i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1

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Dynamic optimization of a multi-stage spherical, radial flow

reactor for the naphtha reforming process in the presence of
catalyst deactivation using differential evolution (DE) method

Mohammad Reza Rahimpour*, Davood Iranshahi, Ali Mohammad Bahmanpour

Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, P.O Box 71345, Shiraz, Iran

article info abstract

Article history: In the present research, differential evolution (DE) method has been used to optimize the
Received 23 March 2010 operating conditions of a radial flow spherical reactor containing the naphtha reforming
Received in revised form reactions. In this reactor configuration, the space between the two concentric spheres is
26 April 2010 filled by catalyst. The dynamic behavior of the reactor has been taken into account in the
Accepted 28 April 2010 optimization process. The achieved mass and energy balance equations in the model are
Available online 2 June 2010 solved by orthogonal collocation method. The goal of this optimization is to maximize the
hydrogen and aromatic production which leads to the maximum consumption of the
Keywords: paraffins and naphthenes. In order to reach this end, the inlet temperature of the gas at
Naphtha reforming the entrance of each reactor, the total pressure of the process, as well as the catalyst
Dynamic optimization distribution in each reactor have been optimized using the differential evolution (DE)
Spherical reactor method. The results of the optimization of the spherical reactor have been compared with
Differential evolution the non-optimized spherical reactor. The comparison shows acceptable enhancement in
Catalyst deactivation the performance of the reactor.
ª 2010 Published by Elsevier Ltd on behalf of Professor T. Nejat Veziroglu.

1. Introduction considering the deactivation of the catalysts due to the coke

Due to the high demand of high-octane gasoline, catalytic
naphtha reforming process warrants and attracts increasing
attention during recent years. Commercial reforming plants
utilize a series of three or four fixed bed reactors to convert the
low-octane hydrocarbons to more valuable materials [1].
Hydrogen and other light gases such as propane and butane
are also produced during this process [2].
Several research efforts have been made to investigate the
naphtha reforming process and enhance the production of the
desired products. Smith [3] suggested a simple model which
presented four main reactions as the dominant reactions in
the naphtha reforming process. Ramage et al. [4] presented
a kinetic model, which described different reactive particular
raw materials and modified the process kinetics by
formation. Bommanna et al. [5] estimated the values of
activation energies according to the plant data. Fathikalajahi
and Rahimpour [6] obtained the optimum catalyst mass
distribution in an industrial naphtha reformer by utilizing the
Smith’s model. Fathi et al. [7] studied the effects of different
parameters on the performance of the industrial naphtha
reformers. Lee et al. [8] modeled a process in which catalysts
were regenerated. Acceptable agreements with plant data
were achieved. Taskar and Riggs [9] developed and optimized
a more detailed model of a semi regenerative catalytic
naphtha reformer involving 35 pseudo components. Kinetic
and deactivation model for the industrial catalytic naphtha
reformers were presented by Rahimpour et al. [10].
Shanyinghu and Zhu [11] developed a homogeneous model
including several reactions to illustrate molecular modeling of

* Corresponding author. Tel.: þ98 711 2303071; fax: þ98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
0360-3199/$ e see front matter ª 2010 Published by Elsevier Ltd on behalf of Professor T. Nejat Veziroglu.
doi:10.1016/j.ijhydene.2010.04.177
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1 7499

Off gas

Reactor 3

S ep e r ato r

Stabilizer
Reactor 2
Reactor1

Reformate to
storage

Heater 1 Heater 2 Heater 3

Catalyst

Feed gas
Hydrogen rich make gas

Fig. 1 e A simple process flow diagram for catalytic naphtha reforming.

the packed bed naphtha reformer. According to this molecular
model, different objective functions were considered in the
optimization process. They showed that the best operating
conditions can be obtained for producing high-quality gaso-
line with constrained benzene and aromatic contents. Maz-
zieri et al. [12] experimentally studied the metallic catalysts,
PteReeSn, for the naphtha reforming process. Rahimpour [13]
proposed a deactivation model for the industrial naphtha
reforming and estimated the deactivation parameters using
experimental plant data.
Furthermore, Mazzieri et al. [14] studied the deactivation
and regeneration of the metal function of PtReSn/Al2O3eCl
and PtReGe/Al2O3eCl for the catalytic naphtha reforming. Lid
and Skogestad [15] applied the simple model of Smith for

