Fuel 97 (2012) 109118

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Boosting the gasoline octane number in thermally coupled naphtha reforming

heat exchanger reactor using de optimization technique
Mohammad Reza Rahimpour a,b,, Davood Iranshahi a, Ehsan Pourazadi a, Ali Mohammad Bahmanpour a
a
b

Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran
Gas Center of Excellence, Shiraz University, Shiraz 71345, Iran

a r t i c l e

i n f o

Article history:
Received 29 October 2010
Received in revised form 9 December 2011
Accepted 9 January 2012
Available online 9 February 2012
Keywords:
DE optimization
Octane boosting
Thermally coupled reactor
Catalytic naphtha reforming
Hydrogenation of nitrobenzene

a b s t r a c t
Since the reneries are benetted mostly from the catalytic naphtha reforming units, these units are of
highly interest. This importance would generate continuous evolution of the technology in both the processing and equipment pieces of the technology. One of the promising developments in the naphtha
reformers would be thermal coupling of the reactors in a heat exchanger conguration. In this study,
the DE optimization technique has been used as a powerful tool to nd the best operating parameters
in the naphtha coupled reactors. Twenty-six decision variables have been considered in this optimization
problem. The endothermic dehydrogenation of the catalytic naphtha reforming is coupled with an exothermic hydrogenation reaction (hydrogenation of nitrobenzene to aniline) through a shell and tube heat
exchanger reactor. Catalyst mass distribution, exothermic inlet temperature, operating pressures, number of tubes in the exothermic side and the total molar ow rates are the most important optimized
parameters. Maximizing the aromatics (octane number) in reformate is the best possible objective function in this research. The results show a signicant increase in hydrogen and aromatics production rate of
the optimized reactor compared with the non-optimized one. Hydrogen and aromatics have increased 72
and 41 kmol/h, respectively. Besides, the exothermic tubes are considered for the third reactor in this
work to maximize the aromatic and hydrogen production rates. These results are valuable for the procedure of designing a reactor in which both reactions are integrated.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
1.1. Naphtha reforming
Considering the worldwide high octane gasoline demand, the
catalytic naphtha reforming units attract increasing attention. Catalytic naphtha reforming process contains the reconstruction of
low-octane hydrocarbons in the naphtha and production of more
valuable high-octane gasoline components without changing the
boiling point range. Naphtha and reformate are complex mixtures
of parafns, naphthenes, and aromatics in the C5C12 range. Catalytic reforming is carried out at 450520 C and moderate pressures (430 bar). The importance of the naphtha reforming
process in the renery would generate continuous evolution of
the technology [1]. Primary attempts have been made to nd a
proper kinetic model for the catalytic naphtha reforming. A simple
model was presented by Smith [2] in which naphtha reforming
was considered as a combination of four main reactions. The
kinetic model of Krane et al. [3] was one of the most elaborated
models which considered all possible reactions in the process.
Corresponding author at: Department of Chemical Engineering, School of
Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran. Tel.:
+98 711 2303071; fax: +98 711 6287294.
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2012.01.015

Ramage et al. [4] developed a comprehensive kinetic model which

attempted to consider the reactivity differences between particular
raw materials and modify the process kinetics by incorporating
deactivation of the catalyst due to coke formation. Also, a new kinetic model developed by Weifeng et al. [5] involving 20 lumped
components and 31 reactions for catalytic reforming process. The
subdivision of 8-carbon aromatics and all the hydrocracking reactions of the parafn lumps were considered in their model.
Stijepovic et al. [6] developed a semi-empirical kinetic model for
catalytic reforming. The most important reactions of the catalytic
reforming process were taken into account in their kinetic model.
One of the advantages of the presented kinetic model was high
predictability of hydrogen and light gases concentration. Other
scholars such as Shanyinghu and Zhu [7], Mazzieri et al. [8],
Salusinszky [9], Towghi et al. [10], Pieck et al. [11], Yan [12], Iranshahi et al. [13,14] and Rahimpour et al. [15,16] investigated
various ways of improving the efciency of the reformers.
1.2. Process intensication (coupled reactors)
Process intensication (PI) is currently one of the most signicant trends in chemical engineering and process technology [17].
It is the strategy of reducing environmental emissions, energy
and materials consumption. Innovations in catalytic reactors,

