i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5

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Simultaneous utilization of two different membranes for

intensification of ultrapure hydrogen production from
recuperative coupling autothermal multitubular reactor

M. Bayat a, M.R. Rahimpour a,b,*

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

article info abstract

Article history: The potential of simultaneous hydrogen production and in situ water removal in a ther-
Received 23 December 2010 mally coupled multitubular two-membrane reactor (TCTMR) were studied numerically.
Received in revised form Methanol synthesis is carried out in exothermic side with H-SOD membrane and supplies
6 February 2011 the necessary heat for the endothermic side. Dehydrogenation of cyclohexane is carried
Accepted 9 February 2011 out in endothermic side with hydrogen-permselective Pd/Ag membrane wall. Therefore,
Available online 11 April 2011 the proposed reactor consists of two membranes, one for separation of pure hydrogen from
endothermic side and another one for separation of water from exothermic side. The
Keywords: motivation for in situ H2O removal during methanol synthesis by using H-SOD membranes
Ultrapure hydrogen production is to displace the wateregas shift equilibrium to enhance conversion of CO2 to improve
H2O removal methanol productivity. A steady-state heterogeneous model is developed to analyze the
Methanol synthesis operation of the coupled methanol synthesis. The proposed model has been used to
Pd/Ag membrane compare the performance of a TCTMR with conventional reactor (CR) and thermally
H-SOD membrane coupled membrane reactor (TCMR) at identical process conditions. This comparison shows
Steady-state heterogeneous model that TCTMR in addition to possessing advantages of a TCMR has a more favorable profile of
temperature and increased productivity compared with other reactors. Furthermore, lower
water production rate in TCTMR reduces catalyst re-crystallization.
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction 1.1. Hydrogen production

According to the problems induced by the shortage of fossil
energy and global warming, hydrogen is expected to be
a promising energy vector for the near future [1]. Hydrogen
has been nominated as a renewable and alternative energy. It
is at best as an energy carrier [2e4].
Hydrogen commercially produces by steam reforming of
methane and other fossil fuels. In such cases, however, the
same amount of carbon dioxide is released during the produc-
tion of hydrogen as that formed by direct combustion of fuels.
This method produces toxic and corrosive components such as

