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

Modeling of an axial flow, spherical packed-bed reactor for


naphtha reforming process in the presence of the catalyst
deactivation
D. Iranshahi, E. Pourazadi, K. Paymooni, A.M. Bahmanpour, M.R. Rahimpour*, A. Shariati
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran

article info

abstract

Article history:

Improving the octane number of the aromatics compounds has always been an important

Received 21 May 2010

matter in refineries and lots of investigations have been made concerning this issue. In this

Received in revised form

study, an axial-flow spherical packed-bed reactor (AF-SPBR) is considered for naphtha

15 July 2010

reforming process in the presence of catalyst deactivation. Model equations are solved by

Accepted 23 August 2010

the orthogonal collocation method. The AF-SPBR results are compared with the plant data
of a conventional tubular packed-bed reactor (TR). The effects of some important param-

Keywords:

eters such as pressure and temperature on aromatic and hydrogen production rates and

Axial-flow

catalyst activity have been investigated. Higher production rates of aromatics can

Spherical packed-bed reactor

successfully be achieved in this novel reactor. Moreover, results show the capability of flow

Catalytic naphtha reforming

augmentation in the proposed configuration in comparison with the TR. This study shows

Dynamic modeling

the superiority of AF-SPBR configuration to the conventional types.

Hydrogen production

2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

Aromatic production

1.

Introduction

Full-range naphtha is the fraction of the crude oil with


a boiling temperature between 30  C and 200  C, and constitutes typically 15e30% by weight of the crude oil. The catalytic
naphtha reforming reactions are carried out over commercial
Pt/Re/Al2O3 catalyst (0.3% Platinum, 0.3% Rhenium). Naphtha
and reformate are complex mixtures of paraffins, naphthenes, and aromatics in the C5eC12 range [1,2]. Naphtha
reforming plays a major role in improving the aromatic and
hydrogen production in petroleum refineries [3,4]. In order to
have an improved process its better to revamp naphtha
reforming strategies due to its impact on overall refinery
profits [5].

2.

Literature review

Naphtha as a complex reforming feedstock is composed of


various hydrocarbons and related isomers. It is too complex to
consider a detailed kinetic model taking into account all
components and reactions [6]. Studies on the catalytic
naphtha reforming process have been categorized in two basic
groups. The first group involves studies on the kinetics of
catalytic naphtha reforming process. Various attempts have
been made to find better lumped groups of reactions to
represent the catalytic reforming reactions. In this regard,
the first significant attempt to model a reforming system has
been made by Smith [7]. He considered naphtha to consist of
three basic components including paraffins, naphthenes, and

* 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 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.08.124

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 2 7 8 4 e1 2 7 9 9

aromatics industrially known as PNA. Thereafter, more


extensive attempts have been made to model reforming
reactions. Juarez and Macias [3] developed a new kinetic
model in which the most important reactions in terms of
isomers of the same nature (paraffins, naphthenes and
aromatics) were taken into account. The average deviation of
the new kinetic model from experimental data was reported
to be less than 3%. Weifeng et al. [8] developed a new kinetic
model including 20 lumped components and 31 reactions.
Boyas and Froment [9] studied a fundamental chemistry of
naphtha. The current model imposed the equilibriums of
hydrogenation and dehydrogenations. Stijepovic et al. [10]
recommended a semi-empirical kinetic model for catalytic
reforming. Their lumping strategy was based on paraffins,
olefins, naphthenes and aromatics (PONA) analyses. Similar
studies in this field were carried out by Ramange et al. [11,12],
Krane et al. [13], Kmak [14] and Marin et al. [15]. The second
group involves studies on the modeling and improvement of
aromatics and hydrogen yields of the conventional reactors. Li
et al. [16] modeled and optimized a semi-regenerative catalytic naphtha reformer by considering most of its key constitutes. Taskar and Riggs [17] done a similar study as Li et al. But
they have used a reaction network composed of 35 reactions
for 35 pseudo components. Juarez et al. [18] modeled and
simulated four serially catalytic reactors for naphtha reforming. Weifeng et al. [6] considered 18-lumped kinetic models to
simulate and optimize a whole industrial catalytic naphtha
reforming process by Aspen Plus platform. Stijepovic et al. [19]
introduced a new simulation and optimization approach for
CRs. They applied a new proposed objective function in which
economical and environmental performance was taken into
consideration. Khosravanipour and Rahimpour [4] presented
a membrane catalytic bed concept for naphtha reforming in
the presence of catalyst deactivation. Weifeng et al. [20]
examined a multi objective optimization strategy for a CR
process in order to obtain aromatic products. Rahimpour [21]
proposed a novel fluidized-bed membrane reactor (FBMR) for
naphtha reforming in the presence of catalyst deactivation.
He shows that the FBMR increases catalyst activity, aromatic
and hydrogen production rates.
In order to enhance the octane number of aromatic
compounds, the reaction conditions have to be improved.
Aromatics are enhanced by shifting the reactions (using
a hydrogen permeselective membrane) or decreasing the
pressure drop. In industrial plants, the pressure drop is
a serious problem in unit operations such as reactors. The
configurations which have much lower pressure drop than the
conventional fixed-bed reactors are radial flow spherical
packed-bed reactors (RF-SPBR) and radial flow tubular packedbed reactors (RF-TPBR). A complete literature review on the
RF-SPBR and RF-TPBR has been prepared by Iranshahi et al.
[22] have recently modeled the RF-SPBR for naphtha reforming
process in the presence of catalyst deactivation. They have
shown that in addition to pressure drop reduction through the
catalytic bed, the amount of aromatic production increases.
The AF-SPBR is an alternative configuration for pressure drop
reduction in high pressure processes such as naphtha
reforming. This novel configuration is not as well known as
the previous ones and little studies have been done on it.
Fogler has modeled the dehydrogenation of paraffins turning

