Chemical Engineering Journal 178 (2011) 264–275

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Chemical Engineering Journal

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

A dynamic membrane reactor concept for naphtha reforming, considering

radial-flow patterns for both sweeping gas and reacting materials
D. Iranshahi a , E. Pourazadi a , K. Paymooni a , M.R. Rahimpour a,∗ , A. Jahanmiri a , B. Moghtaderi b
a
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran
b
Priority Research Centre for Energy, Chemical Engineering, School of Engineering, Faculty of Engineering & Built Environment, The University of Newcastle, Callaghan,
NSW 2308, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Hydrogen will become an essential energy source in the near future. In this regard, refineries can be
Received 7 November 2010 considered as alternative sources of hydrogen production. In the present study, a tubular membrane
Received in revised form 7 July 2011 reactor with radial-flow patterns of the sweeping gas and the naphtha feed named RF-TMR is proposed
Accepted 4 August 2011
as a novel configuration for radial-flow naphtha reformers. Radial-flow reactors are used in refineries as
a remedy for high pressure drop through the catalytic packed-bed reactors which disturbs the reactor
Keywords:
operation. The cross section area of the tubular membrane reactor is divided into some subsections.
Radial-flow tubular membrane reactor
The walls of the gaps are coated by a Pd–Ag membrane layer to separate hydrogen from reaction side
Naphtha reforming
Dynamic operation and enhance the hydrogen and aromatic production rates by 0.33 ton/day and 5.5 ton/day, respectively
Hydrogen separation (compared with the AF-TR). The performance of this novel configuration is investigated and compared
Octane improvement with the axial-flow conventional tubular reactor (AF-TR) and axial-flow tubular membrane reactor (AF-
TMR). Set of coupled partial differential–algebraic equations are solved by the orthogonal collocation
method. Owing to a slight pressure drop in the tube side of RF-TMR, smaller catalysts’ particles with a
negligible internal mass transfer resistance can be used to increase aromatics and hydrogen yields. This
novel approach has the feasibility to be applied in the radial-flow moving bed reformers which are widely
installed in refineries by licensors.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction number of theoretical and experimental studies basically due to

The introduction section is divided into four subsections in order
that each clarifies one specific aspect of this contribution. In the
first place, the importance of the catalytic reformers as a key pro-
cess in refineries for high octane gasoline production is explained;
secondly, the significance of hydrogen production from refiners
viewpoint and global protection is identified. In the last two parts,
the successful application of membrane technology for hydrogen
separation to the conventional separation technologies and the
importance of the pressure drop in the catalytic packed-bed reac-
tors as the heart of chemical processes are discussed.
1.1. Naphtha reforming
Full-range naphtha is the fraction of the crude oil with a boiling
temperature between 30 ◦ C and 200 ◦ C and constitutes typically
15–30% by weight of the crude oil. Naphtha and reformate are
complex mixtures of paraffins, naphthenes and aromatics in the
C5 –C12 ranges [1,2]. Reforming units have been the target of a large
∗ Corresponding author. Tel.: +98 711 2303071; fax: +98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
their strategic and important role in the economical outcome of
the refinery complexes for high octane gasoline production. In
this regard, a vast variety of researches have been implemented
on the catalytic naphtha reforming process. The kinetic of cat-
alytic naphtha reforming has attracted the attentions of many
researchers. Smith [3] was the pioneer of the researchers. He
assumed three pseudo components including paraffin, naphthene
and aromatic (PNA) and four dominant reactions. Ancheyta-Juárez
and Villafuerte-Macías [4] proposed a lumped kinetic model for the
catalytic naphtha reforming process. Their model utilized a lumped
mathematical representation of reactions in terms of isomers of the
same nature. In order to include the effect of pressure and tempera-
ture on the rate constants, the Arrhenius-type variation was added
to the model. Stijepovic et al. [5] proposed a semi-empirical kinetic
model for catalytic reforming. Their lumping strategy was based
on paraffins, olefins, naphthenes and aromatics (PONA) analyses.
Boyas and Froment [6] studied a very detailed model for the cat-
alytic reforming of naphtha from its fundamental chemistry. Their
proposed model provided a thorough insight into the process as
well as a wide predictive potential; however, it contained a huge
number of parameters. Other similar work has been done by Kmak
[7], Weifeng et al. [8], Ramange et al. [9], Marin et al. [10] and
Krane et al. [11]. Furthermore, study of new catalysts’ types with

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.08.005
 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275 265