Off gas
S ep e r ato r

Stabilizer

2nd
1st Reactor 3rd
Reactor Reactor

Reformate to
storage
Catalyst
Heater 1 Heater 2 Heater 3

Feed gas
Hydrogen rich make gas

Compressor

Fig. 2 e Process flow diagram for catalytic naphtha reforming using spherical reactors.
7500 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1
Table 1 e TR, Ed, Kd, and typical properties of catalyst.
Parameter Value Dimension
TR 770 K tions of the spherical reactor have been optimized using
Ed 1.642  105 J mol
Kd 5.926  10 5 h 1
dp 1.2 mm
Pt 0.3 wt%
Re 0.3 wt%
sa 220 m2/g
rB 0.3 Kg/l
e 0.36 e feed gas for each reactor, the total pressure of the process, and
modeling a catalytic naphtha reformer with continuous
catalyst regeneration for four reactors and determined the
optimal operating conditions. Khosravanipour Mostafazadeh
and Rahimpour [16] presented a membrane catalytic bed
configuration for the naphtha reforming process to separate
the produced hydrogen considering the presence of catalyst
deactivation in their model.
The structure of the spherical reactor can effectively
reduce the pressure drop in the process. The catalyst bed is
placed in the middle space between two concentric spheres.
This configuration has been used in many research efforts. Hu
et al. [17] have modeled the spherical reactors for the nuclear
power plant. Malkin et al. [18] have analyzed the possibilities
of numerical solution for the polymerization process in
spherical reactor. Balakotiah et al. [19] have investigated the
effects of the flow direction on performance of the spherical
reactor. Hartig et al. [20] have studied the methanol produc-
tion in the spherical reactor. They have come to the conclu-
sion that considering the high production capacity and low
material costs, these reactors are economically more desir-
able. Guillermo et al. [21] have presented spherical reverse
flow reactor. According to this configuration, the feed gas
enters throughout one hemisphere and leaves through the
other. They determined the influence of the main operational
and design parameters and the potential applications for this
reactor. Rahimpour et al. [22e24] have studied and optimized
the methanol synthesis in a spherical reactor. They have also
suggested the spherical reactor configuration to be used in the
naphtha reforming process.
While utilizing the traditional optimization techniques, the
main issue is the possibility of getting stocked in local
optimum due to their sensitivity to initial guess. Therefore,
they have limited applications. Considering this fact, the need
to invent more practical methods led to the development of
some advanced systems based on natural phenomena
(evolutionary computation) such as simulated annealing (SA)
[25], evolution strategies (ESs) [26], genetic algorithms (GAs)
Table 2 e Strategy and parameters used for optimization.
Parameter Value
Strategy DE/best/1/bin
Number of Population (NP) 50
DE Step Size (F) 0.8
Crossover Probability Constant (CR) 0.8
[27,28] and differential evolution (DE) [29]. These methods are
more applicable considering their essential advantages
compared with traditional techniques. The operating condi-
1
Differential Evolution (DE) method.
Hydrogen and aromatics are the main products of this
process. Our goal in this optimization problem is to maximize
the molar flow rate of these components. Consequently,
maximum conversion of paraffins and naphthenes also will
be achieved. To reach this goal, the inlet temperature of the
the catalyst distribution should be optimized.
2. Process description
2.1. Conventional process
Catalytic naphtha reforming is the main process utilized by
petroleum refineries in order to convert paraffins and naph-
thenes into aromatic [30]. A simplified process flow diagram
for catalytic reforming is presented in Fig. 1. The main
reforming reactions are endothermic in this process. There-
fore, temperature drops within the reactor and the rate of
reaction decreases. To avoid this, three adiabatic reactors
have been designed with inter stage heaters before each
reactor. The feed gas is mixed with recycled gas and heated to
the desired temperature before entering the first reactor
which is smaller compared with other reactors. The outlet
from the third reactor is cooled and separated into gaseous
and liquid products in a flash separator. Reformate is the
liquid product which mainly consists of aromatics.
2.2. Spherical reactor setup
Considering the high pressure drop in the conventional
reactor, the concept of radial flow spherical reactor has been
suggested. A schematic diagram of the spherical reactor is
shown in Fig. 2. The space between two perforated spherical is
packed with catalysts. The feed gas enters the reactor and
flows from the outside through the catalyst bed into the inner
sphere. Slight pressure drop and low manufacturing costs
suggest the spherical-bed reactor configuration to be used
instead of conventional reactors in order to enhance the
production of the desired products.
3. Reaction scheme and kinetics
According to the model developed by Smith [3], the kinetic
scheme of the catalytic naphtha reforming process includes
four main dominant reactions. Utilizing this model, the cata-
lytic reforming system can be simplified significantly. These
four reactions are as follows:
(1) Dehydrogenation of naphthenes to aromatics.
(2) Dehydrocyclization of paraffins to naphthenes.
(3) Hydro cracking of naphthenes to lower hydrocarbons.
(4) Hydro cracking of paraffins to lower hydrocarbons.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1 7501

Table 3 e Comparison between model prediction and plant data for fresh catalyst.
Reactor Inlet Inlet Catalyst Input feedstock (mole %)
number temperature (k) pressure distribution
(kPa) (wt %)

1 777 3703 20 Paraffin 49.3

2 777 3537 30 Naphthene 36
3 775 3401 50 Aromatic 14.7

Reactor number Outlet temperature (k) Aromatic in reformate (mole %)

Plant NPBR SPFR Plant NPBR SPFR

1 722 732.1 727.6 e 42.5 41.0
2 753 757.5 752.0 e 53.1 52.0
3 770 772.5 770.8 57.7 56.9 56.1

Based on this classification, the reactions are: kf3

 
r3 ¼ pn (3)
pt
Naphthenes (CnH2n) 4 DH1 ¼ 71,038.06 kJ/kmol
Aromatics (CnH2n 6) þ 3H2 kf4
 
2. Naphthenes (CnH2n)þH2 4 DH2 ¼ 36953.33 kJ/kmol r4 ¼ pp (4)
pt
Paraffins (CnH2nþ2)
3. Naphthenes (CnH2n) þ n/3H2/ DH3 ¼ 51939.31 kJ/kmol where kf and Ke, are forward rate constant and equilibrium
Lighter ends (C1eC5) constants, respectively. Rase [31] has reported the equations
4. Paraffins (CnH2nþ2) þ (n 3)/3H2/ DH4 ¼ 56597.54 kJ/kmol of these constants for the reactions.
Lighter ends (C1eC5)
E1
 
kf1 ¼ 9:87exp 23:21 a (5)
The rate equations for these reactions are expressed by: 1:8T

