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 ) 1 0 9 8 4 e1 0 9 9 3

Available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Mathematical modeling of a multi-stage naphtha reforming

process using novel thermally coupled recuperative reactors
to enhance aromatic production

Davood Iranshahi, Ali Mohammad Bahmanpour, Ehsan Pourazadi,

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

article info abstract

Article history: In this study, a novel thermally coupled reactor containing the naphtha reforming process
Received 28 April 2010 in the endothermic side and the hydrogenation of nitrobenzene to aniline in the
Received in revised form exothermic side has been investigated. Considering the higher thermal efficiency as well as
5 July 2010 the smaller size of the reactor, utilizing the recuperative coupled reactor is given priority. In
Accepted 14 July 2010 this novel configuration, the first and the second reactor of the conventional naphtha
Available online 21 August 2010 reforming process have been substituted by the recuperative coupled reactors which
contain the naphtha reforming reactions in the shell side, and the hydrogenation reaction
Keywords: in the tube side. The achieved results of this simulation have been compared with the
Naphtha reforming results of the conventional fixed-bed naphtha reforming reactors. Acceptable enhance-
Aromatic production ment can be noticed in the performance of the reactors. The production rate of the high
Recuperative coupling octane aromatics and the consumption rate of the paraffins have improved 17% and 72%,
Nitrobenzene hydrogenation respectively. The conversion of the nitrobenzene is acceptable and the effect of the number
of the tubes also has been taken into account. However, the performance of the new
configuration needs to be tested experimentally over a range of parameters under practical
operating conditions.
ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction the process. Smith [3] classified the naphtha reforming process
into four main reactions. Ramage et al. [4] considered the coke
Catalytic naphtha reforming is one of the main processes to formation and, consequently, the catalyst deactivation in the
produce high octane gasoline. The conventional process process. Fathikalajahi and Rahimpour [5] calculated the
consists of three or four adiabatic reactors in series with optimum catalyst mass distribution in the industrial naphtha
intermediate heaters [1]. Low e octane hydrocarbons such as reforming system according to the Smith’s model. Catalyst
paraffins and naphthenes are converted to high e octane regeneration was suggested by a model presented by Lee et al.
aromatics through this process. Hydrogen and other light [6]. Rahimpour et al [7,8] presented the Kinetic and deactivation
gases such as propane and butane are also produced [2]. model for the industrial catalytic naphtha reformers. Lid and
Several research efforts have been made and some modifi- Skogestad [9] determined the optimal operating conditions for
cations have been proposed to enhance the production of the a catalytic naphtha reformer with continuous catalyst regen-
aromatics and hydrogen, as well as the operating conditions of eration for four reactors utilizing the Smith’s model.

* Corresponding author. Tel.: þ98 711 2303071; fax: þ98 711 6287294.
E-mail address: [email protected] (M.R. Rahimpour).
0360-3199/$ e see front matter ª 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.07.077
 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 ) 1 0 9 8 4 e1 0 9 9 3 10985

Table 1 e Specifications of reactors, feed, product and

Catalysts
Reactor1 catalyst of plant for fresh catalyst.
Parameter Numerical value Unit
3
Naphtha feed stock 30.41  10 Kg/h
Reformate 24.66  103 Kg/h
Heater 2
H2/HC mole ratio 4.74 e
Reactor 2
LHSV 1.25 h1
Mole percent of hydrogen 69.5 e
in recycle
Diameter and length of 1.25, 6.29 M
1st reactor
Heater 3 Diameter and length of 1.67, 7.13 M
Heater 1 2nd reactor
Reactor 3 Diameter and length of 1.98, 7.89 M
Off Gas 3rd reactor

Distillation fraction of naphtha feed and reformate

TBP Naphtha feed ( C) Reformate ( C)
IBP 106 44
Separator

10% 113 73
Stabilizer

30% 119 105

50% 125 123
70% 133 136
90% 144 153
FBP 173 181
Hydrogen rich make gas Typical properties of catalyst
Feed Gas Reformate to
storage dp 1.2 Mm
Pt 0.3 wt%
Fig. 1 e Schematic of the conventional catalytic naphtha Re 0.3 wt%
reforming process. sa 220 m2/g
rB 0.3 Kg/l
3 0.36 e