Nomenclature
Out outlet
Parameter Description P paraffin
a catalyst activity ss steady state
A moles of aromatic formed (kmol h−1 )
Ac cross-section area of reactor (m2 ) Abbreviations
C concentration (kmol m−3 ) AF-TR axial flow tubular reactor
Cj0 inlet concentration of component j (kmol m−3 ) AF-TMR axial flow tubular membrane reactor
Cp specific heat capacity (kJ kmol−1 K−1 ) FBP final boiling pint (◦ C)
dp particle diameter (m) IBP initial boiling pint (◦ C)
De effective diffusivity (m2 s−1 ) LHSV liquid hourly space velocity (h−1 )
Dim diffusivity of component i in the gas mixture NOS number of subsections
(m2 s−1 ) OF objective function
Ed activation energy of catalyst (J mol−1 ) RF-TMR radial flow tubular membrane reactor
Ei activation energy for ith reaction (kJ kmol−1 ) RON research octane number
hf heat transfer coefficient (W m−2 K−1 ) TBP true boiling point (K)
HC hydrocarbon (kmol h−1 ) WHSV weight hourly space velocity (h−1 )
H2 hydrogen (kmol h−1 )
keff effective thermal conductivity (W m−1 s−1 )
Kd deactivation constant of the catalyst (h−1 ) different metal bases has been a matter of new researches to
L length of reactor (m) improve the performance of catalyst and reformers for higher aro-
M number of reaction matic selectivity. Studies in this field were conducted by Pieck et al.
mc mass of catalyst (kg) [12], Martin et al. [13], Mazzieri et al. [14,15], Borgna et al. [16],
Mi molecular weight of component i (kg kmol−1 ) Viswanadham et al. [17] and Benitez et al. [18].
Mw average molecular weight of the feedstock
(kg kmol−1 ) 1.2. Hydrogen
n average carbon number for naphtha
N number of component Hydrogen is not only an essential energy carrier for the future,
NA molar flow rate of aromatic (kmol h−1 ) but also a fundamental raw material and feedstock in petroleum
Ni molar flow rate of component i (kmol h−1 ) and chemical engineering. Increasing demand for hydrotreating
P moles of paraffin formed (kmol h−1 ) (due to stricter legislation on sulfur content of fuels) and the
Pi partial pressure of ith component (kPa) processing of heavier crude oil in refineries [19] have recently
P total pressure (kPa) demonstrated more and more the importance of hydrogen in
Q volumetric flow rate (m3 s−1 ) refineries. On the other hand, the results of global energy scenarios
R radius (m) of IEA’s Energy Technology Prospective and the WETO H2 scenarios
ri rate of reaction for ith reaction (kmol kgcat−1 h−1 ) of the European Commission show the emergence of a considerable
R gas constant (kJ kmol−1 K−1 ) hydrogen demand until 2050 [20]. Therefore, hydrogen production
sa specific surface area of catalyst pellet (m2 kg−1 ) by the catalytic naphtha reforming units can be considered as a
T time (h) solution for these criteria. Also, widespread usage of hydrogen can
T temperature of gas phase (K) alleviate the growing concerns about the world’s energy supply,
Tref reference temperature (K) security, air pollution and greenhouse gas emissions.
TR reference temperature (K)
ur radial velocity (m s−1 ) 1.3. Membrane
yi mole fraction for ith component in gas phase
yis mole fraction for ith component on solid phase Since separation and purification are key steps in the production
of chemicals, there is keen interest in incorporating a membrane
Greek letters
into a reactor in order to reduce the number of operating units
ε void fraction of catalyst bed
(and cost) and enhance the production rates [21]. Separation by
 viscosity of gas phase (kg m−1 s−1 )
membrane is less energy intensive which requires no phase change
vij stoichiometric coefficient of component i in reaction
in the process and typically provides low maintenance operation
j
[22]. There are increasing demands for H2 within refineries, and it
 density of gas phase (kg m−3 )
would seem that one might be able to use the Pd hydrogen perm-
b reactor bulk density (kg m−3 )
selective membranes for this purpose. The Pd–Ag membrane layer
 tensile stress (N m−2 )
with the silver content of 23–25% is extensively used for hydrogen
s sphericity
separation [23,24]. As many as one hundred membrane plants have
been installed in refineries, thus the opportunity exists in the other
Subscript and superscripts
refineries to use this technology for hydrogen production [25]. Key
H heat of reaction (kJ kmol−1 )
requirements for the successful development of palladium-based
A aromatic
membranes are low costs as well as perm-selectivity combined
cal calculated
with good mechanical/thermal and long-term stability [26].
H hydrogen
i numerator for reaction
1.4. Pressure drop
j numerator for component
N naphthene
In gas-phase reactions, the concentration of reactants is signifi-
cantly affected by changes in the total pressure. Indeed, the reaction
266 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275

R-1 R-2 R-3

Off Gas
C: Compressor
R: Reactor
F: Furnace
S-1: Separator
S-2: Stabilizer
S-1 S-2

Reformate to Storage
F-1 F-2 F-3

Naphtha Feed

Hydrogen Rich Gas

C-1

Fig. 1. A simplified process flow diagram for catalytic naphtha reforming (AF-TR).