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into olefins and confirmed that the pressure drop in axial


spherical reactor decreases significantly [23]. Zardi et al. have
modeled the ammonia synthesis in an axial-radial reactor [24].
Moreover, Brumbaugh has patented a modified novel axialflow spherical reactor for naphtha reforming process [25].
The main goal of this work is to investigate the production
yield of aromatics in the AF-SPBR. A comparison between the
AF-SPBR and the TR are carried out in this study. The dynamic
modeling of this novel reactor is done by considering the
catalyst deactivation.
The AF-SPBR configuration is superior to the previous ones
(AF-TPBR and RF-SPBR) briefly as follows:
The AF-SPBR in comparison with the AF-TPBR:
 Lower pressure drop is encountered in this configuration.
 Lower required material thickness (Material thickness for
a spherical and a tubular pipe of the same radius, subjected to
action of an internal pressure, P, are tsph P$r=2s and
ttub P$r=s respectively. Where t is the wall thickness, s is the
tensile stress and r is the radius of the tube and the sphere [26]).
 Consequently the required surface has been decreased
which reduces effectively the costs of investment and
maintenance during the operation (this is a wise decision to
use membranes with lower costs of maintenance).
 Smaller catalytic pellets with higher effectiveness factor can
be applied owing to the reduction of pressure drop in this
configuration.
 Higher molar flow rate can be applied (due to lower pressure
drop) which increases the production rate.
 Lower power supply of recompression is needed.
The AF-SPBR in comparison with the RF-SPBR:
 The feed distribution has been improved (Utilizing the radial
flow pattern to distribute the feed stream is not easily
applicable).
 Modifications have been done on the reactor structure to
provide an effective contact between the reactant gas and
the catalytic bed when the quantity of the applied catalyst is
only a fraction of the designed quantity of catalyst [25].
 Membrane technologies can be easily introduced in the AFSPBR while it is hard to apply the membrane concept in
radial flow spherical packed-bed reactor (RF-SPBR).
A homogeneous one-dimensional model has been
considered. The basic structure of the model consists of heat
and mass balance equations. These equations must be
coupled with the deactivation model, and also thermodynamic and kinetic equations, as well as auxiliary correlations
for predicting physical properties.
The effect of various parameters such as reactor length,
time, variable physical properties, and operating conditions
on the performance of the reactor has been investigated.

3.

Reaction scheme and kinetics

Kinetics of multi-component reactions were presented by


Smith [7]. He assumed some pseudo components in order to

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simplify the feedstock of catalytic naphtha reforming. Four


dominant idealized reactions can be used to simplify the
catalytic reforming system. The following four reactions are
considered in the model:
(1)
(2)
(3)
(4)

Dehydrogenation of naphthenes to aromatics.


Dehydrocyclization of paraffins to naphthenes.
Hydrocracking of naphthenes to lower hydrocarbons.
Hydrocracking of paraffins to lower hydrocarbons.

OF

Naphthenes (CnH2n) 4 Aromatics (CnH2n6) 3H2

(1)

Naphthenes (CnH2n) H2 4 Paraffins (CnH2n2)

(2)

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

(3)

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

(4)

Naphtha reforming reactions are limited by equilibrium. In


order to achieve higher aromatics production, the naphtha
reforming process should be carried out at higher temperatures.
The rate equations of these reactions are as follows:


kf 1 
ke1 pn  pa p3h
Ke1

(5)



kf 2 
ke2 pn ph  pp
Ke2

(6)


r2

(
m
X


3
2 X

2
NA cal  NA plant
TOut cal  TOut plant

i1

The related reactions are

r1

found by minimizing the differences between the calculated


and the observed values of outlet temperature and aromatic
yield of bed simultaneously. A constrained optimization
procedure is used to find the activation energies. The activation energies are adjustable parameters. The objective function to be optimized is:

r3

 
kf 3
pn
pt

(7)

r4

 
kf 4
pp
pt

(8)

where kf and Ke are the forward rate constant and the


equilibrium constant, respectively. Rase [27] reported the
following equations for these constants.


E1
kf 1 9:87exp 23:21 
1:8T

(9)



E2
kf 2 9:87exp 35:98 
1:8T

(10)



E3
kf 3 kf 4 exp 42:97 
1:8T

(11)



46; 045
Ke1 1:04  103 exp 46:15 
1:8T

(12)



8000
Ke2 9:87exp 7:12
1:8T

(13)

where E is the activation energy of each reaction. The activation energies depend on the catalyst which is used.
According to the previous works, the activation energy is

)
(14)

i1

where NA is the aromatic molar flow rate, T is the outlet


temperature of each bed and m is the number if data sets are
used, so the results are:
E1 36,350
E2 58,550
E3 63,800

4.

Process description

4.1.

Conventional configuration

Naphtha reforming is a major process practiced extensively by


petroleum refineries and the petrochemical industry to
convert paraffins and naphthenes into aromatics. A simplified
flow diagram of continuous catalytic reforming process is
shown in Fig. 1. The fresh naphtha feedstock (middle distillate
of atmospheric distillation column) is combined with a recycled gas stream containing 60e90% (by mole) hydrogen.
Hydrogen can adjust the H2/HC molar ratio through the
reactors to prevent coking and also it sweeps the products
through the catalyst pores. The total reactor charges are
heated and passed through the catalytic reformers which are
designed with three adiabatically operating reactors and three
heat exchangers between the reactors to maintain the reaction temperatures at designed levels. The effluent from the
3rd reactor is cooled, and then it enters the separators. Off
gases and reformates are separated from the top and the
bottom of the separator [28]. Table 1 shows the specific
properties and operating conditions of the conventional
naphtha reactors. Boiling point ranges are determined by
Distillation Petro Test D86.

4.2.

Spherical reactor setup

Although, tubular packed-bed reactors are used extensively in


industry [29], due to some disadvantages of this type of reactors the spherical packed-bed reactors attract more attentions. Some potential disadvantages of tubular reactors are
the pressure drop along the reactor, high manufacturing costs
and low production capacity. In order to avoid serious pressure drop in the TR, the effective diameters of the catalyst
particles are usually considered more than 3 mm which lead
to a certain inner mass transfer resistance. In this study, the
AF-SPBR is proposed for naphtha reforming process.
Fig. 2(a) shows the schematic diagram of the spherical
configuration setup. In the AF-SPBR, catalysts are situated

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Off Gas
R: Reactor
EX: Heat
Exchanger
S-1: Separator
S-2: Stabilizer

R-1

R-3

R-2

S-2

EX-1

S-1

Reformate to Storage

Naphtha Feed

EX-2

EX-3

Compressor

Hydrogen Rich Gas

Fig. 1 e A simple process flow diagram for conventional catalytic naphtha reforming (TR).

between two perforated screens. As depicted in Fig. 2(b), the


naphtha feed enters the top of the reactor and flows steadily
to the bottom of the reactor. Attempts should be made to
have a continuous flow without any channeling in the
reactor. The goal is to achieve a uniform flow distribution
through the catalytic bed, because the flow is mainly occurring in an axial direction. The two screens in upper and lower
parts of the reactor hold the catalyst and act as a mechanical
support. Since the cross-sectional area is smaller near the
inlet and the outlet of the reactor, the presence of catalysts in
these parts would cause substantial pressure drop and

consequently, reduce the efficiency of the spherical reactors.


