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 6 ( 2 0 1 1 ) 3 4 8 3 e3 4 9 5

Available at www.sciencedirect.com

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

A comparison of two different flow types on performance of

a thermally coupled recuperative reactor containing naphtha
reforming process and hydrogenation of nitrobenzene
D. Iranshahi, E. Pourazadi, A.M. Bahmanpour, M.R. Rahimpour*
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran

article info

abstract

Article history:

Refineries have been looking for proper ways of improving reformer performance by

Received 20 August 2010

enhancing the octane number of the product via increasing the aromatics compounds. To

Received in revised form

reach this goal, the endothermic catalytic naphtha reforming is coupled with the

20 November 2010

exothermic hydrogenation of nitrobenzene to aniline in a multifunctional heat exchanger

Accepted 8 December 2010

reactor through the process intensification concept. Considering the higher thermal effi-

Available online 13 January 2011

ciency as well as the smaller size of the coupled reactor, utilizing this reactor is given
priority. In this novel configuration, the first and the second reactor of the conventional

Keywords:

naphtha reforming process are exchanged with the coupled reactors contain the endo-

Recuperative coupling

thermic naphtha reforming in the shell side and the hydrogenation reaction in the tube

Catalytic naphtha reforming

side. Both co-current and counter-current modes of flow are examined during the opera-

Hydrogen production

tion considering various studies in literature which show the superiority of co-current flow

Aromatic enhancement

compared with the counter-current flow. The result of current study is compared with the

Nitrobenzene hydrogenation

corresponding results for conventional tubular reactor (CTR). The results show higher
aromatic production as much as 18.73% and 16.48% in the co-current and counter-current
mode, respectively. Hydrogen molar flow rate increases about 5 kmol/h by using countercurrent flow regime, compared with the CTR.
Copyright 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1.

Introduction

1.1.

Catalytic naphtha reforming process

The catalytic reforming unit has an important role in refineries.

This process includes the reconstruction of low-octane
hydrocarbons in the naphtha stream and production of more
valuable high-octane gasoline components without changing
the boiling point range. Over the past decade, refiners have
been forced to maximize their existing asset utilization. With
capital at a premium, refiners must deliver more from the units
they already have. These double pressures from environmental regulations and asset utilization have influenced the

catalytic reformer. The process licensors have responded to

these needs [1]. As a consequence, several research efforts
have been made and some modifications have been proposed
to enhance the production of the aromatic and hydrogen, as
well as the operating conditions of the process.
Studies which have been done on the catalytic naphtha
reforming process are categorized as bellow:

1.1.1. Studies on the kinetics of catalytic naphtha reforming

process
The naphtha feed stream is composed of various hydrocarbons
and related isomers which are normally influenced by various
reactions. Thus a detailed kinetic model considering all the

* Corresponding author. Tel.: 98 711 2303071; fax: 98 711 6287294.

E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
0360-3199/$ e see front matter Copyright 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.12.033

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components and reactions is too complex [2]. Accordingly,

various attempts have been made to find more acceptable
lumped groups of reactions to represent the catalytic reforming
reactions. In this way, the first significant attempt to model
a reforming system was made by Smith [3] who considered only
three basic components in naphtha main structure: These were
paraffins, naphthenes, and aromatics industrially known as
PNA. Weifeng et al. [4] developed a new kinetic model including
20 lumped components and 31 reactions. The subdivision of
8-carbon aromatics and all the hydro cracking reactions of the
paraffin lumps were taken into consideration in their model.
Boyas and Froment [5] studied a very detailed model for the
catalytic reforming of naphtha based on its fundamentals.
The model provided a thorough insight into the process and
a wide predictive potential but contained a huge number of
parameters. The current model also imposed equilibrium for
the hydrogenation and dehydrogenation reactions. Stijepovic et
al. [6] postulated a semi-empirical kinetic model for catalytic
reforming. Their lumping strategy was based on paraffins,
olefins, naphthenes and aromatics (PONA) analysis.