Khosravanipour Mostafazadeh and Rahimpour [10] suggested

a membrane catalytic bed reactor to separate the produced
hydrogen in the naphtha reforming process. The hydrogenation of nitrobenzene to aniline is an
Considering the disadvantages of the methane combustion important process in industry which is highly exothermic [19].
reaction as well as the high rate of energy consumption in the The valuable product of this reaction is produced in large
conventional naphtha reforming process, utilizing the recuper- scale. Therefore, any improvement in the production rate of
ative coupled reactor is suggested in order to solve these issues. aniline attracts attention in industry. Aniline has been applied
Besides, applying this novel configuration may decrease the in methylene diphenyl diisocyanate (MDI) synthesis and also
operational and capital costs [11]. Also the high thermal energy rubber processing. By using nitrobenzene hydrogenation
of the hydrogenation process can be controlled and treated. reaction as the heat source in the exothermic side of the
Generally, the coupled reactors classify into three main reactor, Abo-Ghander et al. achieved 80% nitrobenzene
categories: direct coupling, regenerative coupling, and recu- conversion in their study [20]. This conversion has been
perative coupling. Recently, recuperative coupling has gained improved in the present research.
the interest of many researchers. Itoh and Wu [12] modified the
adiabatic coupled reactors by modeling a palladium membrane
reactor. Elnashaie et al. [13], and also Moustafa and Elnashaie
[14] developed a heterogeneous model for ethyl benzene 2. Process description
dehydrogenation process in a membrane catalytic reactor. The
dehydrogenation of ethyl benzene occurs in the endothermic 2.1. Conventional naphtha reforming process (CNRP)
side, while the produced hydrogen permeates through the
hydrogen perm-selective membrane and provides the A simplified schematic for the conventional catalytic naphtha
exothermic hydrogenation reaction with the necessary reac- reforming process is shown in Fig. 1. The feed gas is mixed with
tant. For this case, the mathematical model is developed and a recycle gas stream containing 60e90% hydrogen. The recycled
the effects of co-current and counter-current flow patterns are hydrogen can adjust the H2/HC ratio through the reactors to
investigated. Ramaswamy et al. [15] applied a one-dimensional prevent coke formation which can jeopardize the performance
plug flow model to discuss different behaviors of coupled first of the catalyst. After mixing, the total reactor charge is heated
order reactions in directly coupled adiabatic reactors. Khademi and passed through three adiabatic catalytic reactors equipped
et al. [16e18] considered methanol synthesis thermally with three intermediate heaters to adjust the reactor’s inlet
coupled with dehydrogenation of cyclohexane, to prepare pure temperatures. Leaving the third reactor, the discharges enter
hydrogen, in a co-current reactor. the separator which produces reformates as the bottom
10986 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 ) 1 0 9 8 4 e1 0 9 9 3

Nitrobenzene
Tank

Catalysts

Water + Hydrogen
Heater 1

Transferred

Separator
Heat

Cooler

Aniline+ Nitrobenzene
Reactor 3
Off Gas
Separator

Stabilizer

Hydrogen rich make gas

Feed Gas
Reformate to
storage

Fig. 2 e Schematic diagram of the coupled reactors.

products. Table 1 shows the specific properties and operational reactions are carried out over commercial Pt/Re/Al2O3 catalyst
conditions of the conventional naphtha reforming reactors. (0.3% Platinum and 0.3% Rhenium). The tube side is filled with
the commercial PdeAl2O3 (1.1 wt.%) catalyst with spherical
shape [19]. Table 2 shows the specific properties and operational
2.2. Thermally coupled naphtha reforming configuration
conditions for the exothermic side (hydrogenation of nitroben-
(TCNRC)
zene). The molar flow rates for nitrobenzene and steam are
considered as those reported by Abo-Ghander et al. [20].
Fig. 2 presents the schematic diagram of the coupled reactors. In
the present research, the first two reactors in the conventional
process have been substituted with the highly efficient recu-
perative reactors which contain the hydrogenation of nitro-
benzene to aniline in the exothermic side and the naphtha 3. Reaction scheme and kinetics
reforming process in the endothermic side which are separated
by solid tube walls. Catalytic reforming is supposed to take place 3.1. Endothermic side
in the shell side whereas the exothermic hydrogenation of
nitrobenzene to aniline is considered to provide the heat for Considering the simplified model suggested by Smith [3], four
reforming process in the tube side. The external walls are main reactions have been defined as the governing reactions
assumed to be adiabatic. The catalytic naphtha reforming of the naphtha reforming process. Generally, these four
 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 ) 1 0 9 8 4 e1 0 9 9 3 10987