The other advantage of these screens is to balance the free
zones (free catalyst zones) to find a desirable pressure drop
during the process. The radial flow is assumed to be negligible in comparison with the axial flow. As a result, the
equations in the axial coordinate are being taken into
account exclusively.

5.

Reactor modeling

5.1.
Axial- flow spherical packed-bed reactor model (AFSPBR model)

Table 1 e Specifications of reactors, feed, product and


catalyst of plant for fresh catalyst.
Parameter
Naphtha feed stock
Reformate
H2/HC mole ratio
LHSV
Mole percent of hydrogen in recycle
Diameter and length of 1st reactor
Diameter and length of 2nd reactor
Diameter and length of 3rd reactor

Numerical
Value
30.41  103
24.66  103
4.73
1.25
69.5
1.25, 6.29
1.67, 7.13
1.98, 7.89

Unit
Kg/h
Kg/h
e
h1
e
m
m
m

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

Reformate
( C)
44
73
105
123
136
153
181

Typical properties of catalyst in use


dp
Pt
Re
sa
rB
3

mm
wt%
wt%
m2/g
Kg/l
e

1.2
0.3
0.3
220
0.3
0.36

Rahimpour et al. have established the dynamic modeling of


spherical packed-bed reactors [30]. In this study, a homogeneous one-dimensional model has been considered. The flow
pattern in the AF-SPBR is assumed to be axial. The basic
structure of the model consists of heat and mass balance
equations. These equations must be coupled with the deactivation model, and also thermodynamic and kinetic relations
as well as auxiliary correlations for predicting physical properties. In order to solve the equations, an element with the
length dz (as shown in Fig. 3) has been considered and the
material and energy balances are written upon this element.
The mass and energy balance equations for fluid phase can be
formulated as follows:

Dej



m
X

vCj
vCj
1 v
1 v

nij ri 3
Ac
Ac uz Cj rB a
vz
vt
Ac vz
Ac vz
i1
j 1; 2; .; n



m
X


1 v
vT
1 v
DHi ri
Ac

rAc uz cp T  Tref rB a
Ac vz
vz
Ac vz
i1



v rcps T  Tref
3
vt

15

keff

(16)

where a is the catalyst activity, i represents the reaction


number and j represents the component number, Dej is the
effective diffusivity of component j, C is the gas phase
concentration, rB is the catalyst bulk density, vij is the

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R: Reactor
EX: Heat Exchanger
S-1: Separator
S-2: Stabilizer

Off Gas
R-3
S-2

R-2

R-1

EX-1

S-1

EX-2

Compressor

EX-3

Reformate to Storage
Hydrogen Rich Gas

Naphtha Feed

Naphtha Feed

Screen z=0

F1

L1
Z

dz

z+dz

L2

F1

Screen z=L1+L 2

Product

Fig. 2 e (a) Spherical axial-flow configuration for catalytic naphtha reforming and (b) conceptual Flow pattern and
specifications for spherical reactor in the catalytic naphtha reforming process.

stoichiometry coefficient of the reactant j in the reaction i, ri is


the reaction rate, keff is the thermal conductivity of the gas
phase, T is the temperature, r is the density of gas phase, CP is
the heat capacity of the gas phase, 3 is the void fraction and DH
is the heat of the reaction.
Its worth mentioning that the cross-section area, Ac, in the
AF-SPBR is a function of reactor length. Therefore it must
remain between the parentheses of the derivative equation of
mass and energy balances. The formulation of cross-section
area, Ac, is described as follows [23]:
i
h
Ac p R2  z  L1 2
The boundary and initial conditions are as follows:

(17)

z 0; Cj Cjo ; T To

(18)

vCj
vT
0;
0
vz
vz

(19)

ss
ss
t 0; Cj Css
j ; T T ; Ts Ts ; a 1;

(20)

z L1 L2 :

where L1 and L2 represent the vertical distance from the center


of the reactor to the top and bottom screens in the axial
coordinate. The superscript ss represents the steady state
condition. The steady state mass and energy balance equations are the same when the accumulation term is set to zero.
Mass and heat transfer coefficients are estimated by several

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 2 7 8 4 e1 2 7 9 9

Fz

6.




da
Ed 1
1
a7
Kd exp 

R T TR
dt

Fz+dz
Fig. 3 e Schematic for differential element along the flow
direction.

auxiliary correlations. These auxiliary correlations are presented in Appendix B. The heat of reactions is reported as
follows (kJ/kmol of H2):
71; 038:06
36; 953:33
51; 939:31
56; 597:54

5.2.

Conventional tubular reactor model (CR model)

The modeling assumptions of TR and AF-SPBR are similar. The


general fluid-phase balance is a model with the balances
typically accounting for accumulation, convection, and reaction. The energy and mass balances for the gas phase can be
written as Eqs. (21) and (22):
Dej

 
m
X
v2 Cj v uCj
vCj
rB a

nij ri 3
vz
vz2
vt
i1

j 1; 2; .; n

i 1; 2; .; m

keff

21

m
X




v2 T v 
v

DHi ri 3
rucp T  Tref rB a
rcp T  Tref
2
vz
vz
vt
i1

(22)
The boundary and initial conditions are as follows:
z 0 : Cj Cj0 ; T T0

(23)

vCj
vT
0;
0
vz
vz

(24)

ss
t 0 : Cj Css
j ; T T ; a 1

(25)

ZL:

5.3.

Pressure drop (Ergun equation)

The pressure drop throughout the catalyst bed is calculated


based on the Ergun equation. This equation covers the entire
range of flow rates by assuming that the viscous losses and
the kinetic energy losses are additive [23]. This equation for
Cartesian systems is derived as below:
2

Catalyst deactivation model

The catalyst deactivation model is used from the previous


work which was presented by Rahimpour [31].

dz

DH1
DH2
DH3
DH4

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dP 150m 1  3 Q 1:75r 1  3 Q

33
Ac
33
dz f2s d2p
Ac
fs dp

(27)

where TR, Ed and Kd are the reference temperature, the activation energy and the deactivation constant of the catalyst,
respectively. The numerical values of TR, Ed and Kd, are 770 K,
1.642  105 J mol1 and 5.926  105 h1, respectively.

7.