* Corresponding author. Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University,
Shiraz 71345, Iran. Tel.: 98 711 2303071; fax: 98 711 6287294.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.02.051
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5
CO, CO2 and H2S in addition to trace amounts of ammonia [5].
Dehydrogenation is an attractive choice and alternative for
hydrogen production due to its essentially zero CO2 impact,
giving a positive environmental contribution and also solves
the troubles and problems in hydrogen storage conditions and
medium preparation, such as metal hydrides [1,6].
1.2. Membrane reactor
In the recent years membranes have been used intensively in
the applicable researches as a function to enhance the prod-
ucts yield/selectivity and thermodynamically shift the reac-
tions toward products. Separation by membrane is less energy
intensive, requiring no phase change in the process and
typically provides low-maintenance operation. Membranes
have been used successfully in a number of industrial appli-
cations, including the production of high purity gases and
recovery of hydrogen from process streams [7].
1.2.1. Pd/Ag membrane
The first large-scale commercial application of membrane gas
separation was the separation of hydrogen from nitrogen,
methane and argon in ammonia purge gas stream [8]. Palla-
dium-based membranes are used commercially to purify
hydrogen and to dehydrogenate organic molecules. The
catalytic ability of the membrane surface combined with the
selectivity of hydrogen permeation makes it possible to
remove hydrogen from a reversible reaction and thereby
shifts the reaction toward the product side [9]. Shu et al.
studied dehydrogenation and hydrogenation reactions on Pd
membranes [10]. Palladium alloys are often used in commer-
cial hydrogen separation applications instead of pure palla-
dium. Palladium combines excellent hydrogen transport and
selectivity properties with resistance to high temperatures,
corrosion and solvents. In Pd/Ag, the most commonly used
alloy for hydrogen extraction, the hydrogen permeability
increases with Silver content to reach a maximum at around
23 wt% Ag [11]. Tosti et al. [12] described different configura-
tions of palladium membrane reactors used for separating
ultrapure hydrogen. Nair and Harold [13] recently carried out
an analysis of conventional Pd and Pd/Ag membranes.
1.2.2. Hydroxy sodalite (H-SOD) membrane
Hydroxy sodalite is a zeolite-like material, consisting of
sodalite cages only. Consequently, the material porosity is
zero dimensional, having no distinct pores or channels, but an
array of cages connected to each other through 4 and 6 rings.
Although the 4-rings are too small to allow permeation of any
molecule, the diameter of the 6-rings is large enough (2.7 
A) to
only allow very small molecules such as helium, ammonia,
and water (kinetic diameters 2.6, 2.55 and 2.65 A respectively
[14]). However, since the cages are blocked with water,
permeation of other molecules can only be feasible upon the
dehydration of the framework. Nonetheless, as the structure
is stabilized through hydrogen bonding between the non-
framework water and the framework oxygen atoms, dehy-
dration of the material leads to the destruction of these
hydrogen bonds resulting in destabilization and partial
collapse of the framework structure [15]. In view of the ideal
window diameter of hydroxy sodalite, absolute separation of
7311
water can be achieved through defect-free membranes.
Separation of water from mixtures such as alcohols or smaller
molecules such as H2 can thus become possible [16]. More-
over, a tubular H-SOD membrane has been used as a highly
water-permselective membrane for water permeation. H-SOD
is a zeolite-like material which consists of sodalite cages
exclusively [14,17]. H-SOD membrane shows excellently ideal
selectivity (near to absolute) of water to hydrogen. In addition,
the membrane demonstrates a good thermal and mechanical
stability. The exceptional property of H-SOD membrane in
comparison with the other widely studied membranes [18,19]
is 100% selectivity of water on the basis of molecular sieving in
hybrid processes [20].
1.3. Methanol
Methanol is an important multipurpose base chemical;
a simple molecule which can be recovered from many
resources, predominantly natural gas. It is produced from
synthesis gas on a large scale worldwide [6]. The Methanol
synthesis reaction is exothermic and the total moles reduce as
the reaction proceeds. In the methanol synthesis, three
overall reactions are possible: hydrogenation of carbon
monoxide, hydrogenation of carbon dioxide and reverse
wateregas shift reaction, which are as follows:
CO 2H2 4CH3 OH; DH298 90:55 kJ=mol (1)
CO2 3H2 4CH3 OH H2 O; DH298 49:43 kJ=mol (2)
CO2 H2 4CO H2 O; DH298 41:12 kJ=mol (3)
Reactions (1)e(3) are not independent so that one is a linear
combination of the other ones. The temperature and pressure
of reaction are 495e535 K and 5e8 MPa, respectively [21].
Rezaie et al. compared the results of heterogeneous and
homogeneous models in a dynamic simulation for fixed-bed
methanol synthesis and reported similar predictions [22].
Rahimpour et al. have studied catalyst deactivation of meth-
anol synthesis and strategies to enhance the ability of meth-
anol synthesis reactor using a mixture of fresh and partially
deactivated catalyst [23e25]. Many efforts have been done to
improve the yield and performance of methanol reactors. In
this way recently a dual-type reactor system instead of
a single-type reactor was developed by Rahimpour et al.
[26e28]. The dual-type methanol reactor is an advanced
technology for converting natural gas to methanol at low cost
and in large quantities.
1.4. Literature review
There are a few investigations on simultaneous pure
hydrogen production and methanol synthesis in autothermal
membrane reactors. Recently, Rahimpour et al. [6] have
considered theoretically the methanol and hydrogen produc-
tion in a thermally coupled membrane single-type reactor in
co-current mode of operation. In their simulated reactor, the
exothermic reaction (methanol synthesis) takes place in the
inner tube and outer tube (third tube) is permeation side.
Besides, shell side and endothermic side (second tube)
7312 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5
separated by a PdeAg membrane and selective permeation of
hydrogen through the Pd/Ag membrane is achieved by
co-current flow of sweep gas through the permeation side.
Moreover, Rahimpour et al. have considered enhancement of
simultaneous hydrogen production and methanol synthesis
in thermally coupled double-membrane reactor [29]. Finally,
methanol synthesis and cyclohexane dehydrogenation in
a hydrogen-permselective membrane and non-membrane
thermally coupled reactor using differential evolution (DE)
method are optimized by Rahimpour et al. [30,31].
From previous studies, it is obvious that there is no infor-
mation available in the literature regarding the use of simul-
taneous Pd/Ag and H-SOD membrane in thermally coupled
reactor for pure hydrogen production and methanol
synthesis. Therefore, it was decided to first study on this
system.
1.5. Objectives
In the present work, production of pure hydrogen and meth-
anol synthesis is investigated theoretically in a thermally
coupled two-membrane multitubular reactor. The endo-
thermic and exothermic reactions are chosen the catalytic
dehydrogenation of cyclohexane to benzene and methanol
synthesis, respectively. The motivation is to combine the
energy efficient concept of the coupling of endo-
thermiceexothermic reactions, the membrane-assisted
selective separation of hydrogen, in situ water removal and
enhancement of simultaneous hydrogen and methanol
production in a single reactor. Using PdeAg and H-SOD
membrane layers for removal of water and hydrogen
production shift the equilibrium reactions to the products
sides (Methanol and hydrogen). The steady state, 1-D mathe-
matical model of the multitubular two-membrane coupled
reactor is presented to evaluate the performance of the
proposed reactor. Numerical simulation results of the TCTMR
were compared with that of conventional reactor and TCMR at
Hydrogen permeation
Heat transfer
Sweep gas
CH3OH
CO2
CO
H2O
H2
N2
CH4
C6H12
Ar
Fig. 1 e Schematic diagram of the co-current mode for a thermally coupled membrane reactor (TCMR) configuration.
same process conditions such as pressure, temperature,
catalyst mass and feed composition.
2. Process description
The conventional reactor is a fixed-bed type resembling
a vertical shell and tube heat exchanger. The tubes are packed
with catalyst pellet and boiling water is circulating in the shell
side to remove the heat of exothermic reactions whereas in
thermally coupled reactor, a catalytic dehydrogenation reac-
tion in the endothermic side is used instead of using cooling
water in the methanol synthesis reactor. The process of
methanol synthesis in the conventional reactor (CR) has been
studied by Rahimpour et al. [22].
2.1. Thermally coupled membrane reactor (TCMR)
The schematic diagram of a thermally couple membrane
reactor is presented in Fig. 1. This system is a three concentric
tubes reactor where the inner tube is used for methanol
synthesis and the second one is used for dehydrogenation of
cyclohexane instead of coolant water in the shell of conven-
tional methanol synthesis reactor. The wall between second
and third tubes is a hydrogen-permselective membrane, so
that the third tube receives hydrogen permeating from the
second one. The characteristics and input data of thermally
coupled membrane reactor are listed in Tables 1 and 2 [32,33].
The operating conditions for exothermic side were extracted
from Rahimpours studies [22].
2.2. Thermally coupled multitubular two-membrane
reactor (TCTMR)
The integrated two-membrane reactor simulated for simul-
taneous methanol and hydrogen production is shown sche-
matically in Fig. 2. Basically, the process in TCTMR is similar to
Pd-Ag membrane layer
C6H12
C6H6
H2
Ar
CH3OH
CO2
CO
Exothermic side H2O
H2
N2
CH4
Endothermic side
Sweep gas+H2
Permeation side
L= 7 m
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5 7313