Table 2 e Operating condition for hydrogenation reaction of nitrobenzene to aniline.

Parameter Numerical Value Unit

Inlet temperature 780 K

Inlet pressure 1.1  105 Pa
Catalyst density 1400 Kg/m3
Diameter of catalyst particle 4.7  103 m
Void fraction 0.46 e

1st Reactor
Available cross-sectional area of the tube side for flow 3.29 m2
Nitrobenzene molar flow rate 7.24 mol/s
Hydrogen molar flow rate 28.98 mol/s
Aniline molar flow rate 0.72 mol/s
Steam molar flow rate 72.46 mol/s

2nd Reactor
Available cross-sectional area of the tube side for flow 2.91 m2
Nitrobenzene molar flow rate 6.41 mol/s
Hydrogen molar flow rate 25.67 mol/s
Aniline molar flow rate 0.64 mol/s
Steam molar flow rate 64.19 mol/s

reactions take place in the endothermic side of the reactor. 3.2. Exothermic side
The reactions are as follows:
The hydrogenation of nitrobenzene to aniline can be
expressed by:

1. Naphthenes (CnH2n) 4 Aromatics DH1 ¼ 71.0 kJ/mol C6 H5 NO2 þ 3H2 /C6 H5 NH2 þ 2H2 O (5)
(CnH2n6)þ3H2
The rate expression provided by Klemm et al. [22] is as
2. Naphthenes (CnH2n)þH2 4 Paraffins DH2 ¼ 36.9 kJ/mol
(CnH2nþ2)
follows:
3. Naphthenes(CnH2n) þ n/3H2 / Lighter DH3 ¼ 51.9 kJ/mol k0 KNB KH2 PNB P:5
H2
ends (C1eC5) r¼ 2 (6)
4. Paraffins (CnH2nþ2) þ (n  3)/ DH4 ¼ 56.6 kJ/mol 1 þ KNB PNB þ KH2 P:5 H2
3H2 / Lighter ends (C1eC5)
The reaction rate constant (k0 ), equilibrium constants (Ki), the
activation energy (E ) and standard heat of reaction ðDH298K Þ
The rate equations for these reactions are expressed by:
are presented in Table 4.


kf1  
r1 ¼ ke1 pn  pa p3h (1)
K e1


4. Mathematical model
kf2  
r2 ¼ ke2 pn ph  pp (2)
K e2 A one-dimensional homogeneous model has been applied to

 develop the mass and energy balance equations for the fluid
kf3
r3 ¼ pn (3) phase in each side. To obtain these equations the following
pt
assumptions have been considered:


kf4
r4 ¼ pp (4)
pt (a) The reactor operates at steady state conditions.
(b) Axial dispersion of heat is neglected.
The reaction rate constants ðkfi Þ, equilibrium constants ðKei Þ,
(c) Plug flow pattern is considered in each side of the reactor.
activation energies ðEi Þ and standard heat of reactions ðDH298K Þ
(d) Heat loss is neglected.
are tabulated in Table 3 [21].

The results are summarized in Table 5. The positive sign in

equation (10) is used for the endothermic side and the nega-
Table 3 e Rate constants and heat of reactions for tive sign for the exothermic side.
naphtha reforming.
k ¼ AexpðB  E=1:8TÞ A B E DH298K
Table 4 e Rate constants and heat of reaction for
k f1 9.87 23.21 36350 71038.06 hydrogenation of nitrobenzene.
k f2 9.87 35.98 58550 36953.33
k ¼ A0 expðB0  E0 =1:8TÞ A0 B0 E DH298K
k f3 1 42.97 63800 51939.31
k f4 1 42.97 63800 56597.54 k0 0.186 0 10 443000
Ke1 1.04  103 46.15 46045 e K H2 4.427  103 0 0 e
Ke2 9.87 7.12 8000 e KNB 1.51  105 0 0 e
10988 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 ) 1 0 9 8 4 e1 0 9 9 3

Table 5 e Mass and energy balances and auxiliary correlations.

