Chin. J. Chem. Eng.

, 15(1) 7580 (2007)

Multiobjective Optimization of the Industrial Naphtha Catalytic Reforming Process*

HOU Weifeng(), SU Hongye()**, MU Shengjing() and CHU Jian()

National Laboratory of Industrial Control Technology, Institute of Advanced Process Control, Zhejiang University,
Hangzhou 310027, China
Abstract In this article, a multiobjective optimization strategy for an industrial naphtha continuous catalytic reforming process that aims to obtain aromatic products is proposed. The process model is based on a 20-lumped kinetics reaction network and has been proved to be quite effective in terms of industrial application. The primary objectives include maximization of yield of the aromatics and minimization of the yield of heavy aromatics. Four reactor inlet temperatures, reaction pressure, and hydrogen-to-oil molar ratio are selected as the decision variables. A genetic algorithm,
which is proposed by the authors and named as the neighborhood and archived genetic algorithm (NAGA), is applied
to solve this multiobjective optimization problem. The relations between each decision variable and the two objectives
are also proposed and used for choosing a suitable solution from the obtained Pareto set.
Keywords multiobjective optimization, catalytic reforming, lumped kinetics model, neighborhood and archived
genetic algorithm (NAGA)

INTRODUCTION
Petroleum refining and petrochemical industries
aim at maximizing one prime product while simultaneously minimizing another accessory product to improve the quality of the prime product. Unfortunately,
the two requirements are often conflicting or inconsistent. It is necessary to determine the trade-off compromises to balance the two objectives[1,2].
As the core of aromatics complex unit, catalytic
reforming is a very important process for transforming
naphtha into aromatics feedstock[3]. In this process,
the yield of aromatics, including benzene, toluene,
para-xylene, meta-xylene, ortho-xylene, ethyl-benzene,
and heavy aromatics (i.e. 9 and more carbon aromatics), are regarded as the main index that determines
the quality. However, heavier aromatics are not required and will increase the load on the downstream
units of the aromatics complex process, especially on
the disproportionation and xylene fractionation units.
Thus, the design and operation of the catalytic reforming process require multiobjective optimization to
balance the various objective functions.
Multiobjective optimization, involving more than
one objective function, was typically modeled and
solved by transforming it into a single objective problem using different methods, such as the restriction
method, the ideal point method, and the linear
weighted sum method. These methods largely depend
on the values assigned to the weighted factors or the
penalties used, which are done quite arbitrarily. Another disadvantage of the above methods is that these
algorithms obtain only one optimal solution at a time
and may miss some useful information[4].
Recently, multiobjective evolutionary algori-thms
are used more popularly in industrial process modeling, optimal design, and operation[4]. These may produce a solution set, which is named as a Pareto set, in
a single run of the algorithms. The Pareto solutions are

extremely useful in industrial operations as these narrow down the choices and help to guide a decision-maker in selecting a desired operating point
(called the preferred solution) among the (restricted)
set of Pareto optimal points, rather than from considerably large number of possibilities[5]. Coello[6] presented comprehensive reviews on the development of
the evolutionary (especially genetic) multiobjective
optimization. When compared with the previous
methods, such as the nondominated sorting genetic
algorithm (NSGA)[7], the niched Pareto genetic algorithm (NPGA)[8], the Pareto archive evolutionary
strategy (PAES)[9], and the strength Pareto evolutionary algorithm (SPEA)[10], the method employed in
this study, the neighborhood and archived genetic algorithm (NAGA)[11,12], offers several advantages: (1)
low computation complexity; (2) insensitivity of the
efficiency to the method parameters; and (3) uniform
distribution on the Pareto front.
In this article, the multiobjective optimization
strategy for an industrial naphtha continuous catalytic
reforming process is built to improve the operation
level. A 20-lumped kinetic model is employed for the
industrial catalytic reforming reaction and the corresponding process model is validated by successful
industrial applications[13]. In the catalytic reforming
unit, the objectives are to maximize the aromatics
yield and minimize the yield of heavy aromatics. The
multiple Pareto optimal solutions of the problem are
obtained by applying the multiobjective genetic algorithm, NAGA. It presents an operating parameter set
for operators for various operational targets.
2 DESCRIPTION OF THE PROCESS AND
MODELING
The simplified continuous catalytic reforming
process flow diagram is shown in Fig.1. The naphtha,
used as the catalytic reformer feedstock usually

Received 2005-11-19, accepted 2006-07-03.