1.1.2. Studies on the modeling and improvement of aromatics

and hydrogen yields of the CTRs
Li et al. [7] and Taskar and Riggs [8] modeled and optimized
a semi-regenerative catalytic naphtha reformer by considering
most of its key constitutes. Juarez et al. [9] modeled and simulated four catalytic reactors in series for naphtha reforming. The
process model used an extended version of the kinetic model
reported by Krane et al. Weifeng et al. [2] considered 18-lumped
kinetic models to simulate and optimize a whole industrial
catalytic naphtha reforming process by Aspen Plus platform.
Khosravanipour and Rahimpour [10] presented a membrane
catalytic bed concept for naphtha reforming in order to enhance
hydrogen and aromatic production yield. Rahimpour et al.
[11e14] have presented novel reactor configurations and modifications which lead to higher production rate of the desired
products. In the previous studies [14], the concept of using
thermally coupled reactors containing naphtha reforming
process and hydrogenation of nitrobenzene has been investigated. In the present research, utilizing co-current and countercurrent flow regimes has been discussed and the related results
have been compared.

1.1.3.

Studies on the catalyst and catalyst regeneration

More studies have been done previously on the new catalyst

preparation and catalyst deactivation due to the coke deposition and sintering. In this way Benitez et al. [15] and Boutzeloit
et al. [16] examined the reforming efficiency and product

enhancement through the catalyst with different metal basis.

Considering the coke deposition phenomenon on the catalyst
surface and regeneration of catalyst some researches have
been made, Mazzieri et al. [17] and Sugimoto et al. [18] investigated the coke formation and regeneration of catalyst during
the catalytic naphtha reforming process.

1.2.

Catalytic hydrogenation of nitrobenzene process

1.2.1.

Literatures for coupled reactors

One of the most important advantages of using thermally

coupled reactors is to save energy which consequently reduces
the capital and operational costs [19]. Considering the lower
capital costs due to the elimination of the inter stage heaters
and related piping system and operational costs due to lower
fuel consumption, as well as higher thermal efficiency, investigation of the thermally coupled reactors has been the first
priority in this research. One should consider the fact that using
the presented configuration leads to combination of two
separate plants which indeed reduces the capital costs. Process
intensification (PI), known as the strategy of miniaturizing
process plants, is a novel design approach which can reduce
equipment size by several orders of magnitude leading to
substantial saving in capital cost, improvement of the safety
of the system and reducing environment impact [20]. In recent
years, many researches have been made in order to apply
this strategy in the coupling process. Bhat and Sadhukhan
[21] reviewed the PI for methane steam reforming by coupling
and using the membrane separation technologies to overcome
the mass transfer, heat transfer and thermodynamic limitations. Altimari and Bildea [22] discussed about the design and
control of plant wide systems of coupling exothermic and
endothermic reactions in a steady state behavior. Patel and
Sunol [23] developed a distributed mathematical model for
thermally coupled membrane reactor to couple the methane
steam reforming through the exothermic methane combustion. Glockler et al. [24] presented a theory to analyze and
optimize the reactor design to couple the exothermic and
endothermic reactions in an adiabatic fixed-bed reactor with
reverse flow mode. AboeGhander et al. [25] investigated
coecurrent and counterecurrent operation modes for the
above configuration.
Based on the researches made in literature, most of the
implemented studies on the coupled reactors have presented
higher conversion in the coecurrent mode compared with the
counterecurrent one. On the other hand, the results of some
specific studies showed the superiority of the counterecurrent
mode of operation [25]. These different results made us compare
the performance of two reactor configurations, simultaneously.

Table 1 e Rate constants and heat of reactions for

naphtha reforming.
k AexpB  E=1:8 T
k f1
k f2
k f3
k f4
Ke1
Ke2

9.87
9.87
1
1
1.04  103
9.87

23.21
35.98
42.97
42.97
46.15
7.12

36,350
58,550
63,800
63,800
46,045
8000

DH298

71,038.06
36,953.33
51,939.31
56,597.54
e
e

Table 2 e Rate constants and heat of reaction for

hydrogenation of nitrobenzene.
k A0 expB0  E0 =1:8 T
0

k
KH2
KNB

A0

B0

E0

DH298

0.186
4.427  103
1.51  105

0
0
0

10
0
0

44,3000
e
e

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Fig. 1 e A simplified process for conventional tubular reactor (CTR).

2.

Reaction scheme and kinetics

2.1.

Endothermic side (catalytic naphtha reforming)

reaction rate and equilibrium constants are temperature

dependent. The temperature dependent equations for calculation of these constants and their related coefficients have
been presented.

Considering the simplified model suggested by smith [3], four

dominant idealized reactions can be used to describe the catalytic reforming process so that the catalytic reforming system
can be simplified significantly. The reactions are as follows:

Table 3 e Specifications of reactors, feed, product and

catalyst of CTR.