Definitions Equations

Fluid phase
g
1 dFi;j
¼ hri;j rb (7)
Ac dz

X
dFt ¼ dFi (8)

dFt
dMave ¼ _
m (9)
F2t

Ftj g
dTj
g
pDi  g g
X  
Cpj ¼ U T2  T1 þ rb hri;j DHf ;i (10)
Ac dz Ac

dP 150m ð1  3Þ2 Q 1:75r ð1  3Þ Q 2

¼ þ (11)
dz f2s d2p 33 Ac fs dp 33 A2c
Boundary conditions
g g g g
z ¼ 0; Fi;j ¼ Fi0;j ; Tg ¼ T0 ; Pg ¼ P0 (12)

Parameter Equations Reference

2
Component heat capacity Cp ¼ a þ bT þ cT þ dT 2
[24]
Mixture heat capacity Based on local compositions
Viscosity of reaction mixtures Based on local compositions
Mixture thermal conductivity Based on local compositions [25]
2Rp ug r
Re ¼
m
Kw [26]
hi ¼ 4ð Þðrug dp =mÞ0:3
dp
Overall heat transfer coefficient o =Di Þ
1
U ¼ h1i þ Ai lnðD
2pLKw þ AAoi 1
ho

naphthene and aromatic) are performed by PONA Test in Stan

5. Simulation and results Hop Seta apparatus. The aromatic is tested especially by
ASTM 2159 equivalent to UOP 273 method.
5.1. Model validation
5.2. Discussion
The validity of the mentioned model has been checked by
comparing the applied data with the observed experimental The results of the present research have been investigated
data of the industrial packed bed reactor at the steady state through the following figures. Fig. 3(a)e(d) show the molar
conditions. Tables 6 and 7 [23] present the experimental and flow rate of main components of the naphtha reforming
theoretical data for the previously mentioned case. Obviously, process for three different cases to compare the results. The
the predicted results do not deviate from the experimental first case is the conventional packed bed reactor, in the second
results significantly. Analyses of the components (paraffin, case the first reactor has been substituted by a thermally

Table 6 e Comparison between model prediction and plant data for fresh catalyst.
Reactor Nu. Inlet temperature (K) Inlet pressure (Kpa) Catalyst distribution (wt%) Input feedstock (mol%)

1 777 3703 20 Paraffin 49.3

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

Outlet temperature (K) Aromatic in reformate (mol%)

Plant CNR TCNR Plant CNR TCNR

1 722 727 752 e e e

2 753 751 780 e e e
3 770 771 779 57.7 56.2 95.8
 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 ) 1 0 9 8 4 e1 0 9 9 3 10989

Table 7 e Comparison between predicted production rate and plant data.

Time (day) Naphtha feed (ton/h) Plant (kmol/h) Model (kmol/h) Devi % (Tubular-plant)

0 30.41 225.9 221.58 1.91

34 30.41 224.25 222.64 0.71
62 31.00 229.65 228.18 0.64
97 30.78 229.65 227.09 1.11
125 31.22 229.65 231.19 0.67
160 31.22 229.65 231.72 0.90
188 28.55 211.6 210.16 0.68
223 30.33 222.75 225.19 1.09
243 31.22 233.05 232.74 0.13
298 30.67 228.65 228.75 0.04
321 30.76 227.64 229.69 0.90
398 42.35 317.3 326.18 2.79
425 42.32 317.94 326.12 2.57
461 42.32 317.94 326.38 2.65
490 42.32 317.94 326.56 2.71
524 42.32 313.09 326.77 4.36
567 42.54 317.94 328.83 3.42
610 42.54 313.9 329.06 4.82
717 37.86 286.15 290.79 1.62
771 38.51 282.1 296.4 5.06

a 140
b 100
1st Case
90
120 2nd Case
80 3rd Case
Naphthene molar flow rate (kmole/hr)
Paraffin molar flow rate (kmole/hr)