Numerical solution

In order to solve the set of coupled partial differentialalgebraic equations a two steps procedure is used. Firstly,
the steady state simulation is carried out to obtain the
initial conditions of the dynamic simulation. In the steady
state simulation all the time variations are considered to be
zero and activity will be considered to be one. Secondly,
the results of the steady state simulation are used as the
initial conditions for the time-integration of the dynamic
state equations in each node through the reactor. The
deactivation model and the conservation rules are ordinary
and partial differential equations, respectively. Moreover,
there would be algebraic equations due to the auxiliary
correlations, kinetics and thermodynamics of the reaction
system. These equations constitute a set of dynamic
equations.
The set of aforementioned equations of the model of
spherical and tubular reactors are solved by means of the
orthogonal collocation method [32,33]. Inner collocation
points are chosen as a root of a Jacobi polynomial. The
orthogonal collocation method is discussed further in
Appendix A. The system of PDEs is transformed into an
ordinary differential equation (ODE) system by means of this
numerical method. An energy balance is developed for each
collocation point, as well as a mass balance for each species.
The energy and mass balance equations of the spherical
reactor are systems of ODEs with initial conditions. The
system of ODEs is integrated by a modified Rosenbrock
formula of order two. It is noted that this method is well
suited for the systems of stiff equations [34]. In addition,
Gears method can be used for solving the set of such stiff
ODEs.

8.

Model validation

8.1.
Model validation with the presence of catalyst
deactivation

(26)

where dP is the pressure gradient, Q is the volumetric flow rate,


dp is the particle diameter, fs is the sphericity (for spherical
particles fs equals one), m is the fluid viscosity and r is the fluid
density.

Model validation is carried out by comparing the TR results


[28] with the proposed configuration over 800 operating days.
The predicted results of the production rate, the corresponding observed data and the residual error are presented in
Table 2. Good agreements between the daily observed plant

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Table 2 e Comparison between predicted production rate and plant data.


Time (day)

Naphtha feed (ton/h)

Plant (kmol/h)

AF-TPBR (kmol/h)

AF-SPBR (kmol/h)

Devi % (Tubular- Plant)

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

221.4080
222.3432
227.7559
226.6038
230.6220
231.0971
209.6965
224.5558
232.0072
228.0081
228.9246
324.2907
324.2216
324.4426
324.6099
324.7952
326.8164
327.0210
289.1475
294.6767

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

data and simulation results are achieved, so this model can


satisfy successfully the industrial conditions. The related
deviations from the plant reported values are due to the fact
that the kinetics and models used for reaction system of
naphtha reforming underestimated the true reaction rate.
Also using the average molecular weights and such other
physical properties for the three groups of pseudo components (PNA), heat transfer coefficients maybe increase the
uncertainties.

8.2.

Steady state model validation

A comparison between the proposed model and TR has been


demonstrated at the steady state condition in Table 3. As seen,
there is a good agreement between the plant data and predicted mole fractions of components at the output of the
system. Analyses of components (paraffin, naphthene and
aromatic) are performed by PONA Test in Stan Hop Seta
apparatus. The aromatic is tested especially by ASTM 2159
equivalent to UOP 273 method [28].

9.

Results and discussion

In order to have a desirable prediction, the appropriate


number of interior collocation points has been evaluated.
According to Fig. 4, the aromatic molar flow rate is plotted
versus the mass of catalysts with different number of interior
collocation points. In Fig. 4(a) one, two and three and in Fig. 4
(b) one, five, and seven interior collocation points have been
used. As it is shown in Fig. 4(a), when the number of interior
collocation points is not enough, the diversity appears
between the curves. But by increasing the number of interior
collocation points as shown in Fig. 4(b), the discrepancy
disappears between the curves. The curves with 5 and 7
interior points cover each other thoroughly. Therefore, the
N 5 is the most accurate choice.
Results of modeling involve the following main issues:
9.1 Changes of parameters along the spherical reactors.
9.2 Changes of parameters as a function of time.

Table 3 e Comparison between model prediction and plant data for fresh catalyst.
Reactor number
1
2
3

Inlet temperature (k)

Inlet pressure (kPa)

Catalyst distribution (wt %)

777
777
775

3703
3537
3401

20
30
50

Reactor number

1
2
3

Outlet temperature (k)

Input feedstock (mole %)


Paraffin
Naphthene
Aromatic

49.3
36.0
14.7

Aromatic in reformate (mole %)

Plant

NPBR

SPFR

Plant

NPBR

SPFR

722
753
770

727.38
751.03
770.54

727.45
751.66
770.75

e
e
57.7

34.78
47.28
56.26

34.77
47.12
56.18

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90

80
75

Paraffin

70
65
one interior collocation point
Ninterior=1

60
55

two interior collocation point


Ninterior=2

50

three interior collocation point


Ninterior=3

45
40

140

120

Molar flow rate (kmole/hr)

Aromatic molar flow rate (kmole/hr)

85

100

Aromatic

80
800th Day
1st Day

60

40
Naphthene
20

0.1

0.2

0.3
0.4
0.5
0.6
0.7
Mass of catalyst (Dimensionless)

0.8

0.9

1
0

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)

90

85

1500

Hydrogen molar flow rate (kmole/hr)

Aromatic molar flow rate (kmole/hr)

80
75
70
65
60

One interior collocation point


Ninterior=1

55

Five interior collocation point


Ninterior=5

50

Seven interior collocation point


Ninterior=7

45
40

0.1

0.2

0.3
0.4
0.5
0.6
0.7
Mass of catalyst (Dimensionless)

0.8

0.9

1450

1st Day

1350

1300

1250

Fig. 4 e Aromatic molar flow rate along the mass of catalyst


(a) with1, 2 and 3 and (b) and 1, 5 and 7 interior orthogonal
collocation points.

800th Day

1400

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Mass of catalyst (Dimensionless)

780

Temperature (K)

770

3750
L=0.10R

L=0.30R

3700
L=0.50R

3650

Pressure (kPa)

L=0.70R

760

750
TR
SR

740

3600
L=0.90R

3550

730

3500
720

3450

L=0.95R

3400
3350
3300
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Mass of catalyst (Dimensionless)


Fig. 5 e Pressure profile along the mass of catalyst (solid
line: tubular reactor, dotted line: spherical reactor).