rates and conversions are strongly reduced as well as total pres-
sure. Consequently, proper accounting for the effects of pressure
drop in the reactors, in many instances, is a key issue in the success
or failure of the reactor operation. Therefore, the pressure drop is a
serious problem in industrial plant operations especially catalytic
reactors. The solution is to use radial-flow reactors. In the radial-
flow reactors, the total feed is distributed over the surface area of
the reactor instead of the cross section area in the axial flow reac-
tors. Moreover, the feed passes through a shorter distance (radius)
compared with the total length of reactor in the axial flow configu-
ration. Thus, the feed encounters with minor loss in its energy and
indeed pressure drop.
All the above issues (octane boosting, higher hydrogen pro-
duction rate and negligible pressure drop) can be addressed by
incorporating membrane concept in the radial-flow reformers as an
alternative configuration for conventional naphtha reforming pro-
cess. In this study, a one-dimensional mathematical model has been
performed to evaluate the performance of RF-TMR with the radial-
flow patterns of the sweeping gas and the naphtha feed in shell and
tube sides as an alternative configuration for naphtha reforming
process. Since this is a novel proposed configuration in the field of
chemical engineering and reactor design, immediate needs for the-
oretical studies are tangible. Mathematical modeling helps policy
makers to identify promising technologies as well as the advan-
tages and disadvantages of such a new configuration. In addition,
it can contribute to considerable savings in money and time dur-
ing the expensive stage of pilot plant development. However, the
lab scale experiment along with the optimal investigation is consid-
ered as the subsequent step before successful commercialization of
this configuration. Some important parameters such as conversion
of reactants, products yield, temperature and pressure profiles are
evaluated in this novel configuration and compared with the ones
in AF-TR and AF-TMR. The effect of catalyst deactivation on the RF-
TMR performance is investigated, too. Owing to the slight pressure
drop (i.e., the possibility of using smaller catalyst particles) and the
hydrogen permeation through the Pd–Ag membrane layer in RF-
TMR, the products yield (hydrogen and aromatics) and reactants
conversion increase in this configuration as will be demonstrated
in later sections.
2. Process description
2.1. Conventional naphtha reforming process (AF-TR)
A simplified process flow diagram for conventional catalytic
naphtha reforming is presented in Fig. 1. Typically the conventional
process is composed of three or four catalytic beds which are
from the smallest to the biggest one. Catalytic reforming consists
of thousands of reactions which are predominantly endothermic.
Consequently, the temperature diminishes along each reactor. This
affects the reaction rates and reduces them. Basically, the first reac-
tor is the smallest one to avoid drastic rate reduction. A recycled
H2 -rich stream is blended with the fresh liquid naphtha feed and
passes through a furnace to enter the first reactor. The reactors are
equipped with pre-furnaces to compensate the temperature drop
and the reaction rate at the inlet of the subsequent reactor. More
descriptions regarding the conventional configuration can be found
in previous work [27].
2.2. Radial-flow tubular membrane reactor (RF-TMR)
A comparison of top and side views of RF-TMR and AF-TMR con-
figurations are shown in Fig. 2(a) and (b). Note that the performance
of AF-TMR and AF-TR is the same except that we have a permeation
side in AF-TMR. In the axial flow reactors, feed is distributed over
the top of the reactor (cross section) and flows axially through the
catalytic bed to the bottom of the reactor however the area accessi-
ble for flow in the radial flow reactors (surface area) is much larger
than the axial flow reactor (see Fig. 2(a)). Two perforated screens
are situated at the top and the bottom of the axial-flow tubular
reactor to distribute the feed more uniformly over the packed-bed
which also plays as a mechanical support. The top view of both
configurations is depicted in Fig. 2(b) which illustrates how mem-
brane concept can be assisted in the radial-flow tubular reactors.
However, the design of RF-TMR is such that the naphtha feed and
the sweeping gas flow radially in tube and shell sides. As seen,
the outer annulus of the reactor is packed by catalysts. Attempts
have been made to achieve a uniform flow distribution in the cat-
alytic bed with the flow predominately in a radial direction. The
chemical reactions take place on catalysts’ surfaces. The internal
design is such that the flow enters the vessel across the entire cross
section of the vessel, first proceeding downwards near the wall of
the vessel and then radially inwards, through the bed of catalytic
particles and finally in a downwards direction via an axial collec-
tor. The reformed naphtha is collected by the axial collector pipe.
More details about the design of RF-TMR are shown in Fig. 2(c).
As seen, the cross section area of the membrane reactor is divided
into some subsections. The walls of the gaps between these sub-
sections are coated by the Pd–Ag membrane layer, thus hydrogen
permeates through the membrane layer and enters the shell side.
Moreover, the sweeping gas flows radially in the shell side and car-
ries the permeated hydrogen. In RF-TMR, the cross section area (Ac )
 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275 267

Inlet naphtha feed

Pd-Ag membrane
Inlet sweep gas

Perforated tube

Perforated screen
Permeated
hydrogen
Flow pattern
of naphtha

Pd-Ag membrane

Catalyst particle

Oulet sweep gas

Reformed naphtha

(a) (b)

Flow pattern of sweep gas

Ra
Inlet naphtha feed
ial

dia
Ra
Ax

Perforated

l
dia
al

tube

l
Axi

Pd-Ag membrane

Reformed
naphtha
Catalyst particle

Solid
Permeated hydrogen wall
Collector
center pipe

Outer wall of reactor

(c) (d)

Pd-Ag Membrane

Inlet Sweep Inlet Naphtha Feed

Gas
Permeated Catalyst Particle
Hydrogen
Perforated Screen

(e)

Fig. 2. A comparison of RF-TMR and AF-TMR configurations (a) side views, (b) top views (note that the cross in circle symbol (⊗) represents the flow with downward direction
(perpendicular to the page)) and (c) the schematic view of RF-TMR.
268 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275

Table 1 4. Mathematical modeling

Specifications of reactors, feed, product and catalyst of RF-TMR.