Naphthenes (CnH2n) 4 Aromatics (CnH2n6) 3H2

(1)

Parameter

Naphthenes (CnH2n) H2 4 Paraffins (CnH2n2)

(2)

Naphthenes (CnH2n) n/3H2 / Lighter ends (C1eC5)

(3)

Paraffins (CnH2n2) (n3)/3H2 / Lighter ends (C1eC5)

(4)

Naphtha feed stock

30.41  103
Reformate
24.66  103
4.74
H2/HC mole ratio
LHSV
1.25
Mole percent of hydrogen in recycle
69.5
Diameter and length of 1st reactor
1.25, 6.29
Diameter and length of 2nd reactor
1.67, 7.13
Diameter and length of 3rd reactor
1.98, 7.89
Distillation fraction of naphtha feed and reformate
TBP
Naphtha
feed ( C)
IBP
106
10%
113
30%
119
50%
125
70%
133
90%
144
FBP
173
Typical properties of catalyst
1.2
dp
Pt
0.3
Re
0.3
220
sa
0.3
rB
e
0.36

The corresponding rate expressions are as follow:



kf1 
ke1 pn  pa p3h
r1
K e1


kf2 
ke2 pn ph  pp
K e2

(5)

r2

(6)

r3


kf3
pn
pt

(7)

r4


kf4
pp
pt

(8)

The reaction rate constants kfi , equilibrium constants

Kei , activation energies (Ei) and standard heat of reactions
(DH298 K) are tabulated in Table 1 [26]. The value of activation
energies and standard heat of reactions are written. The

Numerical
value

Unit
Kg/hr
Kg/hr
e
hr1
e
m
m
m
Reformate
( C)
44
73
105
123
136
153
181
mm
wt%
wt%
m2/g
Kg/l
e

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Fig. 2 e A schematic concept for thermally coupled reactors (TCRs) (a) Co-current and (b) Counter-current.

2.2.
Exothermic side (hydrogenation of nitrobenzene to
aniline)
Over the last 145 years aniline has became one of the hundred
most important building blocks in chemistry. Aniline is
known to be used in more than 300 different end products
such as, isocyanates, rubber processing chemicals, dyes and
pigments, agricultural chemicals and pharmaceuticals [27].
Nitrobenzene is used as row material for aniline production by
almost entire world producers, using fixed-bed or fluidizedbed vapor phase reactors [27,28].

The hydrogenation of nitrobenzene to aniline in the tube

side can be expressed by:
C6 H5 NO2 3H2 /C6 H5 NH2 2H2 O

(9)

The rate expression provided by Klemm et al. [29] is as follow:

k0 KNB KH2 PNB P:5
H2
r
2
1 KNB PNB KH2 P:5
H2

(10)

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

the activation energy (E ) and standard heat of reaction

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 6 ( 2 0 1 1 ) 3 4 8 3 e3 4 9 5

(DH298 K) are all given in Table 2. As in Table 1, the related

values and temperature equations and coefficients have been
presented in Table 2.

3.

Process description

3.1.

Conventional tubular reactor (CTR)

In conventional fixed-bed reforming the naphtha (middle

distillates of atmospheric distillation column or condensate
from gas reservoirs) feedstock is combined with a recycle gas
stream contain 60%e90% (by mole) hydrogen. Hydrogen can
adjust the H2/HC ratio through the reactors to reduce coke
formation and also it sweeps the products through the catalyst pores. The total reactor charge is heated and passed
through the catalytic reformers, which are designed with
three adiabatically operated reactors and three kilns between
the reactors to maintain the reaction temperatures at design
levels. The catalyst weight distribution in the reactors in the
conventional process is 0.2/0.3/0.5 [30]. The effluent from the
last reactor is cooled, and then enters the product separators.
The off gases and reformates are separated from the above
and bottom of the separator, respectively. Fig. 1 shows the
schematic of the process and Table 3 shows the catalyst
specification and operational conditions for the CTR.

3.2.