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Mass of catalyst (Dimensionless)

TR
SR

Fig. 6 e (a) Production and consumption rates versus mass


of catalyst (solid line: the 1st day of production, dotted line:
the 800th day of production), (b) hydrogen molar flow rate
versus mass of catalyst (solid line: the 1st day of
production, dotted line: the 800th day of production) and (c)
the temperature profiles of TR and SR.

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0.95

1st reactor

4000

3500

2nd reactor
3rd reactor

Pressure (kPa)

Catalyst activity

0.9

0.85

3000

2500

0.8

2000

0.75

1500

0.7

100

200

300

400
500
Time (Day)

600

700

1000
0.1

800

Fig. 7 e (a) The catalyst activity during 800 days of


operation for the 1st, the 2nd and the 3rd reactors.

FR=1.0
FR=2.0
FR=2.5
FR=3.0

0.2

0.3

0.4

0.5
L/R

0.6

0.7

0.8

0.9

0.6

0.7

0.8

0.9

0.6

0.7

0.8

0.9

0.36
0.35

The variables that affect the performance of the catalyst,


the yield and quality of reformate are time, feedstock properties, reaction temperature, space velocity, reaction pressure,
and hydrogen per hydrocarbon ratio [35].

FR=1.0
FR=2.0
FR=2.5
FR=3.0

0.34

Aromatic yield

9.3 Effect of operating conditions and a comparison between


tubular and spherical reactors in this regard.

0.33
0.32
0.31
0.3
0.29

0.1

0.2

0.3

0.4

0.5
L/R

0.88
0.87
0.86

Hydrogen yield

0.85
0.84
0.83

FR=1.0
FR=2.0
FR=2.5
FR=3.0

0.82
0.81
0.8
0.79
0.78
0.1

0.2

0.3

0.4

0.5
L/R

Fig. 9 e The effect of different FR ratios on (a) the pressure


versus L/R, (b) the aromatic yield versus L/R and (c) the
hydrogen yield versus L/R.

9.1.

Fig. 8 e (a) Aromatic and paraffin and (b) light end and
hydrogen mole productions during 800 days of operation.

Changes of parameters along the spherical reactors

The changes of parameters along the length of the spherical


reactors in the 1st and the 800th days of operation will be
investigated in the first section.

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1505

0.36
0.35

P=2703 kPa

Hydrogen production (kmole/hr)

0.34

Aromatic yield

0.33
0.32
0.31
0.3
TR
SR

0.29
0.28

P=3070 kPa

1495
TR
SR
1490

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

1480
2000

2200

2400

2600

(B)

2800

3000

3200

3400

3600

3800

4000

Operating pressure (kPa)

Mass of catalyst (Dimensionless)

(A)
1485

P=1703 kPa

0.27
0.26
0.5

1500

Fig. 11 e Hydrogen production versus operating pressure


for spherical and tubular reactor.

0.37
0.36
0.35

Aromatic yield

0.34

P=3703 kPa

a 4000

0.33

3500

0.32

3000

0.3

P=4703 kPa

TR
SR

0.29

0.5

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

Pressure (kPa)

0.31

2500
SR
TR

2000
1500

Mass of catalyst (Dimensionless)


1000

Fig. 10 e Aromatic yield versus mass of catalyst in third


reactor (a) for operating pressures 1703 and 2703 kPa and
(b) for operating pressures 3703 and 4703.

500
0

Feed flow rate scale up ratio

0.4
0.38
0.36

SR
TR

0.34

Aromatic yield

As shown in Fig. 5, the pressure is depicted versus the


dimensionless mass of catalysts of three reactors for various
L/Rs. it can be seen, by increasing L/Rs the pressure drop
increases. Thus, for L/R 0.95 the greatest pressure drop is
achieved. At higher L/Rs, a huge bulk of feed encounters less
empty zones at the inlet and the outlet of the reactor. As
a result, a sudden pressure drop happens in the pressure
profile. The steps indicate the pressure drop in each reactor.
The dimensionless mass of catalyst for the 1st, the 2nd and
the 3rd reactors is in the range of 0e0.2, 0.2e0.5 and 0.5e1,
respectively. The dimensionless mass of catalyst 0 shows
the inlet of the 1st spherical reactor and the dimensionless
mass of catalyst 1 implies the outlet of the 3rd reactor. On
the other hand, if L/R decreases to lower than 0.7, the pressure
drop would decrease too. However, working with the L/R 0.5
is useless because most of the reactor space is empty without
any catalyst. Thus, the L/R 0.7 is chosen not only to reduce
the useless fabrication of materials for free zone but also to
have a little pressure drop. The reason which makes this ratio
a proper choice will be discussed later.
In previous works, the total molar flow rate was assumed
to be constant while it increases throughout the reactor in

0.32
0.3
0.28
0.26
0.24
0.22
0.2

Feed flow rate scale up ratio

Fig. 12 e (a) Pressure versus feed flow rate scale up ratio


and (b) aromatic yield versus feed flow rate scale up ratio at
3703 kPa for tubular and spherical reactors(solid line:
tubular reactor, dotted line: spherical reactor).

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b
4000

0.45

3500

0.4

Aromatic yield

Pressure (kPa)

3000
2500
2000

0.35
0.3
0.25

1500
15

0.2
15
6

10

Catalyst scale up ratio

10

2
0

4
3

Catalyst scale up ratio

Flow scale up ratio

2
1

Flow scale up ratio

c
0.9

Hydrogen yield

0.8
0.7
0.6
0.5
0.4
15
6

10

5
4

Catalyst scale up ratio


0

2
1

Flow scale up ratio

Fig. 13 e 3-D figure which shows the effect of flow scale up ratio and catalyst scale up ratio on (a) pressure and (b) aromatic
yield.

plants. In this study, the total molar flow and also all physical
properties such as heat capacity and thermal conductivity are
assumed to be variable along the reactors.
A scheme of components molar flow rates versus the
mass of catalyst along the reactor for the 1st and the 800th
days of operation is depicted in Fig. 6(a). As seen, the aim of
naphtha reforming is satisfied, because the molar flow rate
of aromatics increases along the reactor and fortunately
the molar flow rates of naphtha and paraffin decrease.
Each break point in this figure indicates the inlet temperature of the following reactor. Because the temperature
increases by using pre heaters at the inlet of each reactor,
the reaction rates change and discontinuities appear in the
figure.
Also, Fig. 6(b) illustrates hydrogen molar flow rate versus
the mass of catalyst along the reactor. Fig. 6(c) presents
the temperature distribution through the TR and SR. As the
naphtha reforming is predominantly endothermic, the
temperature decreases in the reactors.