Parameter Numerical value Unit The mass and energy balance equations (for both shell and tube
Naphtha feed stock 30.41 × 10 3
kg h −1 sides) as well as the pressure drop correlations [28] and a catalyst
Reformate 24.66 × 103 kg h−1 deactivation model [29] are presented in Table 2. The set of dynamic
H2 /HC mole ratio 4.73 – equations of the model have been solved by the orthogonal colloca-
LHSV 1.25 h−1 tion method. A two-step procedure has been used to solve the set of
Mole percent of hydrogen in recycle 69.5 –
coupled partial differential–algebraic equations of the system. The
Inner diameter, outer diameter and length of 0.5, 1.54, 6.16 m
1st reactor procedure consists of a steady-state simulation prior to a dynamic
Inner diameter, outer diameter and length of 0.5, 1.75, 6.99 m simulation to obtain the initial conditions of the dynamic states
2nd reactor along the reactor. More details regarding the orthogonal colloca-
Inner diameter, outer diameter and length of 0.5, 2.05, 8.33 m
tion method and auxiliary correlations were presented by Iranshahi
3rd reactor
The number of sections for the 1st reactor 4 – et al. [30]. The steady state model validation is provided in Table 3.
The number of sections for the 2nd reactor 4 – To investigate the capability of Smith model along with the sim-
The number of sections for the 3rd reactor 4 – plifications, the validity of model has been evaluated under the
Total membrane surface for the 1st reactor 25.63 m2 dynamic operation of plant (see Table 4). Note that the tables of
Total membrane surface for the 2nd reactor 34.89 m2
model validation are provided for the conventional axial-flow reac-
Total membrane surface for the 3rd reactor 51.15 m2
The sweep pressure of 1st reactor 1545 kPa tor. RF-TMR is a novel configuration and there is no experimental
The sweep pressure of 2nd reactor 2250 kPa data regarding that. Suitable mathematical model is required to
The sweep pressure of 3rd reactor 2348 kPa make an appropriate initial sense of what could be achieved in this
reactor before commercialization is initiated. Moreover, this suit-
TBP Naphtha feed (◦ C) Reformate (◦ C)
able mathematical model will then be used for the optimization
Distillation fraction of naphtha feed and reformate of the process conditions and reactor control. Following the best
IBP 106 44 configuration with the optimal geometric and operating variables,
10% 113 73
30% 119 105
improves the reactor performance.
50% 125 123
70% 133 136
90% 144 153
5. Results and discussion
FBP 173 181
Typical properties of catalyst A mathematical model has been developed for RF-TMR config-
dp 1.2 mm uration with the radial-flow patterns of the sweeping gas and the
Pt 0.3 wt%
naphtha feed in shell and tube sides. The performance of RF-TMR
Re 0.3 wt%
sa 220 m2 g−1 configuration is investigated in detail in the following figures.
b 0.3 kg L−1 Initially, the number of subsections is determined. In fact, it
ε 0.36 – affects the membrane area. Although more subsections (i.e., more
membrane area) lead to more hydrogen diffusion, some economical
restrictions due to membrane fabrication expense exist. Increasing
increases while the travel distance for flow (L) decreases therefore
the membrane area causes a decrease in H2 /HC (i.e., hydrogen to
the pressure drop is low (P ∼ L/Ac ) according to the Ergun equa-
hydrocarbon ratio in the reaction side) molar ratio owing to more
tion. Accordingly, smaller catalysts’ particles can be used so that
hydrogen permeation. Thus, the sweeping gas pressure should be
the internal mass transfer resistance of the catalysts is eliminated.
adjusted to control the permeation rate of hydrogen as well as the
The operating conditions, catalyst specifications and some details
H2 /HC molar ratio. Proper ratio reduces the coke polymerization
of the new configuration are presented in Table 1.
on the catalyst surface.
The effect of increasing the number of subsections on hydrogen
3. Reaction scheme and kinetic expressions as well as aromatic yield is illustrated in Fig. 3(a) and (b). As seen,
the hydrogen yield increases with increasing the number of subsec-
A kinetic model is taken into consideration according to the tions. Increasing the number of subsections shifts the first reaction
Smith’s model [3]. Four dominant reactions are considered as fol- toward more aromatics and hydrogen productions. The definition
lows: for hydrogen and the aromatic yields (Y ) is as follows:

• Dehydrogenation of naphthenes to aromatics Fi

Yi = (17)
FParaffin + FNaphthene + FAromatic
Naphthenes(Cn H2n ) ↔ Aromatics(Cn H2n−6 ) + 3H2 (1)
where i represents hydrogen or aromatic.
• Dehydrocyclization of paraffins to naphthenes
Fig. 3(c) illustrates the required pressure of the permeation side
Naphthenes(Cn H2n ) + H2 ↔ Paraffins(Cn H2n+2 ) (2) in order to maintain H2 /HC > 4.73 in three reactors. Although higher
aromatics and hydrogen conversion are achieved by applying more
• Hydro cracking of naphthenes to lower hydrocarbons subsections, the required pressure of the sweeping gas increases
n to avoid excessive hydrogen permeation. Four subsections in the
Naphthenes(Cn H2n ) + ↔ Lighter ends (C1 –C5 ) (3)
3H2 cross section area of the membrane reactor are chosen in order to
make a similar comparison with the previous work. Regarding this,
• Hydro cracking of paraffins to lower hydrocarbons
the membrane areas of this and the previous work [27] will be the
n−3 same. Case study (I) is investigated with the following assumptions
Paraffins(Cn H2n+2 ) + ↔ Lighter ends (C1 –C5 ) (4)
3H2 in this regard. The thickness of membrane layers in three reactors,
hydrogen mole fraction in the recycled stream and the number of
The corresponding rate equations and their constants can be found subsections are chosen as 10 ␮m, 0.695 and 4, respectively. In order
in recent publication [27]. to adjust the H2 /HC (>4.73), the required pressures of the sweeping
 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275 269

Table 2
Mass & energy balances for RF-TMR.

Fluid phase (reaction side)

  m
1 ∂ ∂Cj 1 ∂(ur1 Ac1 Cj ) Ap ∂Cj

Dej Ac1 − + b a ij ri − JH = ε j = 1, 2, . . . , n i = 1, 2, . . . , m (5)
Ac1 ∂r ∂r Ac1 ∂r Ac1 2 ∂t
i=1
      m
1 ∂ ∂T 1 ∂ Ap Ap ∂

keff Ac1 − (Ac1 ur1 Cp (T − Tref )) − JH Cp (TShell − T ) + U(TShell − T ) + B a Hi ri = ε (  Cp (T − Tref )) (6)
Ac1 ∂r ∂r Ac1 ∂r Ac1 2 Ac1 ∂t
i=1

Fluid phase (sweep gas side)

 
1 ∂ ∂Cj 1 ∂(ur2 Ac2 Cj ) Ap ∂Cj
Dej Ac2 − + JH = ε j = 1, 2, ..., n i = 1, 2, ..., m (7)
Ac2 ∂r ∂r Ac2 ∂r Ac2 2 ∂t
     
1 ∂ ∂T 1 ∂ Ap Ap ∂
keff Ac2 − (Ac2 ur2 Cp (T − Tref )) + JH Cp (TShell − T ) − U(TShell − T ) =ε (  Cp (T − Tref )) (8)
Ac2 ∂r ∂r Ac2 ∂r Ac2 2 Ac2 ∂t
Hydrogen permeation rate [31]
Q0 exp(−(EH2 /RT ))   
JH 2 = PHTube − PHShell (9)
ıH2 2 2

−1 −1/2 −1
Q0 = 1.65 × 10−5 mol m s−1 kPa , EH2 = 15.7 kJ mol
Additional relations
 
2rL
Ac1 = (10)
NOS
Ap = 2L (11)
Boundary & initial conditions
r = Ro : Cj = Cj0 , T = T0 (12)
∂Cj ∂T
r = Ri : = 0,
=0 (13)
∂r ∂r
ss
t = 0; Cj = Cj , T = T ss , Ts = Ts ss ; a = 1 (14)
Ergun equation (pressure drop)
2
dP 150 (1 − ε) Q 1.75 (1 − ε) Q 2
= 2 2 + (15)
dz s dp ε3 Ac s dp ε3 Ac 2
Catalyst deactivation
 
da Ed
= −Kd exp − a7 (16)
dt R((1/T ) − (1/TR ))
5 −1 −5 −1
TR = 770 K, Ed = 1.642 × 10 J mol , Kd = 5.926 × 10 h

gas for the first, the second and the third reactors are obtained to performance [2]. The aromatic production rate in the RF-TMR is
be 1545 kPa, 2250 kPa and 2348 kPa, respectively. about 249.5 ton/day compared with the 244 ton/day capacity of
AF-TR (conventional reactor).
5.1. Variation of parameters along RF-TMR and AF-TR The same trend can be recognized for hydrogen yield (Fig. 4(b)).
The small graph reveals interesting results which are not obvi-
The comparison of AF-TR and RF-TMR (for two values of H2 /HC) ous in the magnified one. As clearly seen, the hydrogen yield
is illustrated in the following figures. It is recommended to main- increases steadily in RF-TMR, especially at H2 /HC > 4, however it
tain H2 /HC in the range of 4–6 in order to reduce the problem of shows increasing/decreasing trend (a maximum point) for AF-TR.
coke formation [32]. The aromatic yield along AF-TR and RF-TMR is The main reactions in the third reactor of AF-TR and RF-TMR are
depicted in Fig. 4(a). As seen, the aromatic yield in membrane reac- cracking and dehydrocyclization (i.e., Eqs. (2) and (4)). The amount
tor is higher compared with the AF-TR. Furthermore, the aromatic of hydrogen in AF-TR increases at the end of the third reactor which
yield at H2 /HC > 4 is higher than the one at H2 /HC > 4.73 due to more shifts the equilibrium reaction (Eq. (2)) to the reactant side (accord-
hydrogen removal from the reaction side and change in equilibrium ing to the Le Chatelier’s principle), thus hydrogen yield decreases at
condition. The aromatic compounds have always an octane num- the end of the third reactor. Using membrane in RF-TMR solves this
ber (RON) above 100 and even small variations in aromatic and RON problem properly. The hydrogen production rate is 11.5 ton/day in
values influence significantly the production economics and engine the RF-TMR which is 3% more than the AF-TR capacity.