100
70

60
80
50
60
40

40 30

20
1st Case
20
2nd Case 10
3rd Case
0 0
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)

c 180
d 1550

160
1500
Hydrogen molar flow rate (kmole/hr)
Aromatic molar flow rate(kmole/hr)

140

1450
120

100 1400

80
1350

60

1st Case 1300 1st Case

40 2nd Case
2nd Case
3rd Case 3rd Case
20 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. 3 e Molar flow rate of the main components of the naphtha reforming process for three different cases.
10990 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 ) 1 0 9 8 4 e1 0 9 9 3

a 30 a 1100

1st reactor

Maximum temperature in the exothermic side (K)

1050 2nd reactor
25
Aniline molar flow rate (kmole/hr)

1000
20

950

15
900

10 850

5 800
1st reactor
2nd reactor
750
0 0 100 200 300 400 500 600 700 800 900 1000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Number of tubes
Length of reactor (Dimensionless)

30
b 1100

b N=1
N=10
1st reactor 1050
N=100

Temperature of the exothermic side (K)

25 2nd reactor N=750
Nitrobenzene molar flow rate (kmole/hr)

1000

20 950

900
15

850
10

800

5
750
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Length of reactor (Dimensionless)
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Length of reactor (Dimensionless) Fig. 5 e Effect of the number of the tubes on (a) maximum
temperature in the tube side (b) temperature profile of the
c 110 tube side.

100 1st reactor

2nd reactor
Hydrogen molar flow rate (kmole/hr)

90
tube side and the naphtha reforming process in the shell side.
80 The molar flow rate of paraffin has been investigated in Fig. 3
(a) for the three cases mentioned above. As it can be seen, the
70
effect of the modification is obvious. Lower molar flow rate of
60
paraffin shows the improvement of the naphtha reforming
process. The difference in the consumption rate of paraffin for
50 these cases will be more sensible in the second and third
reactors. This means that the forth reaction will be predomi-
40
nant in these two reactors. Lowering the space velocity or
30 raising the temperature of the naphtha reforming process
may enhance the octane number of the reformate [3]. Utilizing
20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 the thermally coupled reactors may provide higher tempera-
Length of reactor (Dimensionless) ture in the reaction zones and consequently more naphthene
consumption rate as the equilibrium conversion increases
Fig. 4 e Molar flow rate of the components in the tube side
with temperature. Therefore, as it can be noticed in Fig. 3(b),
of the reactor.
the naphthene consumption rate is higher for the third case,
although it does not change in the second case. Fig. 3(c) clearly
coupled recuperative reactor and other two reactors are the magnifies the enhancement of the performance of the reac-
same as the first case. The third case to be studied is to modify tors in the third case. The production rate of aromatic as the
the first two reactors by using the thermally recuperative desired product of the naphtha reforming process obviously
coupled reactors containing the hydrogenation reaction in the increases in the third case. The hydrogen production 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 ) 1 0 9 8 4 e1 0 9 9 3 10991

a 800 150

Consumed heat in the endothermic side

795
Generated heat in the exothermic side
Transferred heat through the tube wall
790

785 100

Heat flux (kw)

Temperature (K)

780

775
0.6
1.5
770 50 0.4
1
0.2
765 0.5
0 0
0 5 10 15 0.2 0.2005 0.201
760 exothermic side -4
x 10
endothermic side
755 0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
Mass of catalyst (Dimensionless) Mass of catalyst (Dimensionless)

b 800 Fig. 7 e Generated and consumed heat in the exothermic

and endothermic sides and the transferred heat from the
790
tube wall for TCR.