Thermally coupled reactor configuration (TCR)

Fig. 2(a) and (b) provide schematic diagram of co and counterecurrent modes of operation for coupled reactors,
respectively. The first and second reactors in the coupled
configuration composed of two compartments separated by
a solid wall. Catalytic reforming is supposed to takes place in
the shell side and the exothermic hydrogenation of nitrobenzene to aniline is considered to provide the heat for
reforming. In the counterecurrent configuration the blend of
nitrobenzene and hydrogen feed the reactors from the
bottom. The external walls are assumed to be adiabatic.
The catalytic naphtha reforming reactions are carried out
over commercial Pt/Re/Al2O3 catalyst (0.3% Platinum, 0.3%
Rhenium). The outer compartment is filled with the spherical
commercial PdeAl2O3 (1.1 wt.%) catalyst [31]. Table 4 shows
the specific properties and operational conditions of the
exothermic side (hydrogenation of nitrobenzene). The molar
flow rates for nitrobenzene and steam are considered as those
reported by AboeGhander et al. [25].

4.

3487

Table 4 e Operating condition for hydrogenation reaction

of nitrobenzene to aniline.
Parameter

Numerical value

Unit

Inlet temperature
Inlet pressure
Catalyst density
Diameter of catalyst particle
Void fraction
1st reactor
Available cross-sectional
area of the tube side for flow
Nitrobenzene molar flow rate
Hydrogen molar flow rate
Aniline molar flow rate
Steam molar flow rate
2nd reactor
Available cross-sectional
area of the tube side for flow
Nitrobenzene molar flow rate
Hydrogen molar flow rate
Aniline molar flow rate
Steam molar flow rate

780
1.1  105
1400
4.7  103
0.46

K
Pa
Kg/m3
m
e

3.29

m2

7.24
28.98
0.72
72.46

mol/s
mol/s
mol/s
mol/s

2.91

m2

6.41
25.67
0.64
64.19

mol/s
mol/s
mol/s
mol/s

positive sign in the left sides of equations (11) and (14) is used
for the coecurrent setup. Simultaneously, the negative one
demonstrates the counterecurrent regime. The negative sign
in the right side of equation (14) is used for the exothermic
reaction in the tube side.

5.

Simulation and results

5.1.

Steady state model validation for CTR

A comparison between the proposed model and conventional

tubular packed bed reactors at steady state condition has been
demonstrated in Table 6. The comparison of experimental
data and the results obtained from the model for 771 days of
operation has been presented in Table 7. As it can be seen,
there is an acceptable agreement between the plant data and
predicted mole fractions of components at the output of the
system. Analysis of the components (paraffin, naphthene and
aromatic) is performed by PONA Test in Stan Hop Seta apparatus. The aromatic is tested especially by ASTM 2159 equivalent to UOP 273 method [30].

Reactor model

In this study a homogeneous oneedimensional model has

been considered. The basic structure of this model is
composed of heat and mass balance conservation equations
coupled through thermodynamic and kinetic relations, as well
as auxiliary correlations for predicting physical properties.
Differential elements (Fig. 3) are considered along the axial
direction inside the reactor configurations (co and counterecurrent). The mass and energy balances are written for fluid
phase in each side. The results are summarized in Table 5. The

Fig. 3 e Axial elements for the co-current and countercurrent configurations.

3488

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Table 5 e Mass & energy balances and auxiliary correlations.

Definitions

Equations

Fluid phase

1 dFi;j
ri;j rb

Acj dz
dFtj

(11)

dFi;j

(12)

dFtj

dMave;j

F2tj

_j
m

(13)



X 

pDj
1 g d Ftj Tj
UTTube  TShell rb
ri;j DHf ;i

(14)
 Cpj
Acj
dz
Acj
i
dP 150m 1  e2 Q 1:75r 1  e Q 2

e3
dz f2s d2p
Ac
fs d p
e3 Ac

(15)

z 0; Fi;j Fi0;j ; T T0
z L; Fi;j2 Fi0;j2 ; T2 T0;2

(16)

Boundary conditions

Parameter

Equation
Cp a bT cT dT
2

Component heat capacity

Viscosity

Reference
2

[32]
[33]

C1 TC2
m
1 CT3 CT24

Thermal conductivity

Based on local compositions

Re

[34]

2Rp ug r
m

.
hi 4Kdwp rug dp m0:3

Overall heat transfer coefficient

5.2.

Endothermic side

5.2.1.