kf1
 
pa p3h E2

 
r1 ¼ ke1 pn (1)
Ke1 kf2 ¼ 9:87exp 35:98 a (6)
1:8T

kf2 
  
E3
 
r2 ¼ ke2 pn ph pp (2) kf3 ¼ kf4 ¼ exp 42:97 a (7)
Ke2 1:8T

Table 4 e Specifications of reactors feed and product of

plant for fresh catalyst.
Table 5 e Comparison between predicted production rate
Parameter Numerical value Unit and plant data.
Naphtha feedstock 30.41  103 Kg/h Time Naphtha Plant Tubular Spherical Devi %
Reformate 24.66  103 Kg/h (day) feed (kmol/hr) (kmol/hr) (kmol/hr) (Tubular-
H2/HC mole ratio 4.74 e (ton/h) Plant)
WHSV 1.25 h 1
0 30.41 225.9 221.58 224.55 1.91
Mole percent of hydrogen 69.5 e
34 30.41 224.25 222.64 225.49 0.71
in recycle
62 31.00 229.65 228.18 230.97 0.64
Diameter and length of first 1.25,6.29 m
97 30.78 229.65 227.09 229.80 1.11
reactor
125 31.22 229.65 231.19 233.87 0.67
Diameter and length of second 1.67,7.13 m
160 31.22 229.65 231.72 234.34 0.90
reactor
188 28.55 211.6 210.16 212.66 0.68
Diameter and length of third 1.98,7.89 m
223 30.33 222.75 225.19 227.73 1.09
reactor
243 31.22 233.05 232.74 235.26 0.13
Distillation fraction of naphtha feed and reformate 298 30.67 228.65 228.75 231.21 0.04
TBP Naphtha feed ( C) Reformate ( C) 321 30.76 227.64 229.69 232.13 0.90
IBP 106 44 398 42.35 317.3 326.18 328.74 2.79
10% 113 73 425 42.32 317.94 326.12 328.89 2.57
30% 119 105 461 42.32 317.94 326.38 329.14 2.65
50% 125 123 490 42.32 317.94 326.56 329.06 2.71
70% 133 136 524 42.32 313.09 326.77 329.24 4.36
90% 144 153 567 42.54 317.94 328.83 331.29 3.42
FBP 173 181 610 42.54 313.9 329.06 331.49 4.82
717 37.86 286.15 290.79 293.13 1.62
771 38.51 282.1 296.4 298.73 5.06
7502 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1

2400
Table 6 e The optimized parameters for spherical
naphtha reforming reactors. OSR
2350 SR
Parameters Optimized

Total molar flow rate (kmole/hr)

value
2300
Inlet temperature at the entrance of the first 776.993
2375
reactor, K 2250
Inlet temperature at the entrance of the second 776.966 2370
reactor, K 2200
2365
Inlet temperature at the entrance of the third 774.996
reactor, K 0.92 0.94 0.96 0.98 1
2150
Total pressure of the process, kPa 2803.593
Catalyst distribution for the first reactor 0.241
(weight fraction) 2100

Catalyst distribution for the second reactor 0.257

(weight fraction) 2050
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Catalyst distribution for the third reactor 0.502
Mass of catalyst (Dimensionless)
(weight fraction)
Fig. 3 e Total molar flow rate.

46045
 
ke1 ¼ 1:04  10 3 exp 46:15 (8)
1:8T where i is the reaction number and j represents the compo-
nent number. The following boundary and initial conditions
8000
 
ke2 ¼ 9:87exp 7:12 þ (9) are applied to solve the model;
1:8T
r ¼ Ro ; Cj ¼ Cjo ; T ¼ To (12)
where a is activity of catalyst and E is activation energy of each
reaction. In order to minimize the difference between the
vCj vT
calculated and observed values of outlet temperature and r ¼ Ri ; ¼ 0; ¼0 (13)
vr vr
aromatic production yield, optimized values of activation
energies have been used [16]:
t ¼ 0; Cj ¼ Css ss
j ; T ¼ T ; a ¼ 1; (14)

E1 ¼ 36,350 kJ/kmol Ri and Ro are the radius of inner and outer spheres and the
E2 ¼ 58,550 kJ/kmol superscript ss represents steady state conditions. Several
E3 ¼ 63,800 kJ/kmol auxiliary correlations have been used to predict the physical
properties and estimate the mass and heat transfer coeffi-
cients. The auxiliary correlations are presented in Appendix B.
4. Mathematical model For the tubular reactor, same assumptions are applied as for
the spherical reactor. The mass and energy balance equations
4.1. Spherical and tubular reactor modeling
for the tubular reactor are expressed by;

In order to derive the mathematical model for the radial flow v2 Cj m

v uCj X vCj
Dej þrB a nij ri ¼ e j ¼ 1;2;.;n; i ¼ 1;2;.;m (15)
spherical reactor, a one dimensional homogenous model has vx2 vx vt
i¼1
been used. The changes in the dynamic model developed by
Rahimpour et al. [32] for tubular flow reactor have been m
v2 T v

X v


applied to develop the governing mass and energy balance keff rucp T Tref þrB a DHi ri ¼ e rcp T Tref (16)
vx2 vx i¼1
vt
equations for this configuration. Kinetic and thermodynamic
relations and also auxiliary correlations have been used to In order to solve these equations, following boundary and
design the basic structure of the model. The achieved mass initial conditions are applied for tubular reactor;
and energy balance equations in the model are solved by
orthogonal collocation method. This method is discussed in x ¼ 0; Cj ¼ Cjo ; T ¼ To (17)
Appendix A. The mass and energy balance equations for the
spherical reactor are as follows; vCj vT
x ¼ L; ¼ 0; ¼0 (18)
vx vx
m
1 v 2 vCj 1 v 2
 