* Supported by the National Natural Science Foundation of China (No.60421002).
** To whom correspondence should be addressed. E-mail: [email protected]

76

Chin. J. Ch. E. (Vol. 15, No.1)

Figure 1 Flowsheet of a continuous catalytic reforming process

containing more than 300 chemical compounds of

paraffins, naphthenes, and aromatics in the carbon
number range of C4 to C12, is combined with a recycle
gas stream containing 60% to 90% (by mol) hydrogen.
The total reactor charge is heated and passed through
the catalytic reformers, which are designed with four
adiabatically operated reactors and four heaters between the reactors to maintain the reaction temperatures at design levels. The effluent from the last reactor is cooled, which then enters the product separator.
The flashed vapor circulates to join the naphtha feedstock as recycle gas. Excess hydrogen from the separator is sent to other hydrogen-consuming units. The
separated liquid that chiefly comprised the desired
aromatics together with light gases and heavy paraffins is sent to the separation system to obtain aromatics products.
The aromatics products are obtained by the conversion of n-paraffins and naphthenes in naphtha to
iosparaffins and aromatics over bifunctional catalysts
such as Pt-Sn/Al2O3 in the four reactors. The dominant reaction types of catalytic reforming are dehydrogenation of naphthenes, isomerization of paraffins
and naphthenes, dehydrocyclization of paraffins, hydrocracking of paraffins, and hydro-dealkylation of
aromatics. Dehydrogenation is the fastest reaction
followed by isomerization, which is moderately fast,
whereas dehydrocyclization and hydrocracking are the
slowest.
As mentioned above, the naphtha feedstock is
very complex and each of these undergoes various
reactions. To reduce the complexity of the model to a
manageable level, the large number of naphtha components are assigned to a smaller set of kinetics lumps,
each of which is composed of chemical species that
are grouped together according to some criteria[14].
Accordingly, various lumped kinetics models with
varying levels of sophistication that represent catalytic
reforming reactions have been reported in the literature[1520].
In the previous study[13], a simple lumped kinetics model for catalytic reforming with 20 lumps
involving 31 reactions was presented. The correFebruary, 2007

sponding reaction network is shown in Fig.2. In this

model, the total reactor charge is characterized as paraffins (P), naphthenes (N), and aromatics (A) lumps
with the carbon number ranging from 6 to
9+(9+indicates a carbon number of 9 and above) and
light paraffins (P1P5), in which the 8-carbon aromatics are subdivided into their four isomeric compounds, i.e. PX (para-xylene), MX (meta-xylene), OX
(ortho-xylene), and EB (ethyl-benzene). The rationale
of selecting these lumps was based on both thermodynamic and kinetics considerations for the aromatization selectivity of paraffins and naphthenes. It is not
necessary to split the paraffin or naphthene lumps into
their individual isomers (e.g., isohexane and n-hexane)
for achieving similar aromatization selectivity for the
two lumps (except for methyl cyclopentane and hexane) and for faster isomerization reaction rates relative
to dehydrocyclization and hydrocracking[15,16]. In
this reaction network, except for isomerization, all the
dominant catalytic reforming reactions are included.

Figure 2

Reaction scheme for naphtha reforming

All the 31 rate equations are nonlinear

pseudo-monomolecular in nature, with the rate coefficients obeying the Arrhenius law, as shown in Eq.(1),

k j = k0 j exp ( E j / RT ) Ph j
0 1, j=131

(1)

Multiobjective Optimization of the Industrial Naphtha Catalytic Reforming Process

Under the normal reformer operating conditions,

radial and axial dispersion effects were found to be
negligible[13]. For the radial flow reactor, the global
material and the heat balance equations are given in
Eqs.(2) and (3), respectively,
dY
2R H
=
Kr Y
(2)
dR (LHSV Vc )
31 ( r j H j )
dT
2R H
=

dR (LHSV Vc ) j =1 ( C p Y )