Paraffin

1
U

h1i

Fig. 4(a) and (b) compares the consumption rates of the reactants
for three configurations (CTR, co-current and counter-current
coupled reactors). Paraffin consumption is not considerable in
the first reactor as it is shown in Fig. 4(a). The dehydrogenation reaction mainly occurs in this reactor. Providing a heating
medium for the reaction side (for endothermic section) can

Ai lnDo =Di
2pLKw

[35]

Ai 1
Ao ho

change the reaction rates and equilibrium conditions. This could

be achieved by utilizing the coupled reactor configuration. The
generated heat in the exothermic side is straightly consumed
by the endothermic section in the co-current regime and
this increases the paraffin consumption rate in the co-current
reactor in comparison with the counter-current one. A sharp
slope in this figure for CTR and TCRs can be seen for the second
and third reactors. This means that the forth reaction will be
predominant in these two reactors.

Table 6 e Comparison between model prediction and plant data for fresh catalyst.
Reactor no.

Inlet temperature (K)

Inlet pressure (Kpa)

Catalyst distribution (wt%)

777
777
775

3703
3537
3401

20
30
50

1
2
3

Outlet temperature (K)

Reactor no.

1
2
3

Plant

722
753
770

CTR

727
751
771

Input feedstock (Mole%)

Paraffin
Naphthene
Aromatic

49.3
36
14.7

Aromatic in reformate (Mole %)

TCR

Plant

Co-current

Counter-current

760.8
801.2
799.6

767.2
802
798.9

e
e
57.7

CTR

e
e
56.2

TCR
Co-current

Counter-current

44.02
62.10
85.77

39.96
53.35
81.75

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Table 7 e Comparison between predicted production rate

and plant data.
Naphtha feed
(ton/h)

Plant
(kmol/hr)

Model
(kmol/hr)

Devi%

30.41
30.41
31.00
30.78
31.22
31.22
28.55
30.33
31.22
30.67
30.76
42.35
42.32
42.32
42.32
42.32
42.54
42.54
37.86
38.51

225.90
224.25
229.65
229.65
229.65
229.65
211.60
222.75
233.05
228.65
227.64
317.30
317.94
317.94
317.94
313.09
317.94
313.90
286.15
282.10

221.5802
222.5122
227.9313
226.7749
230.7985
231.2730
209.8377
224.7291
232.1821
228.1752
229.0932
324.5555
324.4826
324.6987
324.8622
325.0433
327.0586
327.2581
289.3742
294.9026

1.91
0.77
0.75
1.25
0.50
0.71
0.83
0.88
0.37
0.21
0.64
2.28
2.05
2.12
2.17
3.81
2.86
4.25
1.12
4.53

0
34
62
97
125
160
188
223
243
298
321
398
425
461
490
524
567
610
717
771

160

140

Aromatic molar flow rate (kmole/hr)

Time
(day)

The naphthenes consumption profile is illustrated in Fig. 4

(b). The achieved results from the coupled reactor configuration show that the configuration with just two coupled reactors has the same results as the CTR (with three reactor) and
even more acceptable.

120

100
CTR
Co Current
Counter Current

80

60

40

20

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

0.8

0.9

0.8

0.9

Mass of catalyst (Dimensionless)

140

1550

Hydrogen molar flow rate (kmole/hr)

Paraffin molar flow rate (kmole/hr)

120

100

80
Counter Current
Co Current

60

CTR
40

20

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1500

1450

1350

1300

1250

Mass of catalyst (Dimensionless)

CTR
Co Current
Counter Current

1400

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Mass of catalyst (Dimensionless)

100

c
CTR
Co Current
Counter Current

80
70

Light ends molar flow rate (kmole/hr)

Naphthen molar flow rate (kmole/hr)

90

60
50
40

30

3
2

20

1
0.8

10
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.9

0.8

0.9

Mass of catalyst (Dimensionless)

Fig. 4 e Molar flow rates for (a) paraffine and (b) naphthene
vs. the dimensionless mass of catalyst in the endothermic
side for CTR and TCRs.

800

750

CTR
Co Current
Counter Current

700

650

600

550

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Mass of catalyst (Dimensionless)

Fig. 5 e Products molar flow rates of (a) aromatic, (b)

hydrogen and (c) the light ends along the CTR and TCRs.

3490

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Table 8 e Third reactor outlet and Reformate compositions.

Paraffin

Naphthene

Aromatic

Hydrogen

Light end

Third reactor outlet composition (% w/w)

CTR
19.7849
Co-current
4.8546
Counter-current
6.4985

0.7744
0.2776
0.3300

26.8334
31.4891
31.1464

5.1442
5.1226
5.1412

47.4630
58.2560
56.8839

Reformate composition (% w/w)

CTR
41.7468
Co-current
13.2563
Counter-current
17.1126

1.6339
0.7582
0.8690

56.6193
85.9856
82.0183

5.2.2.