Table 3
Comparison between model prediction and plant data for fresh catalyst.

Reactor no. Inlet pressure (kPa) Inlet pressure (kPa) Catalyst distribution (wt%) Input feedstock (mol%)

1 777 3703 20 Paraffin 49.3

2 777 3537 30 Naphthene 36.0
3 775 3401 50 Aromatic 14.7

No. Outlet temperature (K) Aromatic in reformate (mol%)

Plant AF-TR AF-TMR RF-TMR Plant AF-TR AF-TMR RF-TMR

1 722 727.30 727.86 728.16 – 34.67 35.24 35.09

2 753 750.98 751.36 751.93 – 47.19 48.05 47.66
3 770 770.53 770.68 770.45 57.70 56.18 58.23 57.76
270 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275

Table 4
Unsteady state model validation.
 model-Plant 
Time (day) Inlet temperature to Naphtha feed Plant (kmol h−1 ) AF-TR (kmol h−1 ) Devi % Plant
× 100 RF-TMR AF-TMR
the first reactor (K) (ton/h) (kmol h−1 ) (kmol h−1 )

0 777.0 30.41 225.90 221.7819 −1.8230 218.3876 218.8940

34 777.3 30.41 224.25 222.7137 −0.6851 219.4027 219.8799
62 777.8 31.00 229.65 228.1372 −0.6588 224.9257 225.3609
97 778.0 30.78 229.65 226.9795 −1.1629 223.8130 224.2382
125 778.5 31.22 229.65 231.0067 0.5908 227.9161 228.3108
160 778.7 31.22 229.65 231.4815 0.7975 228.4387 228.8198
188 777.2 28.55 211.60 210.0259 −0.7439 206.8139 207.2888
223 778.6 30.33 222.75 224.9212 0.9747 221.8817 222.2788
243 779.3 31.22 233.05 232.3911 −0.2827 229.4424 229.7982
298 779.2 30.67 228.65 228.3803 −0.1179 225.4393 225.8039
321 779.3 30.76 227.64 229.2991 0.7288 226.3849 226.7410
398 786.9 42.35 317.30 324.8447 2.3778 322.9037 322.8099
425 787.0 42.32 317.94 324.7715 2.1487 322.8467 322.7544
461 787.3 42.32 317.94 324.9876 2.2166 323.0858 322.9944
490 787.5 42.32 317.94 325.1511 2.2681 323.2668 323.1762
524 787.7 42.32 313.09 325.3321 3.9101 323.4671 323.3777
567 787.0 42.54 317.94 327.3489 2.9593 325.5222 325.4292
610 787.2 42.54 313.90 327.5484 4.3480 325.7431 325.6518
717 785.8 37.86 286.15 289.6324 1.2170 287.5376 287.5742
771 786.5 38.51 282.10 295.1652 4.6314 293.1431 293.1581

(a) (b)
0.8975 0.364

0.897 0.3635

0.8965 0.363
Hydrogen yield

Aromatic yield

0.896 0.3625

0.8955 0.362

0.895 0.3615

0.8945 0.361

0.894 0.3605
2 3 4 5 6 7 8 9 10 2 3 4 5 6 7 8 9 10
Number of sections Number of sections

(c) 3000
Required pressure of sweep gas (kPa)

2500

2000

1st Reactor
1500 2nd Reactor
3rd Reactor

1000

500
2 3 4 10
5 6 7 8 9
Number of sections

Fig. 3. The effect of number of subsections in the cross section are of membrane reactor on (a) hydrogen yield, (b) aromatic yiel, and (c) required pressure of the sweeping
gas for three reactors in RF-TMR.
 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275 271

(a) 0.4 (b) 1

0.9
0.35

0.8
0.3 0.37
AF-TR
0.7
RF-TMR, H2/HC>4.73

Hydrogen yield
Aromatic yield

0.25 0.36
0.6 RF-TMR, H2/HC>4.00

0.2 0.35 0.5 0.92

0.9 0.95 1
0.4
0.15
0.9
AF-TR 0.3
0.1 RF-TMR, H2/HC>4.73
RF-TMR, H2/HC>4.00 0.2 0.88
0.7 0.8 0.9 1
0.05
0.1

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)

Fig. 4. (a) Aromatic yield. (b) Hydrogen yield along AF-TR and RF-TMR (for two values of H2 /HC).

