of case
IV are four possible Pareto optimal solutions for operation.
When the coefficients w1 and w2 are changed, for example,
due to the increase of the requirement of the product quality,
w1 is enlarged that make the economic profit to decrease
c4-CBA larger than before, while the requirement of increase
the yield is not impendent, which means w2 is decrease
compared with w1 , the optimal operating condition should
be moved to the direction from Op4 to Op1 . Otherwise, when
w1 decrease and w2 increase, in order to maximize the total
operating economic profit will desire the optimal operating
point moved to the direction from Op1 to Op4 .
It is interesting to find that the distances between each two
neighboring Pareto optimal fronts are almost in proportion to
the effects of each new additional variable(s) on the objective
functions. For instance, TR and TC affect the 4-CBA content
more significant than other variables, thereby giving rise to
the distance between cases IV and III is more larger than
both the distances between cases III and II and between
cases II and I. The distances between the two neighboring
Pareto optimal fronts denote the difference of the operating
profits of two cases. Therefore, operating all six variables in
case IV has the greatest profit while only adjusting [Co] in
case I has the least operating profit. The result is acceptable
for that operating all six variables will cause most cost and
highest risk for operating while employ only one variable
occupies least. It is consistent with the famous principle “No
free Lunch”.
6. Conclusion
The present study addresses the real-life challenge of
promoting added value in industrial purified terephthalic
acid (PTA) oxidation process. An improved and validated
semi-empirical model for PTA oxidation process is used to
solve the optimization problem involving two objective func-
tions: minimization of the concentration of 4-CBA in the
crude TA and maximization of the feed flow rate to the pro-
cess. To be better applied in practical industrial process, a
scalable problem containing four sequential operation levels
with different number of decision variables is proposed. By
performing a multi-objective optimization using the neigh-
borhood and archived genetic algorithm (NAGA) technique,
all operating cases are solved and the plant operators are
provided with, not one, but many sets of operating condi-
2229
tions that will yield such an end result. The effects of each
decision variables on the two objective functions are also
obtained by analyzing the results of the four cases, which
are truly consistent with the results of the sensitivity anal-
ysis done in advance. The significance of the study is that
it presents the plant operators with nomographs, which can
be used to quickly arrive at optimal operating parameters
for various operational targets. Operation under the condi-
tions predicted will reduce plant operation cost, improve the
quality of the product, uprate productivity and thereby in-
crease whole profit. The design of multi-objective optimiza-
tion problem for PTA oxidation process and its scalability to
multiple sequential operation stage are used to quite general
and can be applied to other industrial processes. Moreover,
in general optimal operating procedure, the given operating
variables sequence can provide operator the proper operat-
ing order.
Acknowledgements
This work is supported by The National Outstanding
Youth Science Foundation of China (60025308). The au-
thors are also grateful to the engineers of Yizheng Chem-
ical Fibre Co. Ltd. for their support for the work and the
anonymous reviewers for helpful and insightful comments.
Appendix A. Model equations used in this study
The reaction rates rj (j = 1, 2, . . . , 4) of four main reac-
tions are formulated as follows (Wang, 2001):
fj
rj = −kj
4 cj , j = 1, 2, . . . , 4 (A.1)
1 ki c i +ε
where k1 , k2 , k3 , k4 are the reaction rate constants of the
four reactions, which are regards as the functions of reaction
temperature and the concentration of the vent oxygen in the
reactor. The relations between ki0 and reaction temperature
follow Arrhenius law:
ki0 = ki,0 e−Ei /RT (A.2)
where the parameters are listed in Table A1.
The vent O2 content on the rate constants is only in effect
at the range 2–7%. The oxidation reactions of PX and TALD
Table A.1
The parameters for Eq. (A.2)
Rate constants (min−1 ) ki,0 (kg mol−1 min−1 ) Ei (kJ mol−1 )
k10 2.408E+17∗ 37.3
k20 1.158E+8 19.8
k30 2.086E+16 34.5
k40 3.377E+15 32.6
∗
The data are only suitable to the reaction temperature is in the range
[181, 194], ◦ C.
2230 S. Mu et al. / Computers and Chemical Engineering 28 (2004) 2219–2231

are influenced by the vent O2 content whilst those of PT 2. Identify the Pareto optimal solutions from the population
and 4-CBA are independent in essence. The formulations by neighborhood identify method. Calculate and compare
are follow: the objective functions of the initial population and their
 c 0.44 neighborhoods’.
O2
k1 = k10 (A.3a) 3. Perform neighborhood crowding and add the Pareto op-
7.65
 c 0.44 timal solution to the history archive. Assign fitness for
O2
k2 = 1.2 k20 (A.3b) the initial population.
7.65 4. If generation is greater than or equal to Kmax and the
f1 , f2 , f3, f4 are the functions of the concentration of cata- number of solution in the archive is greater than or equal
lyst: to VA, stop.
1 5. Apply selection, crossover and mutation operation to gen-
f1 = 0.4987 − (A.4a) erate new offspring. Preserve the best solution in the cur-
1 + ([Co]/165.1)3.07
rent population.
1 6. Identify the Pareto optimal solution from the offspring
f 2 = 0.5443 − (A.4b)
1 + ([Co]/170)1.3 and assign the fitness of GA for the offspring.
7. Perform neighborhood crowding to judge whether the
f 3 = 0.1178 + 8.26 × 10−4 [Co] (A.4c) identified Pareto optimal solution is a fresh one or not.
f4 = 0.0641 + 5.72 × 10 −4
[Co] (A.4d) Add the fresh Pareto optimal solution to the archive.
8. Return to step 4.
The above expression and data are only suitable to the ratios
This approach is implement by Matlab 5.3 code. The mod-
among [Co2+ ], [Mn2+ ] and [Br− ] are fixed to 1.
ified real-coded genetic algorithm is used, and the selection
The residence time of the tank τ is the function of the
operator, crossover operator and mutation operator are fol-
liquid level and feed rate. Due to the liquid level of oxidation
lowed with weighted roulette wheel procedure, arithmeti-
reactor is almost constant, the residence time of the oxidation
cal crossover and neighborhood mutation, respectively (Mu
reactor, τr is only affected by the feed rate, FFeed , as follows:
et al., 2002).
1.0175 × 107
τr = (A.5)
FFeed
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