110

M.R. Rahimpour et al. / Fuel 97 (2012) 109118

Nomenclature
a
A
Ac
Cp
dp
Ed
Ei
Fi
hf
keff
kf1
kf2
kf3
kf4
Ke1
Ke2
L
Mi
Mw
n
NA
Ni
p
Pi
P
Q
ri
r
R
sa
T
Wi
YFi
yi

catalyst activity
moles of aromatic formed, kmol h1
cross-section area of reactor, m2
specic heat capacity, kJ kmol1 K1
particle diameter, m
activation energy of catalyst, J mol1
activation energy for ith reaction, kJ kmol1
molar ow rate of component i
heat transfer coefcient, W m2 K1
effective thermal conductivity, W m1 s1
forward
rate
constant
for
reaction
(1),
kmol h1 kgcat1 MPa1
forward
rate
constant
for
reaction
(2),
kmol h1 kgcat1 MPa2
forward
rate
constant
for
reactions
(3),
kmol h1 kgcat1 MPa2
forward
rate
constant
for
reactions
(4),
kmol h1 kgcat1 MPa2
equilibrium constant, MPa3
equilibrium constant, MPa1
length of reactor, m
molecular weight of component i, kg kmol1
average molecular weight of the feedstock, kg kmol1
average carbon number for naphtha
molar ow rate of aromatic, kmol h1
molar ow rate of component i, kmol h1
moles of parafn formed, kmol h1
partial pressure of ith component, kPa
total pressure, kPa
volumetric ow rate, m3 s1
rate of reaction for ith reaction, kmol kgcat1 h1
rate of hydrogenation of nitrobenzene, mol kgcat1 s1
gas constant, kJ kmol1 K1
specic surface area of catalyst pellet, m2 kg1
temperature of gas phase, K
catalyst weight fraction of ith reactor
fraction of exothermic feed to the ith reactor
mole fraction for ith component in gas phase

which constitute the heart of the process technologies, are often

the preferred starting point. In this way, multifunctional auto-thermal reactor is an applicable idea in process intensication. Currently, a promising eld of using multifunctional auto-thermal
reactors is the coupling of endothermic and exothermic reactions.
In this type of reactors, an exothermic reaction is used as the heat
producing source to drive the endothermic reaction(s) [18,19].
During recent years, many researchers have focused on the autothermal reactors and their applications [20,21].
The goal of this study, is to enhance maximum possible aromatics production rate (octane number) in reformate and hydrogen
production in a catalytic reformer. A one-dimensional homogeneous mathematical model has been considered in this study and
mass and energy balance equations have been obtained to predict
the coupled conguration behavior. Many different aspects have
been considered in the optimization process in order to achieve
the best possible operating conditions. The main issue while utilizing the traditional optimization techniques is that the global optimum conditions may not be achieved due to the sensitivity of
these techniques to the initial given values. Therefore, more advanced systems based on natural phenomena (evolutionary computation) such as simulated annealing (SA) [22], evolution
strategies (ESs) [23], genetic algorithms (GAs) [24,25] and differen-

Greek letters
void fraction of catalyst bed
viscosity of gas phase, kg m1 s1
density of gas phase, kg m3
reactor bulk density, kg m3
sphericity
DH
heat of reaction, kJ kmol1
z
axial direction

e
l
q
qb
us

Subscript
a
cal
h
i
j
n
NB
out
p
Tube
Shell

and superscript
aromatic
calculated
hydrogen
number of components
number of reaction sides (1: endothermic, 2: exothermic)
naphthene
nitrobenzene
outlet
parafn
tube side
shell side