Aromatics, hydrogen and lighter ends

Fig. 5(a) and (c) reveals the products molar flow rates in the
endothermic section of the coupled reactor configuration. An
interesting result is achieved by the modeling of TCRs (cocurrent and counter-current regimes). Higher aromatic and
lower hydrogen production rates are achieved in co-current
flow compared with the counter-current. This can be seen in
Fig. 5(a) and (b). Generally, the use of proper flow regime of TCRs
depends on the domestic use of plant products and downstream units. The main goal of the catalytic naphtha reforming

2500

is to produce high-octane gasoline. Therefore, the co-current

regime is more favorable. Also the co-current reactors operate
more easily than the counter-current ones. Fig. 5(a) and (b) also
shows higher aromatic and hydrogen production in the outlet
of the second reactor of TCRs configuration in comparison with
the outlet of the third reactor in the CTR. As a result, the third
reactor, with the highest catalyst load (as much as the sum of
the first and second reactors) can be neglected. This achievement leads to a huge capital and operational investment saving
(the catalyst contains Pt metal). Fig. 5 (c) reveals the light end
production. These gases are used as a feed stock for LPG
production. Table 8 shows the composition of reformate and
product stream of the third reactor for each case.

2450

Total molar flow rate (kmole/hr)

5.2.3.
2400
2350
2300
2250
CTR
Co Current
Counter Current

2200
2150
2100
2050

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Change of molar flow rate and molecular weight

As it is demonstrated in Fig. 6(a) the variation of the total molar

flow rate from the entrance of the first reactor to the outlet of
the last reactor is about 350 kmol/h (about 17% changes in
molar flow rate). This is considered during the modeling and
a more comprehensive model compared with previous studies
is present in this research. The TCRs produce lighter hydrocarbons such as lighter ends and aromatics compared with the
CTR. Accordingly, the average molecular weight is lower for
the TCRs (see Fig. 6(b)). Also the Heat capacity, viscosity,
density and other physical properties are considered to be
variable in both shell and tube sides in this study.
0.9

Mass of catalyst (Dimensionless)

28

3800
27.5

3700

CTR
Co Current
Counter Current

26.5
26

CTR
Co Current
Counter Current

3600

Pressure (kPa)

Molecular weight (kg/kmole)

27

25.5
25
24.5

3500

3400

24

3300

23.5
23

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Mass of catalyst (Dimensionless)

Fig. 6 e Variation of (a) total molar flow rate and (b) the
molecular weight in the CTR and TCRs.

3200

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Mass of catalyst (Dimensionless)

Fig. 7 e Pressure drop along the endothermic side.

3491

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 6 ( 2 0 1 1 ) 3 4 8 3 e3 4 9 5

8.5
8

a
CTR
Co Current
Counter Current

800
790

Temperature of shell side (K)

H2/HC molar ratio

7.5

810

6.5
6
5.5
5

780
770
760
Co Current

750

Counter Current
CTR

740

4.5

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

730

Mass of catalyst (Dimensionless)

720

Fig. 8 e H2/HC ratio through the reactor for CTR and TCRs.

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Mass of catalyst (Dimensionless)

2.5

x 10

Endothermic Heat of Reaction

Transfered Heat

Heat (kJ/kg cat. hr)

30

Anilin molar flow rate (kmole/hr)

26.06
24.84

20

Co Current
Counter Current

1400
1.5
1200
1000
1
0.19

0.195

0.2

0.5

15

10

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

0.5

Mass of catalyst (Dimensionless)

5

c
0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

x 10

Heat (kJ/kg cat. hr)

320

H2O molar flow rate (kmole/hr)

314.8
312.5
310
305

Co Current
Counter Current

300

0.5

Mass of catalyst (Dimensionless)

2.5

Enothermic Heat of Reaction

Transfered Heat

1500
1.5

1000
500
0

0.02

0.04

295

0.5

290
285
280

275

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

Mass of catalyst (Dimensionless)

270
265
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)

Fig. 9 e Changes of (a) aniline and (b) water in the

exothermic side for TCRs (co-current and counter-current).

Fig. 10 e (a) Thermal profiles of CTR and TCRs, and the

consumed heat of endothermic side and transfer heat
through the solid walls of (b) co-current and (c) countercurrent.

0.5

3492

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 6 ( 2 0 1 1 ) 3 4 8 3 e3 4 9 5

5.2.4.