X vCj
Dej 2 r r ur Cj þ rB a nij ri ¼ e
r vr vr r2 vr vt t ¼ 0; Cj ¼ Css ss
j ; T ¼ T ; a ¼ 1 (19)
i¼1

j ¼ 1; 2; .; n; i ¼ 1; 2; .; m ð10Þ where L is the length of the tubular reactor.

m
1 v 2 vT 1 v
 
4.2. Pressure drop
X
rr2 ur cp T



keff 2
r Tref þ rB a DHi ri
r vr vr r2 vr i¼1



v r cp T Tref Ergun equation has been used to calculate the pressure drop
¼e i ¼ 1; 2; .; m (11)
vt across the catalyst bed. For the entire range of flow rate
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1 7503

a 130 b 11
SR OSR
10 SR
OSR
125

Naphthene molar flow rate (kmole/hr)

9
Paraffin molar flow rate (kmole/hr)

120
8

115 7

6
110

105
4

100 3
0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
Mass of catalyst (Dimensionless) Mass of catalyst (Dimensionless)

c 135
Aromatic molar flow rate (kmole/hr)

130

125

SR
OSR
120
0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1
Mass of catalyst (Dimensionless)

Fig. 4 e Molar flow rate for (a) Paraffin (b) Naphthene (c) Aromatic, along the third reactor.

discussed in this research, this equation is applicable. The effects of the catalyst deactivation in this research, this model
Ergun equation is derived for Cartesian and spherical systems has been used;
to calculate the pressure drop for tubular and spherical reac-
da Ed 1 1
  
tors, respectively. ¼ Kd exp a7 (22)
dt R T TR

4.2.1. Cartesian system where TR, Ed, and Kd are the reference temperature, activation
energy and deactivation constant of the catalyst, respectively.
dP 150m ð1 eÞ2 Q 1:75r ð1 eÞ Q 2 The catalyst utilized in this process is a bimetallic plati-
¼ þ (20)
dx f2s d2p e3 Ac fs d p e3 A2c numerhenium and promoter on high purity alumina. The
numerical values of TR, Ed and Kd and also the specifications of
4.2.2. Spherical system the catalyst are presented in Table 1.

! !
dP 150m ð1 eÞ2 Q 1 1:75r ð1 eÞ Q 2 1
¼ þ (21) 6. Differential evolution (DE) method
dr f2s d2p e3 4p r2 fs d p e3 ð4pÞ2 r4

where dP and dp are the pressure gradient and the particle Differential Evolution is an efficient and simple optimization
diameter, respectively, and Øs is the sphericity which is unity technique [33]. Considering the type of problem, different
for spherical particles. strategies can be used in DE algorithm. The value of NP
(Number of Population), F (DE step size) and CR (Crossover
probability constant) should be determined by the conditions
5. Catalyst deactivation model of the issue. The first value chosen for NP in this research was
50, which turned out to be an appropriate value. DE step size
Rahimpour [13] has developed a catalyst deactivation model lies in the range of 0.5e1.0. The crossover probability constant
for catalytic naphtha reforming process. In order to study the is in the range of 0.0e1.0. Generally, CR should be as large as
7504 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1

a 140 a 780
120
770
Production rate (kmole/hr)

Aromatic
100
760
Paraffin

Temperature (K)
80 140 OSR Third
120
100 Reactor
0 0.5SR
1 750
60
First
740 Reactor Second
40 Naphthen
Reactor

730
20 OSR
SR
0 720
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mass of catalyst (Dimensionless) Mass of catalyst (Dimensionless)

b 1550 b 0.98
0.97
Hydrogen production rate (kmole/hr)

1500 OSR
0.96 First SR
Reactor
1505 0.95
1450 Catalyst activity
1500 0.94

1495 0.93 Third

1400
Reactor
0.7 0.8 0.9
0.92
OSR Second
1350 SR 0.91 Reactor

0.9
1300
0.89

0.88
1250 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mass of catalyst (Dimensionless)
Mass of catalyst (Dimensionless)
Fig. 6 e (a) temperature distribution and (b) catalyst activity
Fig. 5 e Total production and consumption rate of the (a)
of three reactors.
hydrocarbons and (b) hydrogen.

auxiliary correlations, kinetics and thermodynamics of the

possible [34]. More details of basic version of DE, its strategies,
reaction system. The auxiliary correlations are discussed
and choosing the operating parameters are presented by Babu
further in Appendix B. Inner collocation points were chosen as
and Angira [33], and Babu and Munawar [34]. In this research,
roots of a Jacobi polynomial. The orthogonal collocation
the strategy and parameters used for DE are tabulated in
method is discussed in Appendix A. By utilizing this numerical
Table 2.
method, the system of PDEs was substituted by an ordinary
differential equation (ODE) system. The energy balance
equation was developed for each collocation point, as well as
7. Numerical solution the mass balance equation for each reaction.