Abbreviation
CTR
Conventional tubular naphtha reactor
FBP
nal boiling pint, C
IBP
initial boiling pint, C
LHSV
liquid hourly space velocity, h1
LOD
length over diameter
OTCR
optimized thermally coupled reactor
Pt
platinum
Re
rhenium
RON
research octane number
TBP
true boiling point, K
TCR
thermally coupled reactor
WHSV
weight hourly space velocity, h1

tial evolution method (DE) [26] were invented. These methods are
more useful considering their essential advantages compared with
traditional techniques. In the present research, the operating conditions have been optimized using Differential Evolution (DE)
method. By utilizing this method the hydrogen and aromatics production rate has been maximized and the decision variables have
been assigned according to the dened objective function.
2. Process description
2.1. Conventional tubular naphtha reactor (CTR)
A simplied process ow diagram for conventional catalytic
naphtha reforming is presented in Fig. 1. CTR conguration has
been described extensively in the previous research [27].
2.2. Thermally coupled naphtha reforming reactor (TCR)
A conceptual schematic for the coupled conguration is depicted in Fig. 2. As it is illustrated, the tubes which contain the exothermic reaction are placed in a way to provide the necessary heat
of the endothermic reaction in the shell side. The exothermic reaction occurs on the spherical commercial PdAl2O3 (1.1 wt.%)

111

M.R. Rahimpour et al. / Fuel 97 (2012) 109118

Hydrogen
Compressor

Off Gas
Condenser
Reflux Drum

R-3
R-2

Reformate

R-1
Stabilizer

Sep-1
H-2

H-1

Vapor

H-3

V-1

Reboiler

Cooler
Reformate
E-1

Naphtha Feed
Pump
Fig. 1. Schematic for conventional tubular naphtha process (CTR).

Fig. 2. A conceptual schematic for thermally coupled naphtha reactor (TCR).

catalyst [28] while the catalyst of the naphtha reforming process is

composed of 0.3% Platinum (Pt) and 0.3% Rhenium (Re) on an
alumina basis (Pt/Re/Al2O3). Moreover, unlike the previous research, the third reactor has been substituted by the mentioned
thermally coupled reactor. The specication and details of both
exothermic and endothermic sides have been presented in previous study [29]. Note that the molar ow rates of nitrobenzene
and steam are considered as those reported by Abo-Ghander
et al. [21]. Adding steam to the feed line prevents the coke
formation on the catalysts. It may reduce the temperature along

the hydrogenation side and also reduce the exothermic reaction

rate by diluting the reacting mixture.

3. Reaction scheme and kinetic expressions

3.1. Endothermic side (shell side)
A kinetic model based on the Smiths model is taken into consideration [2]. Four dominant reactions are considered as follows:

112

M.R. Rahimpour et al. / Fuel 97 (2012) 109118

 Dehydrogenation of naphthenes to aromatics

NaphthenesCn H2n $ AromaticsCn H2n6 3H2

FtubeIz

FshellIz

Exothermic side
(nitrobenzene hydrogenation)

 Dehydrocyclization of parafns to naphthenes

Endothermic side
(Naphtha reforming)

NaphthenesCn H2n H2 $ ParaffinsCn H2n2

dz

 Hydrocracking of naphthenes to lower hydrocarbons

NaphthenesCn H2n n=3H2 ! Lighter endsC1 C5

FshellIz+dz

 Hydrocracking of parafns to lower hydrocarbons

FtubeIz+dz

Heat transfer

ParaffinsCn H2n2 n  3=3H2 ! Lighter endsC1 C5

The rate equations of these reactions are expressed in the

previous studies [29].
3.2. Exothermic side (tube side)
Identication of coupled reactions is a controversial and a number of requisites should be considered in order to nd appropriate
reactions which can be thermally coupled. Our strategy here can be
summarized as below:
First and foremost, the exothermic reactions should be took
place in higher temperature in order to have a desirable heat transfer from the exothermic side to the endothermic one while it worth
to mention that the inlet temperature should also be nearly the
same. Secondly, both sides should have approximately the same
amount of heat generation and consumption rates (ri  DHi). Besides, as long as the reactions are selected appropriately, the mass
transfer as well as heat transfer can be carried out between shell
and tube side by aid of membrane technology. This factor has been
considered here in order to use the produced hydrogen from
reforming and manage the exothermic reaction. This feature needs
a consideration of pressures in both sides owing to having a desirable mass transfer gradient (Shell side pressure is higher than the
tubes). From commercial point of view, aniline is an important raw
material for synthetic of more than 300 different end products
such as dyes, rubber chemicals, amino resins, and polyurethane
(MDI). On the other hand, at the present time this product is imported and does not produced domestically. Hence, the hydrogenation of nitrobenzene to aniline has been considered as a part of our
study. The hydrogenation reaction of nitrobenzene to aniline is
given by:

C6 H5 NO2 3H2 ! C6 H5 NH2 2H2 O

The rate expression provided by Klemm et al. [30] is as follows:

0

k K NB K H2 PNB P:5
H2
2
1 K NB PNB K H2 P:5
H2

10

The reaction rate constant (k0 ), equilibrium constants (Ki), the

activation energy (E) and standard heat of reaction (DH298K) are
all discussed in the previous studies [29].
4. Mathematical modeling
In this study, a homogeneous one-dimensional model has been
considered. The basic structure of this model is composed of heat
and mass balance conservation equations obtained by using thermodynamic and kinetic relations, as well as auxiliary correlations
for predicting physical properties. A differential element (Fig. 3)
is considered along the axial direction inside the reactor congurations to derive the mentioned equations. The mass and energy
balance equations are written for uid phase in each side. The nal
results are summarized in Table 1. The positive sign in Eq. (14) is

Fig. 3. A differential element along the axial length of TCR.

used for the endothermic side and the negative sign for the exothermic side.
The following assumptions have been considered in this
research:
(i)
(ii)
(iii)
(iv)

(v)
(vi)
(vii)
(viii)

Steady state conditions.

Plug ow pattern is considered.
Adiabatic reactors have been used.
Catalyst deactivation is not considered (since there is not a
reliable deactivation rate for the hydrogenation of nitrobenzene through the literature under the industrial condition).
Ideal gas behavior on both sides.
Negligible axial heat dispersion.
Porosity is constant along the shell and tube sides.
Pressures along both compartments are calculated based on
Erguns equation [31].

5. Steady state model validation for CTR

The model validation has been investigated considering observed plant data for CTR at steady state condition. Table 2 presents the plant data and predicted mole fractions of the
components at the output of the process. Model results show
acceptable agreement with the plant data (also the model has been
validated for dynamic condition during 800 days of operation
[27]). By utilizing the PONA Test in Stan Hop Seta apparatus, each
component (parafn, naphthene and aromatic) has been analyzed.
The aromatic is tested especially by ASTM 2159 equivalent to UOP
273 method [32].
6. Differential evolution (DE) method
Differential evolution (DE) is a heuristic approach based on
optimization evolutionary algorithms and random search methods.
This technique was presented by Storn and Price [33] for the rst
time and soon it has been paid intensive attention as a fast, easy
to use, and efcient method of optimization. Consequently, this
method has been employed for several kinds of problems with
computation intensive cost functions. DE is used for minimization
of nonlinear, non-differentiable, multimodal and continuous space
functions and is able to handle optimization problems involving
complex mathematical models. It is a self-organizing and stochastic direct search approach which is compatible for numerical optimization and is more likely to nd the global optimum of the
function. These advantages make DE a useful and an applicable
technique especially for chemical engineering relevant problems.
DE has been successfully applied for solving several complex problems and is now being identied as a potential source for more

113

M.R. Rahimpour et al. / Fuel 97 (2012) 109118

Table 1
Mass and energy balance equations.
Denitions

Equations

Nos.