780

activity of the catalyst, the optimal number of the tubes in

770
Temperature (K)

order to minimize the maximum temperature of the

760 exothermic side has been calculated. Fig. 5(a) illustrates the
variation of maximum temperature of the exothermic side
750 with the number of tubes. As it can be seen, the optimum
temperature can be achieved by utilizing 750 tubes for each
740
reactor. The effect of the number of the tubes in each reactor
on the temperature profile of the exothermic side has been
730 TCNRC
CNRP investigated in Fig. 5(b).
720 The temperature profile of both exothermic and endo-
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
thermic sides has been shown in Fig. 6(a). Fig. 7 presents the
Mass of catalyst (Dimensionless)
variation of the generated and consumed heat in the
Fig. 6 e The temperature profiles of (a) exothermic and exothermic and endothermic sides, respectively, and trans-
endothermic sides (b) the endothermic side and the ferred heat from the tube wall along the reactor for TCR. At the
conventional naphtha reforming reactor. entrance of the first reactor, as it can be noticed from Fig. 7
the generated heat in the exothermic side is more than the
transferred heat through the tube wall. Consequently, the
which has been shown in Fig. 3(d) is almost the same for all temperature of the exothermic side rises in the beginning and
three cases. As it can be seen, the profile of hydrogen molar a peak in temperature profile can be seen in this side. Along
flow rate in the third reactor is almost flat which is due to the the first reactor, the consumed heat in the endothermic side is
fact that the net rate of hydrogen production by the first and more than the generated heat in the exothermic side, there-
second reactions is equal to the net consumption rate of fore, the temperature of the system falls as the reactions
hydrogen by the third and fourth reactions in this reactor. proceed. At the entrance of the second reactor, as it has been
The molar flow rate of the components in the tube side of magnified, the transferred heat through the tube wall is more
the reactor has been investigated through Fig. 4(a)e(c). The than the generated heat in the exothermic side, therefore, the
same space velocity used by Abo-Ghander et al. [20] has been temperature of the exothermic side drops at the beginning. As
considered in this research. Although adding steam to the the reactions proceed, the generated heat increases and the
feed line prevents the coke formation on the catalyst, it may system heats up. Clearly, according to Fig. 7, in the second
reduce the temperature along the hydrogenation side and also reactor the generated heat by the exothermic reaction is more
reduce the exothermic reaction rate by diluting the reacting than the consumed heat by the endothermic side of
mixture on the hydrogenation side. The hydrogenation of the reactor. Therefore, the temperature of both sides rises.
nitrobenzene is an irreversible reaction and it is not limited by Fig. 6(b) compares the temperature profile of the endothermic
the thermodynamic equilibrium. side of the reactor with the conventional naphtha reforming
The number of the tubes can affect the achieved results in process for the first two reactors. Utilizing the generated heat
this research. As the number of the tubes increases, the heat in the hydrogenation process, the temperature profile in the
transfer area increases as well which may affect the temper- shell side of the first reactor presented in this research
ature profile in both sides. Considering the effect of temper- maintains higher compared with that of the conventional
ature on sintering phenomena which may jeopardize the reactor. According to Fig. 7, the generated heat in the tube side
10992 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 ) 1 0 9 8 4 e1 0 9 9 3

is more than the consumed heat in the shell side in the second
a 400
st
reactor for the mentioned configuration. Therefore, the
1 reactor
temperature of the shell side rises. But in the second reactor of
Total molar flow rate of the tube side (kmole/hr)

395 2nd reactor

the industrial configuration, the temperature falls due to the
unavailability of a heat source.
390 The total molar flow rate for both sides of the thermally
coupled reactor has been shown in Fig. 8(a) and (b). Obviously,
385
the total molar flow rate in the shell side of the coupled reactor
is higher compared with that of the conventional reactor.
Fig. 9 presents the conversion of nitrobenzene along the
380
reactors. The nitrobenzene conversion in the outlet of the first
and second reactors is 84% and 87%, respectively.
375

370
6. Conclusion
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Length of reactor (Dimensionless)
The performance of the multi-stage conventional naphtha
reforming reactor was enhanced by substituting the industrial
b 2500
reactors with the thermally coupled recuperative reactors.
2450 The system was modeled utilizing a one-dimensional homo-
Total molar flow rate of the shell side (kmole/hr)