(3)

where Y is the vector of the molar flow rates including

20 lumps and H2. Eq.(2) is solved using a mixed numerical algorithm of fourth-order Runge-Kutta and
Gear method, and Eq.(3) is solved using the modified
Euler method. The thermochemical properties of each
lump are computed by taking an arithmetic average of
the properties of the corresponding pure chemical
components constituting the lump.
The product separator was modeled to perform in
isothermal flash operation. A Peng-Robinson equation
was used to compute the vapor/liquid equilibrium
constants. The so-called sequential modular approach
is implemented for the computation of this flowsheet.
Except for the separation system, the reactors, the
heaters, the product separator, and the heat exchangers
are included in this computation.
If the activation energies (E), the pressure exponents (), and the frequency factors (k0) for all 31 reactions are estimated, there will be 93 kinetics parameters in total, and it is very difficult to determine
these parameters synchronously. Generally, E and
values reported by different literatures for the specific
catalyst are similar. To reduce the difficulty experienced in estimating parameters, the parameters E and
in this model are taken from Ref.[18] and only
thirty-one k0, which considers the difference between
the estimation of parameters E and , and the unmodeled kinetics, are estimated.
The procedure of parameter estimation is carried
out by minimization of the sum of the squares of the
deviations between the plant and the calculated values
of the key variables such as the compositions of effluent from the last reactor and the outlet temperatures
of the four reactors. The operating and assaying data
samples of several months for the industrial process,
which are first reconciled by material balance, are used
to estimate k0 by the BFGS optimization algorithm.
3 FORMULATION OF THE OPTIMIZATION
PROBLEM
The variables that affect the catalytic reforming
process are the volume flow of naphtha charge to the
volume of the catalyst (liquid hourly space velocity,
LHSV), the latent aromatics content of naphtha charge
(LA), the four reactor inlet temperatures (T1, T2, T3,
T4), the reaction pressure (pr), the mole flow of hydrogen in the recycle gas to the mole flow of naphtha
charge (hydrogen-to-oil molar ratio, nH 2 / nHC ), the

product separator temperature (Ts), etc.. Among the 9

77

process variables selected using mechanism analysis,

the sensitivity analysis of each variable is performed
using the process model presented in Section 2 to obtain its quantitative corrections with the aromatics
yield and the yield of heavy aromatics. It is shown that
the appropriate set point value of one variable for
maximizing the aromatics yield may not be suitable
for minimizing the yield of heavy aromatics. Therefore, the suitable trade-off solutions for the two optimal objectives should be considered.
For the continuous catalytic reforming process in
this study, the unit is in full load operation and the
value of LHSV cannot be further increased. Similarly,
the quality of naphtha feedstock (e.g. LA) cannot be
changed artificially for most domestic petroleum-refining enterprises. The product separator temperature Ts is not independent of other variables.
Moreover, for further lowering of the temperature,
coolers need to be included in the system, which in
turn increase the operation costs. Hence, the remaining process variables are selected as the decision
variables for optimization in this study. These are the
four reactor inlet temperatures (T1, T2, T3, T4), the reaction pressure (pr), and the hydrogen-to-oil molar ratio
( nH 2 / nHC ).
Thus, the two independent objectives, namely,
the maximization of the aromatics yield (AY) and the
minimization of the yield of heavy aromatics (HAY)
are formulated mathematically as follows:
maximize AY(T1, T2, T3, T4, pr, nH2 / nHC )
minimize

HAY(T1, T2, T3, T4, pr, nH2 / nHC )

subject to
520T1, T2, T3, T4530
0.8pr0.9
3.0 nH2 / nHC 4.0
65AY68
18HAY23
(4)
The bounds of the decision variables and the objectives have been chosen based on industrial practice.
Because NAGA deals with only the minimization
objective[11], the maximization of AY can be replaced
by the minimization of a function f1, where f1=1/AY,
without the replacement changing the location of the
optima. To normalize the objective functions, the function f1 is transformed to f1=Kf/AY, and the function f2
may be simplified as f2=HAY/Kc, where Kf=67 and
Kc=20 are the reference operating values of the aromatics yield and the yield of heavy aromatics, respectively.
4