tube is permeation side and separated by water-permselective

Table 1 e The operating conditions for methanol
synthesis process (exothermic side) in TCMR. membrane from second tube (exothermic side). Catalytic
dehydrogenation of cyclohexane to benzene is assumed to
Parameter Value
take place in the third tube, whereas methanol synthesis
Exothermic side occurs inside the exothermic side, with fixed beds of different
Feed composition (mole fraction) catalysts on both sides. Therefore, the reacting synthesis gas
CH3OH 0.0050
is cooled simultaneously with sweep gas in the inner tube and
CO2 0.0940
reacting gas in endothermic side. Moreover, the wall of the
CO 0.0460
H 2O 0.0004 endothermic side is covered with a PdeAg membrane. Thus,
H2 0.6590 pure hydrogen can penetrate from the endothermic side into
N2 0.0930 the permeation side (outer tube). The specifications of
CH4 0.1026 different sides of TCTMR have been summarized in Table 3.
Total molar flow rate (mol s1) 0.64 The input data and operating conditions are the same as
Inlet pressure (bar) 76.98 TCMR (see Tables 1 and 2).
Inlet temperature (K) 503
Density (kg m3) 1770
Particle diameter (m) 5.47  103
Heat capacity (kJ kg1 K1) 5.0 3. Reaction scheme and kinetics
Specific surface area (m2 m3) 626.98
Bed void fraction 0.39 3.1. Methanol synthesis
Density of catalyst bed (kg m3) 1140
Wall thermal conductivity (W m1 K1) 48 In the methanol synthesis, three overall reactions are possible:
hydrogenation of carbon monoxide, hydrogenation of carbon
dioxide and reverse wateregas shift reaction. In the current
TCMR with exception of some changes. These changes in the work, the rate expressions have been selected from Graaf et al.
new proposed system are as follows: [34]. The rate equations combined with the equilibrium rate
Firstly, the synthesis gas is fed to the shell side of constants [35] provide enough information about kinetics of
exothermic section and sweeping gas flows in the inner tube methanol synthesis over commercial CuO/ZnO/Al2O3 catalysts.
of reactor. Secondly, the walls of tubes between first and
second tube consist of H-SOD membrane. The pressure 3.2. Dehydrogenation of cyclohexane
difference between these layers is the driving force for diffu-
sion of water through the H-SOD membrane layer. On the The reaction scheme for the dehydrogenation of cyclohexane
other word, it consists of four concentric tubes that the inner to benzene is as follows:

C6 H12 4C6 H6 3H2 ; DH298 206:2 kJ=mol (4)

Table 2 e The operating conditions for dehydrogenation The following reaction rate equation of cyclohexane, rc is used
of cyclohexane to benzene (endothermic side) and [36]:
permeation side in TCMR.

Parameter Value k KP PC =P3H2  PB
rc
 (5)
Endothermic side 1 KB KP PC =P3H2
Feed compositiona (mole fraction)
C6H12 0.1 where k, KB and KP are respectively the reaction rate constant,
C6H6 0.0 the adsorption equilibrium constant for benzene and the
H2 0.0 reaction equilibrium constant that are tabulated in Table 4. Pi
Ar 0.9 is the partial pressure of component i in Pa. The reaction
Total molar flow rate (mol s1) 0.1 temperature is in the range of 423e523 K and the total pres-
Inlet pressurea (Pa) 1.013  105 sure in the reactor is maintained at 101.3 kPa. The catalyst is
Inlet temperature (K) 503 Pt/Al2O3 [37].
Particle diameterb (m) 3.55  103
Bed void fraction 0.39

Permeation side
4. Mathematical model
Feed composition (mole fraction)
Ar (sweep gas) 1.0
H2 0.0 The following assumptions are considered during the
1
modeling of one and two-membrane heat exchangers cata-
Total molar flow rate (mol s ) 1.0
lytic reactor:
Inlet temperature (K) 503
Inlet pressure (Pa) 0.1  105
Thermal conductivity of membrane (W m1 K1) 153.95  One-dimensional heterogeneous model (reactions take
place in the catalyst particles)
a Obtained from Kusakabe et al. [32].
 Steady-state conditions
b Obtained from Markatos et al. [33].
 Plug flow pattern is considered in each sides
7314 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5

Hydrogen permeation
Pd-Ag membrane layer
Heat transfer
H-SOD membrane layer
Water permeation

Sweep gas
CH3OH CH3OH
CO2 CO2
CO CO
H2O H2O
H2 H2
N2 N2
CH4 CH4

Sweep gas Permeation

Inner side side
permeation Sweep gas+H2O

C6H12
Exothermic side C6H6
H2
C6H12 Ar
Ar Endothermic side

Outer permeation side Sweep gas+H2

7m

Fig. 2 e Schematic diagram of the co-current mode for a thermally coupled two-membrane reactor (TCTMR) configuration.

 Axial diffusion of heat and mass are neglected compared exothermic side and the negative sign for the endothermic
with the convection side. In equations (10) and (11), b is equal to 1 for hydrogen
 No radial heat and mass diffusion in catalyst pellet component and 0 for the sweep gas. Moreover, in equations
 Bed porosity in axial and radial directions is constant (12) and (13), f is equal to 1 for H2O component and 0 for CO2,
 Gas mixtures considered to be ideal CO, H2, CH3OH and inert components. In the boundary
 Heat loss is neglected condition equations yi0,jg, T0g and P0g are the fluid-phase mole
fraction of ith component, temperature and pressure at the
According to above assumptions and the differential entrance of jth side of reactor.
element along the axial direction inside the reactor, the mole
balance equation and the energy balance equation were 4.1. Pressure drop
obtained. The balances typically account for convection,
transport to the solid phase and reaction. The mass and The Ergun momentum balance equation is used to give the
energy balances and boundary conditions for solid and fluid pressure drop along the reactor:
phases are summarized in Table 5. In equations (6) and (7), h is
effectiveness factor of kth reaction in jth side (the ratio of the dP 1  3 mug 2
1  3ug r 2
150 1:75 (15)
reaction rate observed to the real rate of reaction), which is dz 33 d2p 33 dp
obtained from a dusty gas model calculations [22]. The detail
where the pressure drop is in Pa.
of such a dusty gas model is available in literature [22]. In
equations (8) and (9), b and f are equal to 1 and 0 for the
endothermic and 0 and 1 for the exothermic side, respectively. 4.2. Hydrogen permeation in Pd/Ag membrane
Besides, in equation (9), the positive sign is used for the
The composite membranes in this study are made of a 6 mm
thin layer of palladiumesilver alloy. The membrane is

Table 3 e The characteristics of TCTMR.