Fluid phase

1 dF i;j
Acj dz

(11)

r i;j qb
P
i dF i;j

(12)

dF tj

dM ave;j

dF tj
F 2t

(13)

_j
m

1
Ac j
dP
dz

Boundary
conditions

C gpj

dF t j T j
dz

150l 1e2 Q
2
e3 A c
/2s dp

z 0;

pD

 Ac j UT Tube  T Shell qb

F i F i0 ;

i r i;j DH f ;i

(14)
(15)

1:75q 1e Q 2
/s dp e3 A2c

T T0

(16)

accurate and faster optimization. Complementary description

regarding the DE approach can be found in previous publications
[3437].
7. Optimization
In this study, DE method is used to maximize the aromatic,
hydrogen and aniline molar ow rates as well as the aromatic in
reformate mole fractions:



Out
Out
Out
Sum Y Out
Aromatic = Y Paraffin Y Naphthene Y Aromatic

17

and the sum of aromatic and hydrogen yields:


 
 
 

In
Out
In
Sum YOut
H2 = Y H2 YAromatic = YAromatic

18

where YOut and YIn are the mole fractions in the outlet of the third
reactor and the inlet of the rst reactor, respectively. The constraints of optimization step are determined as follows:
3
X

W Exothermic
1;
i

i1

3
X

W Endothermic
1
i

19

i1



End
< 810 K
Max T Exo
i ; Ti
3
X

20

Y Exo
Fi 1

21

i1

H2 =HC > 4:73

22

where i represents the number of the reactors, Wi is the mass distribution of the catalysts in each reactor, Ti is the temperature in both
exothermic and endothermic sides and YF i is the fraction of exothermic feedstock ow which enters to each reactor. The difference between the inlet and outlet pressure in the shell side of optimized
reactor ought to be lower than that of in the CTR.

Several decision variables are considered to be optimized in this

research. A complete list of optimized variables with their variation range and optimized values has been presented in Table 3.
The total mass of catalyst in both exothermic and endothermic
sides has been assumed to be constant and the related optimum
inlet molar ow rates have been calculated. As it can be seen, by
proper design and catalyst mass distribution in the three reactors
of naphtha reforming, the inlet fresh naphtha feed can be increased
as high as 33.46 % compared with the CTR. In the naphtha reforming process, the hydrogen amount is very effective. The recycle
stream shown in Fig. 1 mainly consists of hydrogen and light-end
components. As a result, the amount of hydrogen entering the
reactor is an effective parameter which determines the H2/HC ratio
and can be adjusted in the process. Considering the increase in the
naphtha molar ow rate, in order to have a xed value of H2/HC ratio, the hydrogen mole fraction in the recycle gas should also increase. H2/HC molar ratio is one of the main parameters in the
reforming units which should be controlled frequently and properly. Low values accelerate the polymerization of the coke on the
catalyst surface. The outlet pressure of the compressor entering
the rst reactor is also optimized. In order to reduce the coke formation on the surface of catalysts, it is generally attempted to increase the pressure while lower pressure increases the aromatic
production [1]. The length to diameter ratio (LOD) is another effective parameter in performance of the reactor that should be optimized. If this ratio increases, the pressure drop inside the reactor
also increases. However, at lower values of this ratio channeling
occurs. On the other hand, decreasing the length to diameter ratio
has the merit of processing excessive feed ow rate entering the
reactor. The achieved result conrms that the total molar ow rate
of the exothermic side has increased about 25.25% in comparison
with the non-optimized conguration. In a short term, more aniline is produced in the optimization process. The exothermic catalyst mass distribution of the third reactor is the least one owing to
a small temperature drop in the shell side of the conventional reactor (naphtha side). As it is evident, the optimum inlet temperature
of rst reactor in the exothermic side is exactly the same as the inlet temperature of endothermic side which reduces the thermal
loss in the coupled conguration.
8. Results and discussion
The results of the optimization process are categorized in two
sections. First, the results of the shell side (naphtha reforming)
are analyzed and then the exothermic side is considered.
8.1. Endothermic side
Aromatics have high octane numbers which is always above
100 (except for benzene) and can be used to compensate the gasoline octane loss due to elimination of MTBE [1,38]. Fig. 4 indicates

Table 2
Comparison between model prediction and plant data for fresh catalyst.
Reactor no.

Inlet temperature (K)

Inlet pressure (kPa)

Catalyst distribution (wt.%)

Input feedstock (mol%)

1
2
3

777
777
775

3703
3537
3401

20
30
50

Parafn
Naphthene
Aromatic

Reactor no.