RESULTS AND DISCUSSION

The solution for the multiobjective optimization
problem described in Section 3 is obtained using
NAGA. Table 1 provides the parameters of NAGA
applied in this study.
Figure 3 shows the typical optimal solutions obtained by a single run of NAGA for the above formulated problem. The top of Fig.3 denotes the relationship
Chin. J. Ch. E. 15(1) 75 (2007)

Chin. J. Ch. E. (Vol. 15, No.1)

78
Table 1

Algorithm parameters used in this study

Parameters
volume of the archive
maximum generation
probability of crossover
probability of mutation
population size
neighborhood size

Values
100
500
0.8
0.01
50
0.05

between the two minimum objectives, f1 vs. f2,

whereas the bottom depicts the solutions of the two
original objectives. The conflict between the effects of
the decision variables on the two objective functions,
results in the optimum being a Pareto-optimal set
rather than a unique solution. The Pareto set has the
property that when one point on the set is moved to
another, one objective function is improved (e.g. the
aromatics yield increases), but the other function becomes worse (e.g. the yield of heavy aromatics increases accordingly). Hence, within the Pareto set,
neither the solution dominates an over the other, and
both indicate the optimal solation for the two objective functions and the minimization of the yield of
heavy aromatics with the given operating bound. The
operators have to use the additional information, such
as the market quotation, the operating cost, and the
corresponding decision variable values to select an
operating point (preferred solution) from the entire
Pareto set for operation.
Each point in Fig.3 represents a Pareto solution,
which is associated with a set of the six decision variables. Fig.4 is a plot of the decision variables corresponding to each of the points on the Pareto set. Ob-

Figure 3
February, 2007

viously, the relations between each decision variable

and the two objectives can also be observed. Among
the six variables, T4 is unique in that all its points are
close to its upper bound, which indicates that increasing T4 results in both an increase in the aromatics
yield and a decrease in the yield of heavy aromatics.
However, increasing the decision variables T1, T2, pr
and nH2 / nHC results in a decrease in the yield of
heavy aromatics, but a decrease in the aromatics yield.
In other words, the four variables have opposing effects on the two minimum objectives f1 and f2. Besides
the effects of the above variables, it is observed that the
effects of T3 on the two objective functions are mild.
All the above phenomena are confirmed by the
process operators. These can also be rationally explained by the reaction mechanism. In the first and
second reactors, the inlet temperature of 520 is
adequate for the complete conversion of naphthenes to
aromatics. A higher temperature is suitable for hydrocracking of paraffins, which results in the decrease of
aromatics. In the fourth reactors, dehydrocyclization
and hydrocracking of paraffins are the major reactions
and are both aided by higher temperatures. In this
study, the competition is more favorable for dehydrogenation and results in an obvious increase in aromatics. In any reactor, exothermic hydrodealkylation of
aromatics increases with an increase of temperature,
which indicates a decrease of heavy aromatics. On the
other hand, lower pressure favors dehydrocyclization
and dehydrogenation, but not hydrocracking and
hydrodealkylation, which result in increase of both
gross aromatics and heavy aromatics. Less nH 2 / nHC
indicates low partial pressure of hydrogen. Hence,
nH2 / nHC and pr have similar effects on the two objectives.

Pareto-optimal set of solutions obtained from the simultaneous optimization in f1 vs. f2 and in the original
objectives of the aromatics yield and the yield of heavy aromatics

Multiobjective Optimization of the Industrial Naphtha Catalytic Reforming Process

79

Figure 4 The decision variables corresponding to each of the Pareto-optimal solutions shown in Fig.3