Parameter Value
Table 4 e The reaction rate constant, adsorption
Thermally coupled two-membrane reactor equilibrium constant, reaction equilibrium constant for
Inner tube or feed synthesis gas side diameter (m) 0.038 dehydrogenation of cyclohexane.
Second tube or exothermic side diameter (m) 0.053
k A exp(B/T ) A B
Third tube or endothermic side diameter (m) 0.068
Outer tube or permeation side diameter (m) 0.0827 k 0.221 4270
Length of reactor (m) 7.022 KB 2.03  1010 6270
Pd/Ag membrane thickness (m) 6  106 KP 4.89  1035 3190
Table 5 e Mass and energy balances and boundary conditions for solid and fluid phases in different sides of TCTMR.
Mass and energy balances equation

Solid phase


g
av cj kgi;j yi;j  ysi;j hri;j rb 0 (6)

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5

 X
N
 
g
av hf Tj  Tsj rb hri;j DHf;i 0 (7)
i1

Fluid phase

Fj dyi;j
g
 JH
g
 av cj kgi;j ysi;j  yi;j  b 2  f  JH2 O 0 (8)
Ac;j dz Ac;j

g  ZT4 ZT2
Fj g dTj g pDi  g g JH pDi  g g pDi  g g
 C av hf Tsj  Tj  U T3  T2  b 2 Cp dT  b U34 T3  T4  f U12 T1  T2  f  JH2 O Cp dT 0 (9)
Ac;j pj dz Ac;j Ac;j Ac;j Ac;j
T3 T1

Outer permeation side

g
dyi;4
F4 bJH2 0 (10)
dz

ZT4
dT4
g
 g g
F4 Cgp4 bJH2 Cp dT pDi U34 T3  T4 0 (11)
dz
T3

Inner permeation side

g
F1 dyi;1
 fJH2 O 0 (12)
Ac;j dz

g ZT2  g g
F1 Cp1 dTg1 pDi U12 T2  T1
 fJH2 O Cp dT 0 (13)
Ac;j dz Ac;j
T1

Boundary conditions
g g g g g g
z 0; yi;j yi0;j ; Tj T0 ; Pj P0 ; j 1; 2; 3; 4 (14)

7315
7316 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5

deposited as a continuous layer on the outer surface of

Table 6 e Physical properties, mass and heat transfer
a thermo stable support. The flux of hydrogen permeating correlations.
through the inner and outer Pd/Ag membrane is assumed to
Parameter Equation Reference
follow the half-power pressure law (Sieverts law) and is
2 2
expressed by: Component heat Cp a bT cT dT
capacity
  Mixture heat Based on local compositions
2pLP0 Ep
p p capacity
JH2
D  exp PH2 ;1  PH2 ;2 (16)
o RT Viscosity of Based on local compositions
ln
Di reaction
mixtures
Mixture Lindsay
PH2 is hydrogen partial pressure in Pa. Do and Di stand for the
thermal and
outer and inner diameters of the Pd/Ag layer. The pre-expo-
conductivity Bromley
nential factor P0 above 200  C is reported as [38]
8 2 1 0.5
6.33  10 mol m s Pa and the activation energy Ep is Mass transfer kgi 1.17Re0.42Sci0.67ug  103 Cussler
15.7 kJ mol1 [28]. coefficient [39]
2Rp ug
between gas Re
m
and solid
m
4.3. Water permeation through H-SOD membrane phases Sci
rDim  104
1y
The flux of water permeation through the H-SOD membrane, Dim P y i [40]
i

JH2 O , depends on the water partial pressure difference between ij Dij

q
two sides of the membrane. 1:43  107 T3=2 1=Mi 1=Mj
Dij p 1=3 1=3
Reid et al.
2Pvci vcj 2