Pressure drop

Since the total molar flow rate increases, the velocity and
related viscose losses as well as the pressure drop increase.
Fig. 7 depicts the pressure profile along the CTR and TCRs. The
related equation (Ergun equation) was shown in Table 5.

5.2.5.

H2/HC ratio

Clearly the H2/HC ratio increases along the reactor according to

the hydrogen production. Increasing this ratio is a guarantee to
enhance the catalyst life time and also reduces load on the
catalyst. On the other hand, it is a constraint and can shift the
dehydrogenation reaction in the reverse direction to reduce
the hydrogen and aromatic productions. Higher temperature in
the TCRs can aid to reduce the undesirable effect of increasing
in the H2/HC. Fig. 8 shows this ratio in the CTR and TCRs.

5.3.

Exothermic side

5.3.1.

Molar behavior

Fig. 9(a) and (b) presents the molar flow rate of the exothermic
side of the reactor for both coecurrent and counterecurrent
mode of operation. The same value for the space velocity

Temperature of exothermic side (K)

Thermall behavior

5.4.1.

Endothermic side

Fig. 10(a) presents the temperature profile in the endothermic

side of the CTR and TCRs simultaneously. The temperature in

1100
N=1
N=10

1050

5.4.

N=100
N=750

1400

N=750

1000

Counter Current

Co Current
1200
Co Current

950

Counter Current

900
850

1000
800
600
400

800

200

750
0.025

0.05

0.075

0.1

0.125

0.15

0.175

0.2

Mass of catalyst (Dimensionless)

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

b 1792

1000

Exothermic Heat of Reaction

Transfered Heat

1600

Counter Current

Co Current
950

1400

900

Heat (kj/kg cat. hr)

1200

850
800
750

N=750

Counter Current

Co Current

1000
800
600
400

N=100
N=750

N=1
N=10

700
650
0.2

Mass of catalyst (Dimensionless)

b
Temperature of exothermic side (K)

Exothermic Heat of Reaction

Transfered Heat

1600

Heat (kj/kg cat. hr)

which was considered by AboeGhander et al. [25] has been

applied in our study. The molar flow rates of the exothermic
components are based on stoichiometric values. Adding steam
to the feed line prevents the coke formation on the catalyst and
reduces the temperature along the hydrogenation side and
maintains it low by diluting the reacting mixture on the
hydrogenation side [25,36]. The hydrogenation of nitrobenzene is an irreversible reaction and it is not limited due to the
thermodynamic equilibrium and it continues to the end. Fuel
depletion will impress the reaction rate and will stop it. The
concentrated feed generates high heat and consequently
a considerable peak in the temperature. So we divided the feed
stream into two parallel lines to avoid this phenomenon. The
conversions for nitrobenzene in the first and the second reactors are 86.40e86.38% and 90.60e90.59% respectively for cocurrent and counter-current regimes.

200
0

0.25

0.3

0.35

0.4

0.45

0.5

Mass of catalyst (Dimensionless)

Fig. 11 e Effect of tubes number on the developed hot spot

in the exothermic sides of co and counter-current reactors
for (a) first reactor and (b) second reactor.

-200
0.2

0.25

0.3

0.35

0.4

0.45

0.5

Mass of catalyst (Dimensionless)

Fig. 12 e Exothermic heat of reaction and the transferred

heat in the TCRs for (a) first reactor and (b) second reactor.

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 6 ( 2 0 1 1 ) 3 4 8 3 e3 4 9 5

the CTR falls in each reactor due to the predominant endothermic reaction. The temperature reduction of the first reactor
in TCR configuration for co-current flow pattern is lower
compared with the CTR because of the heat source (exothermic
reaction in the tube side). Considering the case of co-current flow
in the thermally coupled reactor configuration (Fig. 10b), the
consumption heat in the endothermic side is higher compared
with the transferred heat through the tube wall in the first
reactor. This can justify the temperature reduction along the first
reactor. In the second reactor, the amount of transferred heat is
higher compared with the heat consumption in the endothermic
side which raises the temperature of the system. The heat
transfer for the counter-current flow regime has been shown in
Fig. 10(c). As it can be seen, at the entrance of the reactor, the heat
consumption rate is higher compared with the transferred heat
through the tube wall. Therefore, the temperature of the system
reduces. In a certain axial position in Fig. 10(c), (dimensionless
mass of catalyst 0.1) the amount of transferred heat exceeds
the amount of consumed heat in the endothermic side which
justifies the temperature increase in Fig. 10(a). The same trend
can be seen in the second reactor and a minimum in temperature profile of the endothermic side occurs for the countercurrent flow regime of the TCR in this reactor.

to boost hydrogen production and the co-current mode of

operation enhances the aromatic production rate and ensure
the other desired results, as well. However, an investigation in
relation to the environmental aspects, commercial viability and
economic feasibility of the proposed configuration is necessary
in order to consider commercialization of the process.