9.2.

activity as a function of time in three reactors. As the reactions


proceed, the catalyst activity decreases. The catalyst activity
has an inverse relationship with the temperature, in other
words, as the temperature decreases the catalyst activity
increases.
Fig. 8(a) illustrates the effect of catalyst deactivation on the
product and reactant production rates. By decreasing the
catalyst activity, the aromatic production rate decreases and
hence the amount of unreacted paraffin increases due to
lower reaction rate. As a result of catalyst deactivation, both
the reaction rate and the production rate decrease. The light
end (off gas) production rate as a function of time is depicted
in Fig. 8(b). As seen, this product also decreases in the course
of time due to the catalyst deactivation. An unpredictable
behavior is observed in Fig. 8(b) for hydrogen production. The
catalyst aging acts in a way that hydrogen produces more after
the 800th day of operation compared with the 1st day.

9.3.
Effect of operating conditions and a comparison
between tubular and spherical reactors in this regard

Changes of parameters as a function of time

In the second part, the variation of parameters as a function of


time will be discussed. Fig. 7 reveals the average catalyst

The effect of operating conditions such as flow scale up ratio


(FR), operating pressures and other parameters are studied in
the following section.

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The effect of flow scale up ratio (FR)

The effect of FR on pressure is illustrated first. The pressure


versus L/R for different FRs is shown in Fig. 9(a). FR indicates
that the flow rate of fresh naphtha feed in spherical reactor is
more compared with the feed stream in TR. As seen,
increasing the FR increases the pressure drop and this will be
more significant for higher L/Rs. The slope of curves starts to
change at the L/R 0.7 and the variation of pressure drop
experiences a new trend in spherical reactors. At the L/R 0.7,
the pressure drop increases by increasing the FR. But, the
pressure drop augmentation at this ratio is approximately less
than higher values of L/Rs. Therefore, the L/R 0.7 is an
appropriate choice, due to observation of considerable pressure drop after this point. This is an evidence to show that the
L/R 0.7 is a proper choice. The aromatic yield versus L/R for
different FRs is illustrated in Fig. 9(b). According to the Le
Chateliers principle, for FRs equal to 1e2 the pressure drop at
L/R 0.7e0.9 shifts the reaction to the aromatics and
hydrogen production. The residence time decreases in higher
FRs owing to providing a larger quantity of reactants per unit
of catalyst. Consequently, it decreases the products yield (see
Fig. 9(b)e(c)). Higher pressure drop at FRs of 2.5e3 reduces the
reactants partial pressures and this affects the reaction rates.
It should be mentioned that all the previous results in this part
have been achieved at the constant inlet compressor pressure
of 3703 kPa.

Effect of operating pressure

Fig. 10(a, b) shows the aromatic production in spherical


reactor (SR) and tubular reactor (TR) based on the dimensionless mass of catalyst for various operation pressures. As
seen from Fig. 10(a), when the operating pressure equals
1703 kPa, the aromatic yield in the SR is considerably higher
than the TR. As the operating pressure increases, the difference between the aromatic yields in two reactor configurations decreases (see the graph for Pressure of 2703 kPa). The
intersection of tubular and spherical curves is named
the turning junction point. However, the arrangement of the
curves will change at the turning junction point and the
aromatic yield in TR becomes more than the one in SR (see
Fig. 10(b)). In other words, the TR unlike the SR is incapable of
operating satisfactorily at low pressures. In spite of SR
advantages (lower pressure drop, lower construction material,
lower surface area and lower related maintenance costs), the
operating pressure should be wisely determined when
compared with the TR. The same trend is observed for
hydrogen production rate versus the operating pressure for SR
and TR configurations in Fig. 11.

9.3.3.

The effect of feed flow rate scale up ratio

The capability of spherical reactors in using higher flow rates


in comparison with the tubular ones is clearly represented by
Fig. 12(a). If the feed flow ratio in TR is doubled, the pressure
decreases drastically. On the other hand if the feed flow ratio
in spherical reactor equals to 7, the pressure declines.
Therefore, if the feed flow ratio in spherical reactor increases
more products would be achieved. The effect of flow rate
augmentation on quality is investigated by considering the
product yields. According to Fig. 12(b), the peak is observed for
low feed flow rate in both reactors. Due to low feed flow rate

0.45
CMR=1
CMR=2
CMR=3
CMR=4

0.4

Aromatic yield

9.3.2.

and high catalyst loading, the sufficient time exists for converting the feed to aromatics. Therefore the peak is seen in
low feed flow rates (less than 1). When the feed flow rate scale
up ratio equals to 1, the aromatic yield in the tubular reactor is
slightly higher than the yield in the spherical reactor. By
increasing the scale up ratio in two reactors the aromatic yield
decreases in both reactors but the slope is sharper in TR. The
pressure drop has a strongly negative effect on the aromatic
production in tubular reactors due to the FR. It should be
mentioned that Fig. 12(a, b) are depicted in the constant inlet
pressure of 3070 kPa for tubular and spherical reactors.
The simultaneous effect of catalyst and FRs on pressure,
aromatic and hydrogen yields is investigated in the following
3-D plots. The various catalyst distributions in SR in comparison with the TR are identified by catalyst scale up ratio.
Fig. 13(a) illustrates the simultaneous effect of catalyst and
FR on pressure. For all catalyst scale up ratios the pressure
decreases by increasing the FR. Especially for lower catalyst
scale up ratios, the pressure drop is higher due to lower
reactor diameter and high viscose loss in higher velocities.
When, the catalyst scale up ratio increases to 5, the flux
decreases due to the increase in the reactor diameter. Therefore the pressure becomes approximately constant. In low

0.35
0.338

0.3

0.25

0.2

Flow scale up ratio

1
0.9
0.876
0.8

Hydrogen yield

9.3.1.

0.7
0.6
0.5
CMR=1
CMR=2
CMR=3
CMR=4

0.4
0.3
0.2

Flow scale up ratio

Fig. 14 e The effect of CMR and the flow scale up ratio on (a)
aromatic yield and (b) hydrogen yield.