 [41]
As perm
JH2 O H2 O  PH2 O
$QH2 O $ Pexo (17) 1 1 A lnDo =Di Ai 1
Vr Overall heat i
U hi 2pLKw Ao ho
transfer
coefficient
where QH2 O is water permeation and it is a specific property of h Cp m 2=3 0:458 rudp 0:407
Heat transfer [42]
the membrane. QH2 O is constant with respect to temperature Cp rm K 3B m
coefficient
and the H2O permeance is in a range of 106 and 107 mole/ between gas
m2 s Pa [18]. phase and
reactor wall

4.4. Auxiliary correlations

6. Results and discussions

Auxiliary correlations should be added to solve the set of
differential equations. The correlations used for heat and
6.1. Model validation
mass transfer between two phases, physical properties of
chemical species and overall heat transfer coefficient
The model of methanol synthesis side was validated against
between two sides are summarized in Table 6. The heat
conventional methanol synthesis reactor for a special case of
transfer coefficient between gas phase and reactor wall is
constant coolant temperature under the design specifications.
applicable for heat transfer between gas phase and solid
The comparison between simulation and plant data for
catalyst phase.
conventional methanol synthesis reactor is shown in Table 7.

5. Numerical solution Table 7 e Comparison between simulation and plant data

for conventional methanol synthesis reactor.
The formulated model composed of 17 ordinary differential Reactor inlet Reactor outlet
equations and the associated boundary conditions lends itself
to be an initial value problem. The algebraic equations in the Exp. Calc. Error%
model incorporate the initial conditions, the reaction rates, Composition (mol%)
the ideal gas assumption, as well as aforementioned correla- CO2 3.45 2.18 2.26 3.67
tions for the heat and mass transfer coefficients and the CO 4.66 1.44 1.5 4.167
physical properties of fluids. These equations along with the H2 79.55 75.71 76.37 0.87
CH4 11.72 12.98 12.88 0.77
discretized ordinary differential equations using backward
N2 0.032 0.16 0.15 6.66
finite difference form a set of non-linear algebraic equations. H2O 0.08 1.74 1.66 4.598
The reactor length is then divided into 100 separate sections CH3OH 0.032 5.49 5.23 4.736
and the GausseNewton method in MATLAB programming
Feed flow rate (mol s1) 0.565 0.51 0.5 1.96
environment is used to solve the non-linear algebraic equa-
Temperature (K) 503 528 524.3 0.7
tions in each section.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5
It was observed that the model performed satisfactorily well
under special case of industrial conditions and the observed
plant data were in good agreement with simulation data.
In this section, various steady-state behaviors observed in
the co-current coupled reactor are analyzed and the predicted
molar flow rate, yield, conversion and temperature profiles are
presented. The performance of the thermally coupled reactor
is analyzed, using different operating variables, for methanol
yield, cyclohexane conversion and hydrogen recovery yield as
follows:
FH2 ;3
Hydrogen recovery yield
FC6 H12 ;in
FCH3 OH;out
Methanol yield
FCO;in FCO2 ;in
FCH3 OH;out
Methanol selectivity    
FCO;in FCO2 ;in  FCO;out FCO2 ;out
FC6 H12 ;in  FC6 H12 ;out
Cyclohexane conversion
FC6 H12 ;in
Furthermore, an obvious measure for the performance of
the reactor concept is how much heat has to be supplied
through the exothermic reaction to maintain the endothermic
reaction. The relative heat supply is defined by the fuel ratio J:
Available heat of exothermic reaction
J (22)
Maximum required heat of endothermic reaction
As efficiency of the reactor we define:
Heat actually consumed for endothermic reaction
x (23)
Heat actually released for exothermic reaction
Optimal conditions imply j / 1 and x / 1.
6.2. Molar flow rate behavior
6.2.1. Exothermic side
Fig. 3(a)e(e) shows the comparison of components molar flow
rate in exothermic side of thermally coupled two-membrane
reactor with TCMR and CR. The figures show significant
difference between the outputs of TCTMR and two other
reactors due to water permeation from exothermic side to
inner permeation side which results in a considerable
enhancement of the reaction yield. Certainly, these figures
represent the effect of using membrane in exothermic side in
enhancing exothermic reaction conversion. The reactor
length can be divided into two sections. The upper section
where the reaction kinetic controlling and in the other section
the equilibrium is controlling. The difference between simu-
lation results pattern of thermally coupled reactors and
conventional reactor is due to delay in thermodynamics
equilibrium. The delay in equilibrium for TCMR and TCTMR is
due to lower temperature in the endothermic side, provided
by the dehydrogenation of cyclohexane, compared to the
saturated water in the conventional reactor. The small
difference between simulation results pattern of TCTMR and
TCMR is attributed to the effect of lower temperature in the
7317
exothermic side due to utilizing sweeping gas in inner tube
side of TCTMR. As can be seen in Fig. 3(b)e(e), the molar flow
rate of CO2, CO, H2O and H2 has been compared for three types
of reactor. In situ H2O removal accelerates the reverse WGS of
CO2 with H2 toward CO, then CO2 and H2 consumption is
increased (see Fig. 3(b) and (e)) and also CO and H2O produc-
tion is suppressed along the thermally coupled two-
membrane reactor relative to TCMR and CR (see Fig. 3(c) and
(d)). Additionally, lower water production rate in TCTMR
reduces catalyst re-crystallization.
(18)
6.2.2. Endothermic side
Fig. 4(a) and (b) illustrates the molar flow rate of components
in the endothermic sides of TCMR and TCTMR. As can be seen,
(19)
the highest reaction yield is achieved in TCTMR. Using
hydrogen permselective membrane in the endothermic side
enhances hydrogen and shifts the reaction to benzene
production so higher yield of reaction achieves in the ther-
(20) mally coupled reactors. The small difference between TCTMR
and TCMR performances is attributed to the positive effect of
water permeation into the inner permeation side due to
(21) utilizing membrane between exothermic side and inner
permeation side in TCTMR.
6.2.3. Outer permeation side
The comparison of hydrogen molar flow rate along the ther-
mally coupled membrane reactor (TCMR) and thermally
coupled two-membrane reactor (TCTMR) is presented in Fig. 5.
As can be seen, there is an enhancement in amounts of
hydrogen molar flow rate in TCTMR due to the increase of
hydrogen partial pressure in the endothermic side of TCTMR
relative to TCMR.
One of the greatest advantages of thermally coupled
reactors is production of useful chemicals, simultaneously.
The performance of CR, TCMR and TCTMR in the catalytic
conversion of synthesis gas to methanol and also in the
catalytic dehydrogenation of cyclohexane to benzene in order
to methanol and pure hydrogen production is summarized in
Table 8. The performance of the TCTMR was better than CR
and TCMR, as shown in Table 8.
Generally, using water permeation membrane in
exothermic side increases the hydrogen recovery, benzene,
and methanol yield in both reaction sides. The simulation
results represent 6.03 and 7.56% enhancement in the meth-
anol yield in comparison with TCMR and CR, respectively, as
shown in Table 8. However, the change in the reactor config-
uration does not affect significantly the methanol selectivity.
Besides, 8.2284 and 12.521% enhancement in the hydrogen
recovery yield and cyclohexane conversion (or benzene yield)
in comparison with TCMR are seen, respectively. The purity of
hydrogen recovery in the thermally coupled reactors is 100%
due to using hydrogen permselective PdeAg membrane
between permeation and endothermic side.
According to the above table, this configuration of reactor
suggests that the concept of thermally coupled two-
membrane reactor is an interesting candidate for production
of pure hydrogen and methanol. However, from an industrial
point of view there are still many issues to be addressed before
putting a case for successful commercialization, such as:
7318 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5