Outlet temperature (K)

Plant

1
2
3

722
753
770

CTR

726.13
751.75
770.83

49.3
36
14.7

Aromatic in reformate (mol%)

TCR

Plant

Non-optimized

Optimized

760.77
801.19
799.59

751.95
796.49
808.52



57.7

CTR

35.1422
47.4499
56.0612

TCR
Non-optimized

Optimized

44.0261
62.1032
85.7659

42.4436
58.3719
88.3592

114

M.R. Rahimpour et al. / Fuel 97 (2012) 109118

Table 3
Optimized parameters and their values.
No.

Decision variable

Min.

Max.

Optimized value

Endothermic side (naphtha reforming)

1
Total fresh naphtha feed to the 1st reactor (kmol/h)
2
Hydrogen mole fraction in the recycle gas
3
Catalyst mass distribution for the 1st reactor (weight fraction)
4
Catalyst mass distribution for the 2nd reactor (weight fraction)
5
Catalyst mass distribution for the 3rd reactor (weight fraction)
6
Naphtha compressor outlet pressure (kPa)
7
LOD of the 1st reactor
8
LOD of the 2nd reactor
9
LOD of the 3rd reactor
10
Inlet naphtha feed temperature to the 1st reactor

266
0.65
0.1
0.1
0.1
2000
1.5
1.5
1.5
677

360.00
0.81
0.5
0.5
0.5
3703
2.07
1.8
2.8
777

355
0.76
0.22
0.29
0.49
3526
2.01
1.62
2.66
777

Exothermic side (nitrobenzene hydrogenation)

11
Total molar ow rate for the exothermic side
12
Exothermic side molar ow rate to the 1st reactor (% of total molar ow rate)
13
Exothermic side molar ow rate to the 2nd reactor (% of total molar ow rate)
14
Exothermic side molar ow rate to the 3rd reactor (% of total molar ow rate)
15
Catalyst mass distribution for the 1st reactor (weight fraction)
16
Catalyst mass distribution for the 2nd reactor (weight fraction)
17
Catalyst mass distribution for the 3rd reactor (weight fraction)
18
Exothermic side temperature to the 1st reactor (K)
19
Exothermic side temperature to the 2nd reactor (K)
20
Exothermic side temperature to the 3rd reactor (K)
21
Inlet pressure of the exothermic side for the 1st reactor (kPa)
22
Inlet pressure of the exothermic side for the 2nd reactor (kPa)
23
Inlet pressure of the exothermic side for the 3rd reactor (kPa)
24
Number of tubes for the 1st reactor
25
Number of tubes for the 2nd reactor
26
Number of tubes for the 3rd reactor

100
0.1
0.1
0.1
0.1
0.1
0.1
777
777
777
70
70
70
1
1
1

1000
0.5
0.5
0.5
0.5
0.5
0.5
800
800
800
300
300
300
1000
1000
1000

992
0.41
0.48
0.11
0.33
0.38
0.29
777
782
790
293
281
109
882
881
860

successful aromatic production in the OTCR. The aromatic molar

ow rate increases 41 and 65 kmol/h compared with the TCR and
CTR, respectively. The aromatic yield increases about 26.30% in
comparison with the CTR. The related yield denition is as follows:

YieldAromatic

F Out
Aromatic

23

F Fresh naphtha feed

The related rate for aromatic production (reaction No. 1) is depicted

in Fig. 5. The dimensions are considered in a way that the area under
each graph shows the aromatic production in the reactor. The total
areas for CTR, TCR and OTCR are 94.34, 118.08 and 158.93 kmol/h,
respectively.
The superiority of the OTCR for hydrogen production is demonstrated in Fig. 6. Hydrogen demand has increased recently in the
reneries mainly due to: (a) Stricter legislation on sulfur content

in fuels increases the need for hydrotreating and (b) Processing

of heavier crude oils and reduced market for heavy fuels is forcing
to greater use of hydrocracking and the catalytic reformers are under pressure to response such an urgent need. The outlet hydrogen
production in TCR is even less compared with the CTR case. Most of
the hydrogen is produced in the rst reactor which is due to the
dehydrogenation reaction (No. 1).
In addition to the temperatures of the reactors, the inlet H2/HC
ratio of the rst reactor should be controlled continuously. This
ratio has a dual role in the unit. First, the proper ratio will reduce
the probability of coke formation on the catalyst surface and on
the other hand, lower ratios shift the reactions toward hydrogen
and aromatic production. Accordingly, the superiority of using
membrane reactors becomes noticeable. Membrane layers may extract the extra hydrogen from the reaction side which reduces the