The above relations between each decision variable and the two objectives are useful for selecting a
suitable solution from the entire Pareto set. For example, the decision variable values and the corresponding
objectives of several typical solutions, points A, B, C,
D, and E in Fig.3, are listed in detail in Table 2. The
point N denotes the industrial normal operating point,
which is above the Pareto solution front that is obtained. If the aim is to increase the aromatics yield, it
may be feasible to increase T4 and (or) decrease pr and
nH2 / nHC , as listed in point A or C. While aiming to
decrease the yield of heavy aromatics, it may be feasible to increase T1, T2, T4, and (or) increase pr and
nH2 / nHC , as listed in point B or E. In actual industrial
operations, pr and nH2 / nHC are always maintained at
higher values to protect the catalyst from rapid coking.
As a solution to the above-mentioned problem, when
other decision variables are approximately constant,
Table 2

only increasing T4 by about 5 can lead to beneficial

effects, an increase of 0.18% (by mass) in the aromatics yield and a decrease of 1.77% (by mass) in the
yield of heavy aromatics, as listed in point D. The law
that the increase of aromatics yield can only be obtained by slightly increasing T4 has been validated in
the same industrial continuous catalytic reforming unit,
as reported in the previous literature[21].
5

CONCLUSIONS
The real-life challenge of promoting added value
in the industrial naphtha continuous catalytic reforming process is described in this article. A 20-lumped
kinetics model for catalytic reforming is used to solve
the multiobjective optimization problem: maximization of the aromatics yield and simultaneous minimization of the yield of heavy aromatics. By performing
the optimization based on the neighborhood and

Comparison of the decision variables and objectives for normal operation and
five possible cases of optimal operations

Points

T1,

T2,

T3,

T4,

pr, MPa

Parameters
nH 2 / nHC , molmol1

AY, % (by mass)

HAY, % (by mass)

522.1

521.3

522.6

524.0

0.88

3.5

66.85

22.60

520.0

520.0

523.8

528.6

0.80

3.0

67.63

22.57

523.1

527.5

523.8

529.3

0.85

3.6

66.79

20.76

520.2

520.6

524.5

528.6

0.83

3.4

67.20

21.71

521.5

521.0

523.8

529.3

0.88

3.6

67.03

20.83

523.1

522.0

530.0

530.0

0.90

4.0

66.17

19.51

Chin. J. Ch. E. 15(1) 75 (2007)

Chin. J. Ch. E. (Vol. 15, No.1)

80

archived genetic algorithm (NAGA), a Pareto-optimal

set and several corresponding sets of decision variable
values are obtained. The relations between each decision variable and the two objectives are also proposed
and used for selecting the suitable solution from the
Pareto set that is obtained. This multioptimization
strategy will reduce the plant operation cost, improve
the quality of products, and thereby increase the total
profit. Moreover, the multioptimization method may
also be applied to other industrial processes.

7
8

NOMENCLATURE
AY
Cp
E
f1, f2

H
H
HAY
Kr
k
k0
LA
LHSV
nH 2 / nHC
ph
pr
R
r
T
Ts
T1, T2, T3, T4
Vc
Y

aromatics yield, % (by mass)

specific heat, kJkmol1K1
activation energy, kJmol1
objective functions (f1=Kf/AY, f2=HAY/Kc,
Kf=67, Kc=20)
height of the catalyst bed, m
heat of reaction, kJkmol 1
the yield of heavy aromatics, % (by mass)
matrix for the reaction ratecoefficients
reaction rate coefficient,
h 1
1
frequency factor, s MPa
latent aromatics content of naphtha charge, %
(by mass)
liquid hourly space velocity, h1

hydrogen-to-oil molar ratio, molmol 1

partial pressure of hydrogen, MPa
reaction pressure, MPa
radius of the catalystbed, m (or gas contant)
reaction rate, kmolh 1
reaction temperature, K
product separator temperature,
four reactor inlet temperatures, (14 indicates the number of reactors)
catalyst volume, m3
molar flow rate, kmolh1

9
10

11

12

13

14
15

catalyst deactivation factor

Superscripts

16

Subscripts

17

pressure exponent

reaction number (j=131)

REFERENCES
1

2
3

Gao, Y., Shi, L., Yao, P.J., Waste minimization through

process integration and multi-objective optimization,
Chin. J. Chem. Eng., 9(3), 267272(2001).
Mu, S.J., Su, H.Y., Gu, Y., Chu, J., Multi-objective optimization of industrial purified terephthalic acid oxidation
process, Chin. J. Chem. Eng., 11(5), 536541(2003).
Hou, W.F., Su, H.Y., Hu, Y.Y., Chu, J., Simulation of
industrial catalytic reforming process by development
users module on ASPEN PLUS platform, J. Chem. Ind.
Eng., 56(9), 17141720(2005).
Li, S.J., Wang, H., Qian, F., Multi-objective genetic algorithm and its applications in chemical engineering,
Comput. Appl. Chem., 20(6), 755760(2003). (in Chinese)
Yuen, C.C., Gupta, A., S.K., Ray, A.K., Multi-objective