a 0.035 CR b 0.06 CR
TCMR TCMR
0.03 TCTMR 0.058 TCTMR
Methanol molar flow rate (mole/s)

0.056

CO2 molar flow rate (mole/s)

0.025
0.054

0.052
0.02
0.05

0.015 0.048

0.046
0.01
0.044

0.042
0.005
0.04
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
Dimensionless length Dimensionless length

c 0.03 d 0.016
Exothermic side
CR CR
TCMR TCMR
0.014
TCTMR TCTMR

0.012
H2O molar flow rate (mole/s)
CO molar flow rate (mole/s)

0.025
0.01

0.008

0.006
0.02

0.004

0.002

0.015 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
Dimensionless length Dimensionless length

e Exothermic side

0.42 CR
TCMR
0.41 TCTMR

0.4
H2 molar flow rate (mole/s)

0.39

0.38

0.37

0.36

0.35

0.34

0.33
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Dimensionless length

Fig. 3 e Comparison of (a) methanol, (b) CO2, (c) CO, (d) H2O and (e) H2 molar flow rate along the reactor axis between
exothermic sides of TCTMR, TCMR and CR.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5 7319

a 0.01
TCTMR
0.01
Table 8 e Comparison of reactors performance.
TCMR Reactor Conversion Selectivity Yield
0.008 0.008
(%) (%)
C6H12 molar flow rate (mole/s)