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catalyst scale up ratios, the pressure drop increases by


increasing the FR. Fig. 13(b) illustrates the simultaneous effect
of catalyst and FRs on the aromatic yield. In each FR, if the
catalyst scale up ratio increases, the aromatic yield will
increase. In general, the catalyst scale up ratio causes higher
aromatic yield for each FR. However, increasing FR decreases
the aromatic yield in each catalyst scale up ratio. The simultaneous effect of catalyst and FR is considered on hydrogen
yield in Fig. 13(c).
The effect of FR on aromatic yield for different catalyst
mass ratios (CMRs) is depicted in Fig. 14(a) for SR. The
aromatic yield is considered to be 0.338 in industry and the
industry data for CMR 1 is depicted as solid line. If the FR
equals 2, in order to achieve the same (0.338) aromatic yield
the CMR should be a little less than 2 (1.9 times). Similarly, if
the FR equals 3, the CMR should be a little less than 3(2.85
times) in fixed aromatic yield. In high CMRs, as FR increases,
the difference between the fixed aromatic yield (0.338) and the
obtained aromatic yield increases. In general, in order to have
a specific flow (FR) a little less than the specified value is
needed for catalyst loading. The difference between these two
values is larger for higher FRs. The effect of FR on hydrogen
yield in different CMRs is depicted in Fig. 14(b). In CMR 1, as

0.9
0.85

Hydrogen yield

0.8
0.75
0.7
T1=777, T2=777
T1=777, T3=775

0.65
0.6

T2=777, T3=775

0.55
0.5
0.45
650

700

750

800

850

Inlet temperature (K)

0.5

0.45

FR increases hydrogen yield decreases and a peak is observed


in the figure. Hydrogen yield becomes constant for the CMRs
higher than 3. If higher FRs is desired, the CMR should be more
than 3. In order to achieve the fixed hydrogen yield (0.87),
when the FR is less than 3, it is satisfactory to work with
minimum CMR which equals to 2.

9.3.4.

The effect of temperature on the products yields

In order to consider the effect of temperature, the inlet


temperatures of two reactors out of three is considered to be
constant and the inlet temperature of the other reactor
changes to examine the effect of temperature. Fig.15(a, b)
illustrates the effect of temperature on hydrogen and
aromatic yield, respectively. As the temperature exceeds,
hydrogen is consumed and the yield decreases. The results
show that increasing the 1st reactor temperature (dotted lines
in Fig.15(a, (b)) is more efficient in order to hydrogen and
aromatic production.

10.

Conclusion

In any process, a significant incentive to minimize the pressure drop has led to developing a number of alternatives on
the flow configurations. According to this concept, one
potentially interesting idea for catalytic naphtha reforming
process is the application of AF-SPBR. The pressure drop
problem is successfully overcome in this new configuration. In
this study, the AF-SPBR is proposed for catalytic naphtha
reforming process. The effect of several parameters on
aromatic and hydrogen yields is investigated. Most of the
parameters of the system are considered to be variable such as
heat capacity, viscosity, molecular weight, pressure, density
and the total molar flow. Optimum pressure and L/R are
determined. The dynamic model is solved by the orthogonal
collocation method and the results are much better in
comparison with the other conventional methods such as
finite difference method. Results show that the AF-SPBR can
be properly applied instead of TR. This study shows that for
naphtha reforming process the AF-SPBR configuration is more
efficient than the previous ones. The practical operating
conditions data together with the mathematical model can be
used to develop the AF-SPBR model for new plant setups and
revamps of process in future.

Aromatic yield

0.4

0.35

Acknowledgement
0.3
T1=777, T2=777
T1=777, T3=775

0.25

The authors would like to thanks gratefully to Samira Hafeziyeh for her helpful recommendation to improve the English
language of the manuscript.

T2=777, T3=775
0.2

650

700

750

800

850

Appendix A. Orthogonal Collocation method

Inlet temperature (K)

Fig. 15 e The effect of inlet temperatures on (a) hydrogen


and (b) aromatic yields.

Jacobi polynomials
a;b

The Jacobi function, JN x, is a polynomial of degree N that is,


orthogonal with respect to the weighting function xb 1  xa .

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 2 7 8 4 e1 2 7 9 9

The Jacobi polynomial of degree N has the power series as


follow:
N
X
a;b
JN x
 1Ni gN;i xi
(A e1)
i0

The domain of x is in the range [0, 1].


The evaluation of coefficients is done by using the
following recurrence formula
gN; i
Ni1 Niab

$
gN; i1
i
ib


T
y y1 ; y2 ; y3 ; .; yN ; yN1

y0 A$y
y00 B$y

gN,i are constant coefficients, and a and b are parameters


characterizing the polynomials.

Lagrange Interpolation Polynomials


For a given set of data points (x1, y1), (x2, y2),.,(xN, yN) and
(xN1, yN1) an interpolation formula passing through all
(N 1) points is an Nth degree polynomial. A suitable interpolation polynomial for the orthogonal collocation method is
Lagrange interpolation polynomial, which passes through the
interior collocation points, roots of Jacobi polynomials, and it
is expressed as
yN x

yj lj x

(A e4)

j1

li x

j1
jsi



x  xj


xi  xj

Furthermore,

0 isj
1 ij

 
li xj

(A e5)

The first and second derivative at the interpolation points


are:
N1
dlj xi
dyN xi X
yj

dx
dx
j1

(A e7)

N1 2
d lj xi
d2 yN xi X

yj
dx2
dx2
j1

(A e8)

For i 1; 2.; N; N 1:
The first derivative vector, composed of (N 1) first derivatives at the (N 1) interpolation points is:
y0N

T
dyN x1 dyN x2
dyN xN dyN xN1
;
; .;
;
dx
dx
dx
dx

(A e9)

Similarly, the second derivative vector is defined as


y00N

#T
"
d2 yN x1 d2 yN x2
d2 yN xN d2 yN xN1
;
;
.;
;
dx2
dx2
dx2
dx2

(A e10)

The function vector is defined as values of y at (N 1)


collocation points as

)
d2 lj xi
bij
; i; j 1; 2; .; N; N 1
dx2

(A e13)

(A e14)

The matrices A and B are (N 1, N 1) square matrices.


Once the (N 1) interpolation points are chosen, then all the
Lagrangian building blocks, li(xi), are completely known, and
thus the matrices A and B are also known [36].

Appendix B. Auxiliary Correlations


B.1.

Gas phase viscosity

Viscosity of reactants and products is obtained from the


following formula:
C1 TC2
C3 C4

1
T T2

(B e1)

where m is the viscosity in Pa.s and T is the temperature in K.


Viscosities are at 1 atm [37].

B.2.