February, 2007

18

19

20

21

optimization of membrane separation modules using genetic algorithm, J. Membr. Sci., 176, 177196(2000).
Coello, C.C.A., A short tutorial on evolutionary multiobjective optimization, In: Proceedings of the First International Conference on Evolutionary Multi-criterion
Optimization, Zitzler, E., Deb, K., Thiele, L., Coello,
C.C.A., Corne, D., Eds., Springer, Zurich, Switzerland,
6781(2001).
Srinivas, N., Deb, K., Multiobjective optimization using
nondominated sorting in genetic algorithms, Evol.
Comput., 2(3), 221248(1994).
Horn, J., Nafpliotis, N., Goldberg, D.E., A niched
Pareto genetic algorithm for multiobjective optimization, In: Proceedings of the First IEEE Conference on
Evolutionary Computation, IEEE World Congress on
Computational Intelligence, IEEE Press, Piscata- way,
New Jersey, 1, 8287(1994).
Knowles, J.D., Corne, D.W., Approximating the nondominated front using Pareto archived evolution strategy, Evol. Comput., 8(2), 149172(2000).
Zitzler, E., Thiele, L., Multiobjective evolutionary algorithms: A comparative case study and the strength Pareto
approach, IEEE Trans. Evol. Comput., 3(4), 257
271(1999).
Mu, S.J., Su, H.Y., Wang, Y.X., Chu, J., An efficient
evolutionary multi-objective optimization algorithm, In:
Proceedings of the IEEE Congress on Evolutionary
Computation, Canberra, 2, 914920(2003).
Mu, S.J., Su, H.Y., Jia, T., Gu, Y., Chu, J., Scalable
multi-objective optimization of industrial purified
terephthalic acid (PTA) oxidation process, Comput.
Chem. Eng., 28, 22192231(2004).
Hou, W.F., Su, H.Y., Hu, Y.Y., Chu, J., A lumped kinetics model and its on-line application to a commercial
catalytic naphtha reforming process, J. Chem. Ind. Eng.,
57(7), 16051611(2006). (in Chinese)
Smith, R.B., Kinetic analysis of naphtha reforming with
platinum catalyst, Chem. Eng. Progr., 55(6), 76
80(1959).
Ramage, M.P., Graziani, K.R., Krambeck, F.J., Development of Mobils kinetic reforming model, Chem. Eng.
Sci., 35, 4148(1980).
Taskar, U., Riggs, J.B., Modeling and optimization of a
semiregenerative catalytic naphtha reformer, AIChE J.,
43, 740753(1997).
Rahimpour, M.R., Esmaili, S., Bagheri, G.N.A., Kinetic
and deactivation model for industrial catalytic naphtha
reforming, Iranian J. Sci. Tech., Trans. B: Tech., 27,
279290(2003).
Weng, H.X., Jiang, H.B., Chen, J., Lumped model for
catalytic reforming () Experiment design and kinetic
parameter estimation, J. Chem. Ind. Eng., 45(5), 531
537(1994). (in Chinese)
Xie, X.A., Peng, S.H., Liu, T.J., Establishment and
commercial application of kinetics models for catalytic
reforming reactions (1) Establishment of physical model,
Petro. Ref. Eng., 25(6), 4951(1995). (in Chinese)
Zhou, Q.H., Hu, S.Y., Li, Y.R., Shen, J.Z., Wei, Z.W.,
Molecular modeling and optimization for catalytic reforming, Comput. Appl. Chem., 21(3), 447452(2004).
(in Chinese)
Hou, W.F., Su, H.Y., Hu, Y.Y., Chu, J., Modeling, simulation and optimization of a whole industrial catalytic
naphtha reforming process on Aspen Plus platform,
Chin. J. Chem. Eng., 14(5), 584591(2006).