0.14

140

First reaction rate (kmole/kg cat. hr)

Aromatic production (kmole/hr)

160

120
100
80
60
CTR
TCR
OTCR

40
20
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Length of reactor (Dimensionless)

Fig. 4. Total molar ow rate of produced aromatic compounds in the CTR,
optimized and non-optimized TCR.

0.12
0.1

CTR
TCR
OTCR

0.08
0.06
0.04
0.02
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Length of reactor (Dimensionless)

Fig. 5. Change of dehydrogenation reaction rate (reaction No. 1) along the three
reactors of CTR, optimized and non-optimized TCR.

115

M.R. Rahimpour et al. / Fuel 97 (2012) 109118

810
800

300

790
250
200

Temperature (K)

Hydrogen production (kmole/hr)

350

235.6
235.4
235.2

150

235
234.8

100

CTR
TCR
OTCR

50
0

0.998

780
770
760

CTR
TCR
OTCR

750

740
730

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

720

0.1

Length of reactor (Dimensionless)

0.4

0.5

0.6

0.7

0.8

0.9

Fig. 8. Temperature prole of shell side (endothermic side) for three possible case
studies.

8.5

8
7.5
7

820
810

CTR
TCR
OTCR

800

Temperature (K)

H2 /HC molar ratio

0.3

Length of reactor (Dimensionless)

Fig. 6. Total molar ow rate of produced hydrogen.

0.2

6.5
6
5.5

790
780
770

Endothermic side
Exothermic side

5
760

4.5

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

750

Length of reactor (Dimensionless)

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Length of reactor (Dimensionless)

350

300

x 10

250

reaction rate (kmole/kg cat.hr)

Light ends production (kmole/hr)

CTR
TCR
OTCR

200
150
100
50
0

Endothermic heat of reaction

Transfered heat

6
5
4
3
2
1

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Length of reactor (Dimensionless)

Fig. 7. (a) H2/HC molar ratio and (b) the light ends production rate along the CTR,
optimized and non-optimized TCR.

H2/HC ratio and increases the aromatic production, simultaneously. H2/HC ratio along the reactors is shown in Fig. 7a. The
light ends are other promising products in the reneries. These

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Length of reactor (Dimensionless)

Fig. 9. A comparison between (a) thermal proles of exothermic and endothermic
sides and (b) the endothermic heat of reaction and transferred heat for optimized
TCR.

gases are used as LPG feed stock. It is claimed that more LPG can
be produced by using the OTCR (Fig. 7b).

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M.R. Rahimpour et al. / Fuel 97 (2012) 109118

7

4.5

x 10

x 10

hr)

1.2

2.5

1.15

1.1
1.05

1.5

x 10

1.26

2.5

1.25

2
1.24

1.5

0.6227

0.5
0

3.5

0.3255 0.326 0.3265

Transfered heat
Exothermic heat of reaction

3.5
3

x 10

4.5

Transfered heat
Exothermic heat of reaction

cat.

cat.

hr)

Heat flux (kJ/kg

Heat flux (kJ/kg

0.6228

0.5
0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

Length of reactor (Dimensionless)

0.45

0.5

0.55

0.6

Length of reactor (Dimensionless)

18

x 10

16
Transfered heat
Exothermic heat of reaction

Heat flux (kJ/kg

cat.

hr)

14
12
10

1.71

x 10

1.7

1.69

1.68
1.67

4
2
0

0.65

0.7

0.75

0.8

0.85

0.9999

0.9

0.95

Length of reactor (Dimensionless)

Fig. 10. A comparison between the generated heat in the exothermic side and transferred heat from exothermic section in the (a) rst reactor, (b) second reactor and (c) third
reactor of optimized TCR.