Nomenclature

a
A
Ac
cp
dp
Ed
Ei
Fi
hf
H2
keff
kf1
kf2

5.4.2.

Exothermic side

Fig. 11(a) and (b) shows the exothermic temperature profiles in

the first and second reactors for both co and counter-current
flows. As the number of tubes increases, the hot spot decreases
and the thermal behavior improves.
Fig. 12 demonstrates the heat generation in the exothermic
sides for co-current and counter-current flows. The generated
heat in the exothermic side is higher for the co-current configuration in the first reactor (also the transferred heat through
the solid wall). Accordingly, the temperature of the exothermic
side remains higher (higher maximum temperature for cocurrent). Fig. 12(b) demonstrates a reverse phenomenon for the
exothermic side of the second reactor (higher maximum
temperature for counter-current).

6.

Conclusion

In order to save energy and minimize the capital and operational

costs, a novel reactor configuration has been proposed for the
catalytic naphtha reforming process in previous studies. In this
research, two different modes of operation have
been investigated in order to determine their advantages and
disadvantages. Considering aromatics and hydrogen as the
main products of the naphtha reforming process, the variation
of the production rate of these two components may clarify the
situation. According to the calculations made by this research
group, higher aromatics production rate can be achieved by
utilizing the co-current mode of operation. On the other hand,
by utilizing the counter-current flow regime, the hydrogen
production rate increased by about 5 kmol/h compared with the
co-current flow. The pressure and temperature profile also has
been presented in this study. Generally, according to all the
calculations made in this research, utilizing the co-current
mode of operation is given priority. These results suggest that
the counter-current configuration can be a compelling way

3493

kf3
kf4
Ke1
Ke2
L
Mi
Mw
n
NA
Ni
p
Pi
P
Q
ri
R
sa
T
yi
e
m
r
rb
fs
DH
a
cal
h
i
j
n

catalyst activity
moles of aromatic formed, kmol h1
cross-section area of reactor, m2
specific heat capacity, kJ kmol1 K1
particle diameter, m
activation energy of catalyst, J mol1
activation energy for ith reaction, kJ kmol1
molar flow rate of component i
heat transfer coefficient, W m2 K1
hydrogen, kmol h1
effective thermal conductivity, W m1 s1
forward rate constant for reaction (1),
kmol h1 kg cat1 MPa1
forward rate constant for reaction (2),
kmol h1 kg cat1 MPa2
forward rate constant for reactions (3),
kmol h1 kg cat1 MPa2
forward rate constant for reactions (4),
kmol h1 kg cat1 MPa2
equilibrium constant, MPa3
equilibrium constant, M Pa1
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 flow rate of aromatic, kmol h1
molar flow rate of component i, kmol h1
moles of paraffin formed, kmol h1
partial pressure of ith component, kPa
total pressure, kPa
volumetric flow rate, m3 s1
rate of reaction for ith reaction, kmol kg cat1 h1
gas constant, kJ kmol1 K1
specific surface area of catalyst pellet, m2 kg1
temperature of gas phase, K
mole fraction for ith component in gas phase
void fraction of catalyst bed
viscosity of gas phase, kg m1 s1
density of gas phase, kg m3
reactor bulk density, kg m3
sphericity
heat of reaction, kJ kmol1
aromatic
calculated
hydrogen
number of components
number of reaction sides (1: Endothermic, 2:
Exothermic)
naphthene

3494

out
p
CTR
FBP
HC
IBP
LHSV
Pt
Re
RON
TBP
TCR
WHSV

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 6 ( 2 0 1 1 ) 3 4 8 3 e3 4 9 5

outlet
paraffin
conventional tubular reactor
final boiling pint,  C
Hydrocarbon, kmol h1
initial boiling pint,  C
liquid hourly space velocity, hr1
platinum
rhenium
research octane number
true boiling point,  K
thermally coupled reactor
weight hourly space velocity, hr1

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