The H2 /HC molar ratio along AF-TR and RF-TMR is demonstrated 6.4
in Fig. 5. This ratio is one of the key parameters in the controlling
unit of the naphtha reforming process. If H2 /HC becomes lower than 6.2

4, the catalysts will be subjected to coking and rapid deactivation. It

6
imposes a huge burden on catalysts and jeopardizes the catalyst life.
On the other hand, high ratios have undesirable effects on the pro- 5.8
H2 /HC molar ratio

cess conversion. In RF-TMR, the membrane layer maintains H2 /HC

at approximately the inlet ratio of 4.73 by means of the perme- 5.6
ation pressures. The difference in permeation and production rates
AF-TR
causes maximums in the RF-TMR profile. Unlike membrane reac- 5.4
RF-TMR
tors where it maintains approximately constant, H2 /HC increases
5.2
gradually in AF-TR mainly due to hydrogen production in the reac-
tion side.
5
The pressure profiles of AF-TR and RF-TMR are shown in Fig. 6(a).
The pressure drop in RF-TMR is noticeably less than the one in AF- 4.8
TR. The pressure drop in RF-TMR is approximately 3 kPa while it is
about 400 kPa in AF-TR. This is one of the main superiority of RF- 4.6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
TMR to AF-TR which can be recognized from this figure. In RF-TMR,
Mass of catalyst (Dimensionless)
the feed passes through a shorter distance of catalytic bed therefore
there is a negligible pressure drop. Moreover, the total feed dis- Fig. 5. The H2 /HC molar ratio along AF-TR and RF-TMR.
tributed over the surface area of the reactor which is much greater
than the cross section area in AF-TR. The temperature profile of

(a) 3750
(b) 780

3700
770
Temperature of tube side (K)

3650 3703

3600 3702 760

Pressure (kPa)

3550 3701
750
3500 3700
0 0.5 1

3450 AF-TR 740 AF-TR

RF-TMR RF-TMR
3400
730
3350

3300 720
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mass of catalyst (Dimensionless) Mass of catalyst (Dimensionless)

Fig. 6. (a) Pressure profile. (b) Temperature profile of tube side along AF-TR and RF-TMR.
272 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275

780 0.8

Hydrogen mole fraction in shell side

0.79
Temperature profiles in RF-TMR (K)

770 AF-TMR
0.78
RF-TMR
0.77
760
Tube Side 0.76
Shell Side
0.75
750
0.74

740 0.73

0.72

730 0.71

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

Fig. 7. Temperature profile of shell and tube sides along RF-TMR. Fig. 8. Hydrogen mole fraction in shell sides of AF-TMR and RF-TMR.

the tube side along AF-TR and RF-TMR is expressed by Fig. 6(b). in the previous work [27]. The aromatic yield is compared in these
Temperature profiles of two configurations are approximately the configurations for a wide range of operating pressures as shown
same. in Fig. 9(a). In a whole range of operating pressure, the aromatic
The temperature profile of RF-TMR (for shell and tube sides) yield in both membrane reactors is higher compared with the AF-
is depicted in Fig. 7. Since naphtha reforming is an endothermic TR. In a lower range of operating pressure, RF-TMR performs better
process, the tube side temperature decreases. Owing to the heat than AF-TMR. However, AF-TMR performs better than RF-TMR in
transfer from the shell side to the tube side, the shell side tempera- a higher range of operating pressure. In a higher range of operat-
ture (i.e., sweeping gas temperature) decreases, too. In fact, the shell ing pressure, it is recommended to use smaller catalyst particles
side temperature provides a heating medium for the reaction side. to improve the performance of RF-TMR. Since the pressure drop in
Hydrogen mole fraction in the shell side along AF-TMR and RF- RF-TMR is slight, smaller catalyst particles with higher efficiency
TMR is illustrated in Fig. 8. The initial hydrogen mole fraction in can be applied. The same trend is observed for hydrogen yield as it
the sweeping gas is 0.695 and it increases as proceeding along the is clear from Fig. 9(b).
reactors. The sweeping gas lines in AF-TMR and RF-TMR configura- The required pressures of the permeation side for a wide range
tions are in the parallel mode. As seen, hydrogen mole fraction in of operating pressure in AF-TMR and RF-TMR are depicted in
the shell side increases along the reactors owing to the hydrogen Fig. 10(a)–(c). In order to maintain H2 /HC > 4.73, the only adjustable
permeation from the reaction side to the shell side. parameter for case study (I) is the sweeping gas pressure. As a result,
the required pressure of the sweeping gas increases with increas-
5.2. A comparison of radial-flow tubular membrane reactor ing the operating pressure. Lower pressures of the sweeping gas
(RF-TMR) with axial-flow tubular reactor (AF-TR) and axial-flow are required in RF-TMR in comparison with the ones in AF-TMR
tubular membrane reactor (AF-TMR) based on the Sievert’s law. In this regard, another case study can
be proposed where thicker membrane layers are applied. In case
In this section, a comparison between AF-TR, AF-TMR and RF- study (II), the required pressures of the sweeping gas for the first,
TMR is performed. The AF-TMR configuration has been investigated the second and the third reactors decrease considerably to 175 kPa,

(a) 0.37 (b)

0.9
0.36

0.85
0.35
Hydrogen yield
Aromatic yield

0.8
0.34
AF-TR AF-TR
AF-TMR 0.75 AF-TMR
0.33
RF-TMR RF-TMR

0.32 0.7

0.31 0.65

0.3
1500 2000 2500 3000 3500 4000 4500 5000 1500 2000 2500 3000 3500 4000 4500 5000
Pressure of naphtha feed (kPa) Pressure of naphtha feed (kPa)

Fig. 9. A comparison of (a) aromatic yield and (b) hydrogen yield versus the operating pressure in AF-TR, AF-TMR and RF-TMR.
 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275 273