8.2. Exothermic side

Fig. 9a compares the temperature proles in both exothermic
and endothermic sides of OTCR and Fig. 9b clearly justies the
behavior of Fig. 9a for the endothermic side. At the rst reactor,
the transferred heat from exothermic side to the endothermic
one is lower compared with the consumed heat in the reforming
process. Consequently, the temperature of shell side falls gradually.
Fig. 10ac explains the generated and transferred heat from the
exothermic side. Since the generated heat is more compared with
the transferred one at the entrance of the rst reactor, a peak is
generated in the thermal prole of exothermic side (see Fig. 9a).
Fig. 10bc magnies the thermal behavior in the other two reactors (the second one and the third one).
Generally, Nitrobenzene has been used as the raw material in
order to produce aniline by utilizing xed-bed or uidized bed
vapor phase reactors [40,41]. Over the last 145 years, aniline has
become one of the hundred most important building blocks in

100
90

Nitrobenzene conversion

The thermal behavior of endothermic side is investigated in

Fig. 8. A rule of thumb for estimating the effect of temperature is
that the octane number increases by one unit for an increase in
the reaction temperature of catalyst 2.8 C [39].

80
70
60
50
TCR
OTCR

40
30
20
10
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Length of reactor (Dimensionless)

Fig. 11. (a) Nitrobenzene molar ow rate and (b) nitrobenzene conversion in the
exothermic side of optimized TCR.

chemistry. Aniline is known to be used in the production procedure

of more than 300 different end products such as, isocyanates,

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M.R. Rahimpour et al. / Fuel 97 (2012) 109118

Table 4
Comparison between Conventional, optimized and non-optimized thermally coupled naphtha reforming reactor.
No.

1
2
3

Reformate production (kmol/h)

Aniline production (kmol/h)

CTR

TCR

OTCR

263.7
256.6
237.9

259.0
224.6
183.3

346.3
309.4
239.0

rubber processing chemicals, dyes and pigments, agricultural

chemicals and pharmaceuticals [40]. Fig. 11 presents the nitrobenzene conversion vs. the dimensionless length of reactors. Note that
the length of the reactors is not the same in TCR and OTCR. It
should be mentioned that the mass of catalyst is the same for both
TCR and OTCR. However, the total mass of catalyst is distributed in
three reactor of OTCR while it is situated in the rst and second
reactors of TCR. The optimization allows us to increase the total
aniline production as high as 39.21% compared with non-optimized TCR conguration.
The pressure drop in the CTR is about 400 kPa. Temperature increases along the TCR and consequently the viscosity and related
losses are increased. Since the length to diameter ratio of the optimized reactor is lower compared with the non-optimized reactor,
the pressure drop in the OTCR decreases signicantly. This is favorable and reduces the operational costs of recompression. The optimization program dened the value of 3526 kPa as the best outlet
pressure of the compressor for naphtha feed. Depletion in the pressure is just about 120 kPa for OTCR.
Finally, Table 4 is prepared to show the best possible results
according to the optimization process and compares the conventional, thermally coupled and optimized thermally coupled
reactors.

9. Conclusion
Considering the higher thermal efciency as well as the lower
operational costs, utilizing thermally coupled conguration has
been given priority in this study. Differential Evolution (DE) method has been used in order to obtain the best possible operating
conditions. Twenty-six decision variables have been assigned to
control every aspect of the process. Catalyst mass distribution, exothermic inlet temperature, operating pressures, number of tubes in
the exothermic side and the total molar ow rates are the most
important optimized parameters. By controlling these decision
variables, the hydrogen and aromatic production rates have been
improved compared with the non-optimized situation. Keeping
the H2/HC molar ratio in the acceptable range and considering
the fact that the sum of the catalyst weight fraction for the three
reactors should be unity are among the main constraints in the
optimization process. The obtained results imply that using the
optimized thermally coupled reactor conguration can be a compelling way to boost the hydrogen and aromatic production rate.

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