The procedure of solving the set of coupled partial differential

equations (PDEs) of the system consists of two main steps. 8. Optimization and results
A steady state simulation of the process is investigated to
predict the initial conditions of the second step which is the 8.1. Model validation
dynamic behavior of the reactors. Steady state simulation of
the reactor is achieved by setting all the time variations of the 8.1.1. Steady state model validation
states equal to zero and also by considering a fresh catalytic The model validation has been investigated considering
bulk. The deactivation model equation and the conservation observed plant data for conventional packed bed reactor at
rules, as well as the algebraic equations provide a set of steady state conditions. Table 3 presents the plant data and
dynamic equations consists of simultaneous ordinary and predicted mole fractions of the components in the output of
partial differential equations developed according to the the process. Model results show acceptable agreement with
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1 7505

1 6.4
SR
OSR 6.2
0.95

6
0.9

H2/HC mole ratio

5.8

0.85
Catalyst activity

5.6 OSR
Catalyst activity SR
at the 100th day Catalyst activity 5.4
0.8
at the 800th day

5.2
0.75
5

0.7
4.8

0.65 4.6
0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mass of catalyst (Dimensionless) Mass of catalyst (Dimensionless)

Fig. 7 e Catalyst activity for the third reactor at the 100th Fig. 8 e H2/HC ratio.
and 800th day of the operation.

conventional naphtha reforming process for fresh catalyst

the plant data. By utilizing the PONA Test in Stan Hop Seta mentioned in Table 4 this ratio is kept more than 4.71 in the
apparatus, each component (paraffin, naphthene and optimization process for each reactor. Therefore, the
aromatic) has been analyzed. The aromatic is tested especially constraints will be:
by ASTM 2159 equivalent to UOP 273 method.
ðH2 =HCÞi > 4:71 (24)

8.1.2. Model validation considering the catalyst deactivation

3
Table 4 presents the input data of the reactor for fresh
X
Wi ¼ 1 (25)
catalyst obtained from the operating data of catalytic i¼1

reformer unit [35]. The model was validated by comparison of
model results of tubular reactor with the process data for
a period of 771 operating days. The predicted results of
production rate, the corresponding observed data and the
residual error are presented in Table 5. A satisfactory agree-
ment between daily-observed plant data and simulation data
can be noticed and the model performed well under indus-
trial conditions.
8.2. Optimization
where i represents the number of the reactors and Wi is the
weight fraction of the catalysts in each reactor. All the
constraints should be considered in the optimization process.
To insert these constraints, penalty function method has been
used. In this method, a penalty parameter is defined in a way
to eliminate the unacceptable results automatically. 105 is the
penalty parameter in this research, but this parameter
depends on the order of magnitude of the decision variables.
The objective function to be minimized is:

In this research, DE method has been used to maximize the

production of aromatics and hydrogen. Therefore, the objec- 785

tive function is expressed by: 784 1st reactor

2nd reactor
Sum ¼ YHOut =YHIn2 þ Yaromatic
Out In
=Yaromatic (23) 783
Inlet temperature of the reac tors (K)

2 3rd reactor
Out In 782
where Y and Y are the mole fractions in the outlet of the
third reactor and the inlet of the first reactor, respectively. 781
Therefore, both hydrogen and aromatic production have been
780
considered in the optimization process.
Seven decision variables should be controlled in this 779

problem; the inlet temperature of the gas at the entrance of 778

each reactor, the pressure of the gas at the outlet of the
777
compressor which is almost constant through the process due
to the slight pressure drop in the spherical reactors, and the 776

catalyst distribution for each reactor. 775

0 100 200 300 400 500 600 700 800
In the naphtha reforming process the hydrogen amount is
Time (Day)
important. Low H2/HC ratio means low hydrogen production.
Also it can cause catalyst deactivation due to the coke Fig. 9 e Optimized inlet temperature of the reactors as
formation. Considering the H2/HC ratio applied in the a function of time.
7506 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1
5
X 1
Results ¼ Sum þ 105 G2i
i¼1
where:


G1 ¼ max 0; 4:71 ðH2 =HCÞ1


G2 ¼ max 0; 4:71 ðH2 =HCÞ2


G3 ¼ max 0; 4:71 ðH2 =HCÞ3
G4 ¼ maxf0; ð1:0001 ðW1 þ W2 þ W3 ÞÞg
G5 ¼ maxf0; ððW1 þ W2 þ W3 Þ 0:9999Þg
Differential evolution method has been applied to solve this
problem.
8.3. Optimization results
As previously mentioned, the inlet temperature of the gas at
the entrance of each reactor, the total pressure of the gas in
the process, and the catalyst distribution for each reactor are
the decision variables in this problem. Differential evolution
(DE) method has been used and the obtained results are
tabulated in Table 6.
The results of this study are shown in the following figures.
In all previous studies, the total molar flow rate is assumed to
be constant in the reactors while in plant, it increases during
the process. Therefore, the assumption of constant molar flow
rate for this system is not logical. The total molar flow rate
during the process is shown in Fig. 3. As it can be seen, the
total molar flow rate slightly increases at the outlet of the third
reactor for the case of optimized spherical reactor (OSR)
compared with non-optimized spherical reactor (SR). As it can
be seen in Section 2, the products of the governing reactions of
the naphtha reforming process have higher stoichiometric
coefficients compared with the reactants. Therefore, higher
total molar flow rate means shifting the equilibrium to the
production side in the reversible reactions and increasing
the desired products which is further illustrated by Fig. 5(a)
and (b).
Fig. 4 presents the molar flow rates for each component
(paraffin, naphthene and aromatic) along the third reactor.
Higher aromatic molar flow rate is completely desirable as one
of the main products of the naphtha reforming process. As
presented in Section 2, paraffin and naphthene are the main
reactants of this process. Higher consumption rate of these
components results in higher production rate of hydrogen and
aromatic. Therefore, minimizing the molar flow rate of these
components is desired in the optimization process. Fig. 5(a)
illustrates the total production and consumption rate of the
hydrocarbons and the hydrogen production rate is shown in
Fig. 5(b). These figures show the higher consumption rate of
naphthene and also the higher production rates of aromatic
and hydrogen in OSR system. The paraffin’s consumption rate
is almost the same for both cases.
H2 production rate increases during the process but in the
third reactor, the hydrogen molar flow rate reaches
a maximum value and becomes constant due to the
(26)
3rd reactor
0.95
2nd reactor
1st reactor
Av erage c ataly s t ac tiv ity
(27) 0.9
(28) 0.85
(29) 0.8
(30)
0.75
(31)
0.7
0 100 200 300 400 500 600 700 800
Time (Day)
Fig. 10 e Optimized average catalyst activity of each
reactor.
thermodynamic limitation. As a suggestion, the third reactor
could be replaced by a membrane reactor in order to shift the
thermodynamic equilibrium and, consequently, increase the
hydrogen production. But one should consider the fact that
the membrane reactor cannot be used in radial flow pattern.
Catalytic naphtha reforming is an endothermic process.
Therefore, the temperature falls as the reactions proceed.
Fig. 6(a) illustrates the temperature distribution for both cases
of optimized and non-optimized spherical reactor. As it can be
seen, for the first and second reactors, the optimized
temperature is slightly more than the temperature of the
non-optimized spherical reactor. However, the case for the
third reactor is vice versa. The temperature strongly affects
the catalyst activity; the activity increases as the temperature
decreases. Therefore, as it can be noticed from Fig. 6(b), the
catalyst activity of the first and second optimized reactors
deteriorates to some extent, but low relative temperature of
the third optimized reactor boosts the activation of the
catalyst.
Fig. 7 presents the catalyst activity for the third reactor at
the 100th and 800th day of operation. Obviously, the activity of
the catalyst entirely decreases with time due to the sintering
phenomena.
The H2/HC ratio is presented in Fig. 8. Clearly, the ratio in
the optimized spherical reactor has improved. Higher H2/HC
ratio prevents the coke formation in the reactor and, conse-
quently, enhances the performance of the catalyst. Moreover,
higher hydrogen production can be achieved.
Considering the dependence of the catalyst activity on
time, the conditions of the optimization problem and there-
fore, the calculated optimized inlet temperature of the gas at
the entrance of each reactor, change with time. In order to
control this issue, the inlet temperature has been calculated
for the period of 800 days of operation. Fig. 9 presents the
calculated optimized inlet temperature of the reactors as
a function of time. According to the deterioration of the
performance of the catalysts during the operation, the calcu-
lated optimal inlet temperature of the reactors may change by
time. Therefore, in order to achieve the best possible results
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1 7507

a 112
b 5.5

110

Naphthen molar flow rate (kmole/hr)

5
paraffin molar flow rate (kmole/hr)

108
4.5

106

4
104

3.5
102
OSR OSR
SR SR
100 3
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Time (Day) Time (Day)

c 135 d 1504
134.5 SR
1503
OSR
OSR

Hydrogen production (kmole/hr)H

Aromatic molar flow rate (kmole/hr)

134
1502 SR
133.5
1501
133

132.5 1500

132 1499

131.5
1498
131
1497
130.5

130 1496
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Time (Day) Time (Day)

Fig. 11 e the molar flow rate of the (a) Paraffin (b) Naphthene (c) Aromatic and (d) The hydrogen production rate.

during the mentioned time interval, the optimal inlet rate for the optimized case is more desirable compared with
temperature should change with time. the non-optimized spherical reactor as can be noticed in
As mentioned before, the optimal parameters change Fig. 11(b). Aromatic and hydrogen molar flow rate decreases
during operation because of the catalyst deactivation and with time as expected but higher molar flow rate of the
therefore they are not unique over different time intervals desired products can be achieved easily by controlling the
[23]. According to this issue, different parameters are inves- operating conditions in their optimum situation.
tigated as time goes by. The modeling results show the cata-
lyst activity and the molar flow rate of the components as
functions of time. Fig. 10 presents the optimized average 9. Conclusion
catalyst activity of each reactor. Therefore, the dependence of
the catalyst activity on time is investigated in this figure. Decreasing the pressure drop in an industrial process is an
Clearly, the catalyst activity decreases with time as important issue. Considering this fact, utilizing a radial flow
expected. Due to the reduction of the catalyst activity, the spherical reactor, which has a low pressure drop through the
production rate of the hydrogen and aromatic decreases with catalytic bed, is a potentially interesting idea for industrial
time. For the same reason, the consumption rate of the naphtha reforming. A one dimensional model was used for
paraffin and naphthene decreases, therefore the molar flow optimization of the spherical reactor for catalytic naphtha
rate of these components increases with time. The discussed reforming process. Orthogonal collocation method was
molar flow rates are plotted in Fig. 11(a)e(d). As it can be seen, applied to solve the mass and energy balance equations. This
the paraffin molar flow rate increases with time according to method has been investigated through Appendices A and B.
the lower consumption rate of the reactants caused by the The differential evolution (DE) method was used as the opti-
deterioration of the catalyst activity. The result is the same for mization technique. Our goal was to maximize the hydrogen
both cases of optimized and non-optimized spherical reactor. and aromatic production rate. The variability of the total
The naphthene molar flow rate also increases as time goes by molar flow rate was considered in this research which
due to the mentioned reason. Nevertheless, the molar flow improved our calculation results. The catalyst distribution in
7508 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1

all three stages was optimized in a way to maximize the Nþ1

Y x xj
production of the desired products. In this study, the li ðxÞ ¼
(A-5)
xi xj
j¼1
maximum possible inlet temperature of the gas at jsi
the entrance of the reactors was defined 777 K according to the
Furthermore,
plant data (Table 3). However, by utilizing higher thermal
capacity furnaces and raising the inlet temperature of the gas