2400
geneous model. The hydrogenation reaction of nitrobenzene
to aniline occurred in the tube side of the reactor to provide
2350 the necessary heat, while the endothermic naphtha reforming
process occurred in the shell side of the reactor. According to
2300
the calculated results, the production rate of aromatic and the
2250 consumption rate of the paraffin have improved 17% and 72%,
respectively.
2200
To avoid the possibility of quick deactivation of the cata-
2150 lysts in the exothermic side, 750 tubes were considered in the
recuperative reactors to minimize the maximum temperature
2100 TCNRC
of the exothermic side. The nitrobenzene conversion was
CNRP
2050 investigated along the reactors. The nitrobenzene conversion
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 in the outlet of the first and second reactors was 84% and 87%,
Length of reactor (Dimensionless)
respectively.
Fig. 8 e The total molar flow rate for both sides of TCR. By utilizing the profile of the heat fluxes along the reactor,
the temperature profile for both sides was justified and the total
molar flow rate of both sides also was investigated. The total
molar flow rate of the endothermic side has increased 3.75%.
These results suggest that this configuration can be a compel-
ling way to boost aromatic production and ensure the other
desired results, as well. However, an investigation in relation to
90 the environmental aspects, commercial viability and economic
feasibility of the proposed configuration is necessary in order to
80 consider commercialization of the process.
70
Nomenclature
Nitrobenzene Conversion %

60

50
Ac cross-section area of reactor, m2
40 Cp specific heat capacity, kJ kmol1 K1
ap particle diameter, m
30 E activation energy for ith reaction, kJ kmol1
hi heat transfer coefficient, W m2 K1
20
H2 hydrogen, kmol h1
10 1st reactor kf1 forward rate constant for reaction (1),
2nd reactor kmol h1 kgcat1 MPa1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 kf2 forward rate constant for reaction (2),
Length of reactor (Dimensionless) kmol h1 kgcat1 MPa2
kf3 forward rate constant for reactions (3),
Fig. 9 e Conversion of nitrobenzene along the reactors. kmol h1 kgcat1 MPa2
 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 ) 1 0 9 8 4 e1 0 9 9 3 10993