(A e6)



dlj xi
; i; j 1; 2; .; N; N 1
aij
dx
(

where yN is the Nth degree polynomial, yi is the value of y at


the point xi, and li(x) is defined as
N
1
Y

(A e12)

Where the matrices A and B are defined as


(A e2)

(A e3)

N1
X

(A e11)

By means of these definitions of vectors y and derivative


vectors, the first and second derivative vectors can be written
in terms of the function vector y using matrix notation

Starting with
gN;0 1

12797

Gas phase Heat capacity

Heat Capacity of reactants and products at Constant Pressure


is obtained from the following formula:
2
2
32
32
C3
C5
6
6
7
7
6
6
T 7
T 7
(B e2)
Cp C1 C2 6
7 C4 6
7
4
4
C3 5
C5 5
sin h
cos h
T
T
where cp is in J/(kmol K) and T is in K [37].
To complete the simulation, extra correlations should be
added to the model. In the case of heterogeneous model,
because of transfer phenomena, the correlations for estimation of heat and mass transfer between two phases should be
considered. It is because of the concentration and heat gradient
between bulk of the gas phase and the film of gas on the catalyst
surface, which caused by the resistance of the film layer.

B.3.

Mass transfer correlations

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


following equation [38]:


1=2 
kci dp 3 1
u
m
(B e3)

Dim 1  3 g
m1  3g
rDim
where dp is particle diameter (m), 3b is void fraction of packed
bed, is shape factor of pellet, u is superficial velocity through

12798

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 2 7 8 4 e1 2 7 9 9

packed bed (m/s), is viscosity of gas fluid phase (kg/m s) and is


fluid density (kg/m3).
Diffusivity of component i in the gas mixture is given by
Ref. [39].
Dim



1  yi


P

yi =Dij

B.4.

(B e4)

(B e5)

Heat transfer correlation

The heat transfer coefficient between the gas phase and solid
phase is obtained by the following correlation [41]:


hf cp m2=3 0:458 rudp 0:407

cp rm K
m
3b

kf3
kf4

The binary diffusivities are calculated using the Fullere


SchetterGiddins equation which is reported by Reid et al.
[40]. In the following FullerSchetterGiddins correlation, vci,
Mi are the critical volume and molecular weight of component
i which are reported in.

1=2
107 T3=2 1=Mi 1=Mj
Dij

2
Pt vci3=2 vcj3=2

kf2

(B e6)

where in the above equation, u is superficial velocity of gas


and the other parameters are those of bulk gas phase, dp is the
equivalent catalyst diameter, K is the thermal conductivity of
gas, r, m are density and viscosity of gas, respectively and 3 is
void fraction of catalyst bed. To see the constants which are
used in these equations please see reference [22].

Appendix C. Nomenclature

Parameter description
a
catalyst activity, e
element of matrix A, e
aij
A
moles of aromatic formed, kmol h1
A
matrix defined in Eq. (Ae12), e
cross-section area of reactor, m2
Ac
B
matrix is defined in Eq. (Ae12), e
element of matrix B, e
bij
C
concentration, kmol m3
Ci
coefficient of Eqs. (B-1) to (B-2), e
inlet concentration of component j, kmol m3
Cj0
cp
specific heat capacity, kJ kmol1 K1
dp
particle diameter, m
effective diffusivity, m2s1
De
Dim
diffusivity of component i in the gas mixture, m2 s1
Ed
activation energy of catalyst, J mol1
Ei
activation energy for ith reaction, kJ kmol1
hf
heat transfer coefficient, W m2 K1
HC
hydrocarbon, kmol h1
H2
hydrogen, kmol h1
J
jacobi function, e
effective thermal conductivity, W m1 s1
keff
kci
mass transfer coefficient for component i, m h1
kf1
forward rate constant for reaction (1), kmol h1
kg cat1 M Pa1

Ke1
Ke2
Kd
L
lj
m
m
mc
Mi
Mw
n
n
N
NA
Ni
p
Pi
P
Q
r
ri
R
Ri
Ro
sa
t
T
Tref
TR
ur
x
yN
yi
yis
vc
y0N
y00N
a
b
g
3
m
vij
r
rB
s
fs
DH
a
cal
h
i
j

forward rate constant for reaction (2), kmol h1


kgcat1 MPa2
forward rate constant for reactions (3), kmol h1
kg cat1
forward rate constant for reactions (4), kmol h1
kg cat1
equilibrium constant, MPa3
equilibrium constant, MPa1
deactivation constant of the catalyst, h1
length of reactor, m
building block of jacobi polynomial, e
number of data sets used, e
number of reaction, e
mass of catalyst, kg
molecular weight of component i, kg kmol1
average molecular weight of the feedstock, kg kmol1
average carbon number for naphtha, e
number of component, e
degree of Jacobi function, e
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
radius, m
rate of reaction for ith reaction, kmol kg cat1 h1
gas constant, kJ kmol1 K1
inner radius of spherical reactor, m
outer radius of spherical reactor, m
specific surface area of catalyst pellet, m2 kg1
time, h
temperature of gas phase,  K
reference temperature,  K
reference temperature,  K
radial velocity, m s1
variable represent length of reactor, m
jacobi polynomial of degree N, e
mole fraction for ith component in gas phase, e
mole fraction for ith component on solid phase, e
critical volume, cm3 kmol1
first derivative of jacobi Equation, e
second derivative of jacobi Equation, e
characteristic parameter of Jacobin equation, e
characteristic parameter of Jacobin equation, e
coefficient of equation (Ae1), e
void fraction of catalyst bed, e
viscosity of gas phase, kg m1 s1
stoichiometric coefficient of component i in
reaction j, e
density of gas phase, kg m3
reactor bulk density, kg m3
tensile stress, Nm2
sphericity, e
heat of reaction, kJ kmol1
aromatic, e
calculated, e
hydrogen, e
numerator for reaction, e
numerator for component, e

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 2 7 8 4 e1 2 7 9 9

n
naphthene, e
out
outlet, e
p
paraffin, e
ss
steady state, e
T
transpose, e
AF-SPBR axial-flow spherical packed-bed reactor, e
AF-TPBR axial-flow tubular packed-bed reactor, e
FBP
final boiling pint,  C
IBP
initial boiling pint,  C
LHSV
liquid hourly space velocity, hr1
OF
objective function, e
Pt
platinum, e
RF-SPBR radial flow spherical packed-bed reactor, e
RF-TPBR radial flow tubular packed-bed reactor, e
Re
rhenium, e
RON
research octane number, e
Sph.
spherical reactor, e
tub
tubular reactor, e
TBP
true boiling point, K
WHSV weight hourly space velocity, h1

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