0 isj
entering the reactors up to 840 K, more desirable results will li xj ¼ (A-6)
1 i¼j
be achieved. The effects of temperature and time on the
The first and second derivatives at the interpolation points
catalyst activity have been investigated in the results.
are:
Acceptable enhancement in the performance of the reactor
can be noticed. The results suggest that this configuration can Nþ1
dyN ðxi Þ X dlj ðxi Þ
be a compelling way to boost hydrogen and aromatic ¼ yj (A-7)
dx j¼1
dx
production. However, an investigation in relation to the
environmental aspects, commercial viability and economic
2 Nþ1 2
feasibility of the proposed configuration is necessary in order d yN ðxi Þ X d lj ðxi Þ
¼ yj (A-8)
to consider commercialization of the process. dx2 j¼1
dx2

For i ¼ 1; 2.; N; N þ 1:
Appendix A. Orthogonal collocation method
The first derivative vector, composed of (N þ 1) first deriv-
Jacobi Polynomials atives at the (N þ 1) interpolation points, is:
T
dyN ðx1 Þ dyN ðx2 Þ dyN ðxN Þ dyN ðxNþ1 Þ

ða;bÞ
The Jacobi functionJN ðxÞ, is a polynomial of degree N that is, y0N ¼ ; ; .; ; (A-9)
dx dx dx dx
orthogonal with respect to the weighting function xb ð1 xÞa .
The Jacobi polynomial of degree N has the following power Similarly, the second derivative vector is defined as:
series:
" #T
2 2 2 2
d yN ðx1 Þ d yN ðx2 Þ d yN ðxN Þ d yN ðxNþ1 Þ
N y00N ¼ ; ; .; ; (A-10)
ða;bÞ
ð 1ÞN i gN;i xi dx2 dx2 dx2 dx2
X
JN ðxÞ ¼ (A-1)
i¼0
The function vector is defined as the values of y at N þ 1
The domain of x is in the range [0, 1].
collocation points as:

 T
y ¼ y1 ; y2 ; y3 ; .; yN ; yNþ1 (A-11)
The evaluation of coefficients is done by using the following
recurrence formula: By means of these definitions of vectors y and derivative
vectors, the first and second derivative vectors can be written
in terms of the function vector y using matrix notation:
gN;i N iþ1 Nþiþaþb
¼ $ (A-2)
gN;i 1 i iþb y0 ¼ A$y
(A-12)
y00 ¼ B$y
Starting with
Where the matrices A and B are defined as:
gN;0 ¼ 1 (A-3)
dlj ðxi Þ
 
gN,i are the constant coefficients, and a and b are the param-
A¼ aij ¼ ; i; j ¼ 1; 2; .; N; N þ 1 (A-13)
eters characterizing the polynomials. dx

2
( )
d lj ðxi Þ
Lagrange interpolation polynomials B¼ bij ¼ ; i; j ¼ 1; 2; .; N; N þ 1 (A-14)
dx2

For a given set of data points (x1, y1),(x2, y2),.,(xN, yN) and The matrices A and B are (N þ 1, N þ 1) square matrices. Once
(xNþ1,yNþ1) an interpolation formula passing through all the (N þ 1) interpolation points are chosen, then all the
(N þ 1) points is an Nth degree polynomial. A suitable inter- Lagrangian building blocks, li(xi), are completely known, and
polation polynomial for the orthogonal collocation method is thus the matrices A and B are also known [36].
Lagrange interpolation polynomial, which passes through
interior collocation points and roots of Jacobi polynomials,
and it is expressed by:
Appendix B. Auxiliary correlations
Nþ1
X
yN ðxÞ ¼ yj lj ðxÞ (A-4) B.1. Gas phase viscosity
j¼1

Where yN is the Nth degree polynomial, yi is the value of y at Viscosity of the reactants and the products is obtained from
the point xi, and li(x) is defined as the following formula:
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1 7509

C1 TC2


1 yi
m¼ (B-1) Dim ¼P (B-5)
C3 C4


1þ þ yi =Dij
T T2
The binary diffusivities are calculated using the Full-
Where m is the viscosity in Pa s and T is the temperature in K.
ereSchettereGiddins equation which is reported by Reid et al.
Viscosities are at 1 atm [37].
[40]. In the following FullereSchettereGiddins correlation, vci
and Mi are the critical volume and molecular weight of
component i which are reported in Table B.1.

Table B.1 e Constant of Eq. (B-1) for reactant and product. 10 7 T3=2 1=Mi þ 1=Mj

1=2
Dij ¼ (B-6)
Component C1 C2 C3 C4  2
Pt vci3=2 þ vcj3=2
8
CnH2nþ2 4.1306  10 0.9074 78.2449 0
7
CnH2n 6 3.6249  10 0.6063 208.5202 0
7
CnH2n 3.6744  10 0.5868 235.1696 0
7
H2 1.797  10 0.6850 0.59 140
8
L.E 4.9054  10 0.90125 0 0
Table B.3 e Molecular weights and critical volumes of the
components and other specifications of feed at inlet
conditions.
B.2. Gas phase heat capacity Parameter Value Dimension

Heat capacity of the reactants and products at constant Mwm 21.8 g/mol
rg 12.37 kg/m3
pressure is obtained from the following formula:
cpg 88.3 kJ/kmol k
2
" #2 " #2 m 2.87  10 cp
C3 C5
Cp ¼ C1 þ C2 T