kf4 forward rate constant for reactions (4), [8] Rahimpour MR. Operability of an industrial catalytic naphtha
kmol h1 kgcat1 MPa2 reformer in the presence of catalyst deactivation. Chem Eng
ke1 equilibrium constant, M Pa3 Technol 2006;5:29.
[9] Lid T, Skogestad S. Data reconciliation and optimal operation of
ke2 equilibrium constant, M Pa1
a catalytic naphtha reformer. J Process Control 2008;18:320e31.
n average carbon number for naphtha [10] Khosravanipour Mostafazadeh A, Rahimpour MR. A
Fi molar flow rate of component i, kmol h1 membrane catalytic bed concept for naphtha reforming in
Pi partial pressure of ith component, kPa the presence of catalyst deactivation. Chem Eng Process
P total pressure, kPa 2009;48:683e94.
Q volumetric flow rate, m3 s1 [11] Dautzenberg FM, Mukherjee M. Process intensification using
ri rate of reaction for ith reaction, kmol kg cat1 h1 multifunctional reactors. Chem Eng Sci 2001;56:251.
[12] Itoh N, Wu TH. An adiabatic type of palladium membrane
Sa specific surface area of catalyst pellet, m2 kg1
reactor for coupling endothermic and exothermic reactions.
T temperature of gas phase,  K J Membr Sci 1997;124:213e22.
[13] Elnashaie SSEH, Moustafa T, Alsoudani T, Elshishini SS.
Greek letters Modeling and basic characteristics of novel integrated
3 void fraction of catalyst bed dehydrogenationehydrogenation membrane catalytic
m viscosity of gas phase, kg m1 s1 reactors. Comput Chem Eng 2000;24:1293e300.
r density of gas phase, kg m3 [14] Moustafa TM, Elnashaie SSEH. Simulation production of
rb reactor bulk density, kg m3 styrene and cyclohexane in an integrated membrane reactor.
J Membr Sci 2000;178:171e84.
fs sphericity
[15] Ramaswamy RC, Ramachandran PA, Dudukovic  MP.
DH heat of reaction, kJ mol1 Recuperative coupling of exothermic and endothermic
i numerator for component reactions. Chem Eng Sci 2006;61:459e72.
j numerator for compartment [16] Khademi MH, Jahanmiri A, Rahimpour MR. A novel
FBP final boiling pint,  C configuration for hydrogen production from coupling of
HC Hydrocarbon, kmol h1 methanol and benzene synthesis in a hydrogen perm selective
membrane reactor. Int J Hydrogen Energy 2009;34:5091e107.
IBP initial boiling pint,  C
[17] Khademi MH, Rahimpour MR, Jahanmiri A. Differential
LHSV liquid hourly space velocity, h1
evolution (DE) strategy for optimization of hydrogen
Pt platinum production, cyclohexane dehydrogenation and methanol
Re rhenium synthesis in a hydrogen-perm selective membrane
RON research octane number thermally coupled reactor. Int J Hydrogen Energy 2010;35:
TBP true boiling point, K 1936e50.
WHSV weight hourly space velocity, h1 [18] Khademi MH, Setoodeh P, Rahimpour MR, Jahanmiri A.
Optimization of methanol synthesis and cyclohexane
dehydrogenation in a thermally coupled reactor using
differential evolution (DE) method. Int J Hydrogen Energy
references 2009;34:6930e44.
[19] Amon B, Redlingsho fer H, Klemm E, Dieterich E, Emig G.
Kinetic investigations of the deactivation by coking of
[1] Ancheyta-Juárez J, Villafuerte-Macı́as E. Kinetic modeling of a noble metal catalyst in the catalytic hydrogenation of
naphtha catalytic reforming reactions. Energy Fuels 2000;14: nitrobenzene using a catalytic wall reactor. Chem Eng
1032e7. Process 1999;38:395e404.
[2] D’Ippolito SA, Vera CR, Epron F, Especel C, Marécot P, [20] Abo-Ghander NS, Grace JR, Elnashaie SSEH, Lim CJ. Modeling
Pieck CL. Naphtha reforming PteReeGe/g-Al2O3 catalysts of a novel membrane reactor to integrate dehydrogenation of
prepared by catalytic reduction Influence of the pH of the Ge ethyl benzene to styrene with hydrogenation of
addition step. Catal Today; 2008:133e5. nitrobenzene to aniline. Chem Eng Sci 2008;63:1817e26.
[3] Smith RB. Kinetic analysis of naphtha reforming with [21] Rase HF. Chemical reactor design for process plants. John
platinum catalyst. Chem Eng Prog 1959;55(6):76e80. Wiley & Sons, Inc.; 1977.
[4] Ramage MP, Graziani KR, Krambeck FJ. 6 Development of [22] Klemm E, Amon B, RedlingshoK fer H, Dieterich E, Emig G.
mobil’s kinetic reforming model. Chem Eng Sci 1980;35(1e2): Deactivation kinetics in the hydrogenation of nitrobenzene
41e8. to aniline on the basis of a coke formation kinetics
[5] Fathikalajahi J, Rahimpour MR. Sensitivity of catalytic investigations in an isothermal catalytic wall reactor. Chem
naphtha reformers to different parameters. Iranian J Sci Eng Sci 2001;56:1347e53.
Technol 1992;16(1):57e67. [23] Operating Data of Catalytic Reformer Unit, Domestic
[6] Lee JW, Ko YC, Jung YK, Lee KS, Yoon ES. A modeling and Refinery, 2005.
simulation study on a naphtha reforming unit with catalyst [24] Perry RH, Green DW, Maloney JO. Perry’s chemical engineers’
circulation and regeneration system. Comput Chem Eng Handbook. 7th ed. New York, NY: McGraw-Hill; 1997.
1997;21:S1105e10. [25] Reid RC, Sherwood TK, Prausnitz J. The properties of gases
[7] Rahimpour MR, Esmaili S, Bagheri GNA. Kinetic and and liquids. 3rd ed. New York: McGraw-Hill; 1977.
deactivation model for industrial catalytic naphtha [26] Wen Dongsheng, Ding Yulong. Heat transfer of gas flow
reforming. Iran J Sci Technol Trans B Tech 2003;27:279e90. through a packed bed. Chem Eng Sci 2006;61:3532e42.