(a)
Required pressure of sweeping gas in the first reactor (b)
2500 3500

Required pressure of sweep gas in the second reactor

3000
2000 AF-TMR
RF-TMR AF-TMR
2500 RF-TMR

1500
2000

1500
1000

1000

500
500

0 0
1500 2000 2500 3000 3500 4000 4500 5000 1500 2000 2500 3000 3500 4000 4500 5000
Pressure of naphtha feed (kPa) Pressure of naphtha feed (kPa)

(c)
3500
Required pressure of sweep gas in the third reactor

3000
AF-TMR
RF-TMR
2500

2000

1500

1000

500

0
1500 2000 2500 3000 3500 4000 4500 5000
Pressure of naphtha feed (kPa)

Fig. 10. The required pressure of the sweeping gas in (a) the first reactor, (b) the second reactor and (c) the third reactor versus the operating pressure in AF-TMR and RF-TMR.

320 kPa and 190 kPa as a result of increasing the thickness of mem- reaction and as a reactant in accordance with the second, the third
brane layers to 27 ␮m, 50 ␮m and 80 ␮m (ı1 = 27 ␮m, ı2 = 50 ␮m, and the fourth reactions. Owing to the catalyst deactivation, the
ı3 = 80 ␮m), respectively. Higher membrane thicknesses results in hydrogen production by the first reaction and the hydrogen con-
higher initial costs and lower operating charges. The operating costs sumption by the second, the third and the fourth reactions decrease
decrease considerably owing to lower required pressures of the
sweeping gas (compressor electricity supply). Consequently, case
study (II) is preferred and proposed for future investigations.

5.3. Effect of time 3rd Rea ctor

2nd Rea ctor
1st Reactor

The catalyst activity as a function of time and reactor length 1

is expressed by Fig. 11. The catalyst activity equals one for fresh 0.95
catalysts. The activity deteriorates with time owing to coking and
Activity of catalyst

0.9
sintering. However, the deactivation rate is lower as proceeding
along the reactor due to temperature falling. 0.85
The variation of reactant conversion and products yield over 0.8
a period of 800 days of operation is investigated in the follow-
0.75
ing figures. The percentage of naphthene conversion with time for
AF-TR and RF-TMR is shown by Fig. 12(a). More naphthene turns 0.7 800

into products in RF-TMR compared with AF-TR. The naphthene 600

)
0.65
400 ay
conversion to products decreases with time owing to the catalyst 1 e
(D
0.8 200 m
deactivation. The same trend is presented for paraffin conversion 0.6
0.4 Ti
Mass of catalyst 0.2 0
in Fig. 12(b). Therefore, higher product yield is achieved in RF-TMR (Dim ensionle ss)
(see Fig. 12(c) and (d)). Hydrogen has a dual role in naphtha reform-
ing, i.e., it acts simultaneously as a product according to the first Fig. 11. The catalyst activity as a function of time and RF-TMR length.
274 D. Iranshahi et al. / Chemical Engineering Journal 178 (2011) 264–275

(a) (b)
95.95 28

95.9
Percentage of naphthene conversion

26
95.85 AF-TR
AF-TR

Percentage of paraffin conversion

RF-TMR
RF-TMR
95.8
24
95.75

95.7 22

95.65
20
95.6

95.55
18
95.5

95.45 16
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Time (Day) Time (Day)

(c) (d)
0.365 0.9

0.898

0.36 0.896

AF-TR 0.894
Yield of Aromatic

Hydrogen yield

RF-TMR
0.355 0.892

AF-TR
0.89
RF-TMR
0.35 0.888

0.886

0.345 0.884

0.882

0.34 0.88
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Time (Day) Time (Day)

Fig. 12. The percentage conversion of (a) naphthene, (b) paraffin, and (c) aromatic yield, and (d) hydrogen yield with time in AF-TR and RF-TMR.

in comparison with the first day. The decrement in hydrogen con- optimization of the membrane thickness can be proposed as a
sumption rate prevails over the decrement in its production rate, future work owing to a remarkable decrease in the operating and
and consequently it slightly increases in the course of time. initial costs.

6. Conclusion
A novel configuration assisting the membrane technology is pro-
posed for the radial-flow naphtha reactors. The performance of
RF-TMR has been investigated and compared with the AF-TR and
AF-TMR. The effect of parameters has been compared along the
reactors and in the course of time considering the catalyst deacti-
vation. The set of differential–algebraic equations have been solved
by the orthogonal collocation method. In this novel configuration,
four subsections in the cross section area of the membrane reactor
have been taken into consideration. In order to model RF-TMR, the
radial-flow pattern is considered in tube and shell sides. The per-
formance of RF-TMR improves by applying the radial-flow pattern
which lessens the pressure drop problem and also the Pd–Ag mem-
brane layer which leads to an increase in percentage conversion
of reactants and products yield. Thus, the aromatic and hydrogen
yield increase considerably in this novel configuration by about
2.26% and 1.50%, respectively. Two case studies are proposed in this
study; the required pressure of the sweeping gas decreases notice-
ably if the membrane thicknesses increase (i.e., case study (II)). The
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