þC4 T
(B-2) K 0.181 w/m k
C3 C5


sin h T
cos h T vcp 0.486 m3/kmol
vcn 0.460 m3/kmol
Where cp is in J/(kmol K) and T is in K [37]. vca 0.375 m3/kmol
vch 0.064 m3/kmol
vcl.e 0.124 m3/kmol
Mwn 113.9 g/mol
Mwp 115.9 g/mol
Table B.2 e Constant of Eq. (B-1) for reactant and product.
Mwa 107.9 g/mol
5 5 3 5
Component C1  10 C2  10 C3  10 C4  10 C5

CnH2nþ2 1.3781 4.4988 1.6369 3.053 746.85

CnH2n 6 1.166 4.6381 1.672 3.2894 781.46
CnH2n 0.8102 3.4545 1.5531 2.459 700.922 B.4. Heat transfer correlation
H2 0.27617 0.0956 2.466 0.037 567
L.E 0.5192 1.9245 1.6265 1.168 723.6 The heat transfer coefficient between the gas phase and the
solid phase is obtained by the following correlation [41]:

0:407
To complete the simulation, extra correlations should be hf cp m2=3 0:458 rudp
 
¼ (B-7)
added to the model. In the case of heterogeneous model, cp rm K eb m
because of the transfer phenomena, the correlations for the
Where u is the superficial velocity of the gas and the other
estimation of heat and mass transfer between two phases
parameters are those of bulk gas phase, dp is the equivalent
should be considered.
catalyst diameter, K is the thermal conductivity of the gas, r, m
are the density and viscosity of the gas, respectively and e is
the void fraction of the catalyst bed.
B.3. Mass transfer correlations

To flow through a packed bed, the correlation is given by the

following equation [38]:
Nomenclature

1=2 
kci dp e 1 u
 
m
¼ (B-4) A catalyst activity, [ ]
Dim 1 e g mð1 eÞg rDim
aij element of matrix A, [ ]
Where dp is the particle diameter (m), eb is the void fraction of A moles of aromatic formed, [kmol h 1]
the packed bed, g is the shape factor of the pellet, u is the A matrix defined in Eq. (A-12), [ ]
superficial velocity through the packed bed (m/s), m is the Ac cross-section area of reactor, [m2]
viscosity of the gas fluid phase (kg/m s) and r is the fluid B matrix defined in Eq. (A-12), [ ]
density (kg/m3). bij element of matrix B, [ ]
Diffusivity of component i in the gas mixture is given by C concentration, [kmol m 3]
[39]. Ci coefficient of Eq. (B-1) and (B-2), [ ]
7510 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 5 ( 2 0 1 0 ) 7 4 9 8 e7 5 1 1

Cj0 inlet concentration of component j, [kmol m 3] yN Jacobi polynomial of degree N, [ ]

cp specific heat capacity, [kJ kmol 1 K 1] yi mole fraction for i component in gas phase, [ ]
dp particle diameter, [m] yis mole fraction for i component on solid phase, [ ]
De effective diffusivity, [m2 s 1] y0N first derivative of Jacobi Eq., [ ]
Dim diffusivity of component i in the gas mixture, y00N second derivative of Jacobi Eq., [ ]
[m2 s 1]
Ed activation energy of catalyst, [J mol 1] Greek letters
Ei activation energy for i reaction, [kJ kmol 1] a characteristic parameter of Jacobin equation, [ ]
Ft total molar flow rate, [kmol h 1] b characteristic parameter of Jacobin equation, [ ]
G constraint, [ ] g coefficient of eq. (A-1), [ ]
hf heat transfer coefficient, [W m 2 K 1] e void fraction of catalyst bed, [ ]
HC hydrocarbon, [kmol h 1] m viscosity of gas phase, [kg m 1 s 1]
H2 hydrogen, [kmol h 1] vij stoichiometric coefficient of component i in reaction
i numerator, [ ] j, [ ]
j numerator, [ ] rb reactor bulk density, [kg m 3]
J Jacobi function, [ ] r density of gas phase, [kg m 3]
keff effective thermal conductivity, [W m 1 s 1] DH heat of reaction, [kJ kmol 1]
kci mass transfer coefficient for component i, [m h 1] fs sphericity, [ ]
kf1 forward rate constant for reaction (1),
[kmol h 1 kgcat 1 MPa 1] Subscripts and superscript
kf2 forward rate constant for reaction (2), a aromatic, [ ]
[kmol h 1 kgcat 1 MPa 2] cal calculated, [ ]
kf3 forward rate constant for reactions (3), h hydrogen, [ ]
[kmol h 1 kgcat 1] i numerator for reaction, [ ]
kf4 forward rate constant for reactions (4), j numerator for component, [ ]
[kmol h 1 kgcat 1] n naphthene, [ ]
Ke1 equilibrium constant, [MPa3] out outlet, [ ]
Ke2 equilibrium constant, [MPa 1] p paraffin, [ ]
Kd deactivation constant of the catalyst, [h 1] ss steady state, [ ]
L length of reactor, [m] T transpose, [ ]
lj building block of Jacobi polynomial, [ ]
m number if data sets used, [ ] Abbreviation
m number of reaction, [ ] FBP final boiling pint, [ C]
mc mass of catalyst, [kg] IBP initial boiling pint, [ C]
Mi molecular weight of component i, [kg kmol 1] NPBR normal packed bed reactor, [ ]
Mw average molecular weight of the feedstock, SPBR spherical packed bed reactor, [ ]
[kg kmol 1] sph spherical reactor, [ ]
n average carbon number for naphtha, [ ] TBP true boiling point, [K]
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Ni molar flow rate of component i, [kmol h 1]
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