C6H6 molar flow rate (mole/s)

C6H12 CH3OH CH3OH C6H6 H2
recovery
0.006 0.006
CR e 1.09 0.3533 e e
TCMR 81.59 1.1 0.3591 0.8159 2.4757
TCTMR 93.26 1.1031 0.3822 0.9326 2.6979
0.004 0.004

0.002 0.002 difficulties to construct a leak-free membrane reactor with

two sides, the catalysts would not age identically, the cost of
membranes and it would require a situation where the
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 quantities of the materials to be processed by the two reac-
Dimensionless length
tions be in the proper balance.

Endothermic side
b 0.03
TCMR 6.3. Thermal behavior
TCTMR
0.025
Fig. 6(a)e(c) shows axial temperature profiles for CR and
H2 molar flow rate (mole/s)

thermally coupled membrane and two-membrane reactor in

0.02
different sides of reactor configurations. The highest
temperature is observed at the exothermic side, since this is
0.015 where heat is generated. Part of this heat is used to drive the
endothermic reaction and the rest is used to heat the
0.01 mixtures in both reaction sides (in case of both thermally
coupled reactors) and inner permeation side (in case of
0.005
TCTMR). The temperature of the endothermic side is always
lower than that of the exothermic side in order to make
a driving force for heat transfer from the solid wall. Along the
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 exothermic side of thermally coupled reactors, temperature
Dimensionless length
increases smoothly and a hot spot develops as demonstrated
Fig. 4 e Comparison of (a) C6H12, C6H6 and (b) H2 molar flow in Fig. 6(a) and then decreases. The exothermic temperature
rate along the reactor axis between endothermic sides of control of the TCTMR is easier due to lower hot spot. There is
TCMR and TCTMR. not a sudden rises of temperature for this system at reactor
entrance. Thus, the most favorable exothermic temperature
profile seems that belongs to TCTMR system as a result of
simultaneously heat transfer with permeation side in inner
Outer permeation side tube and reacting gas in endothermic side. At the entrance of
0.35 endothermic side of TCRs, the temperature decreases rapidly
TCMR
and a cold spot forms and then the temperature increases (see
TCTMR
0.3 Fig. 6(b)). In situ water removal from the exothermic side
shifts the reaction to methanol production and higher yield of
reaction achieves and thus more reaction heat is released.
H2 molar flow rate (mole/s)

0.25
This is the reason why endothermic temperature of TCTMR is
higher than that of TCMR. As it can be seen in Fig. 6(c), the
0.2
temperature profile pattern in outer and inner permeation
sides is the same as temperature profile pattern in endo-
0.15
thermic side.
Fig. 7 shows the comparison of fuel ratio and reactor effi-
0.1 ciency for both of thermally couple reactors. As it can be seen
in this figure, fuel ratio and reactor efficiency values of TCTMR
0.05 are closer to the optimal conditions relative to those of TCMR.
Therefore, the exothermic and the endothermic reaction can
0
be more efficiently coupled in this configuration and an effi-
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
cient autothermal coupling is achieved without the occur-
Dimensionless length
rence of extremely high temperatures.
Fig. 5 e Comparison of hydrogen molar flow rate between Overall, the operating and design parameters chosen for
outer permeation sides of TCTMR and TCMR. the reactor configuration lead to efficient coupling of the two
7320 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5

1.3
a 530
TCTMR
TCMR
Temperature of gas phase in exothermic side (K)

1.2
525

1.1 Optimal condition

520
1

Value
515 0.9

0.8
510

0.7

505
CR 0.6
TCMR
TCTMR
500 0.5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Reactor efficiency Fuel ratio
Dimensionless length

Fig. 7 e The comparison of values of fuel ratio and reactor

b 514
TCMR efficiency for the thermally coupled membrane and two-
Temperature of gas phase in endothermic side (K)

TCTMR
512 membrane reactors.

510

508 6.4. Influence of inlet temperature of endothermic

stream
506

As it can be seen in Fig. 6(b), there is a cold spot in the endo-

504
thermic side. This may be attributed to the reasons such as
502
dissimilar reaction rates and heats of exothermic and endo-
thermic reactions. One way of eliminating this cold spot is by
500 using non-similar feed temperature for the exothermic and
endothermic streams. Fig. 8 shows the influence of inlet
498
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 temperature of endothermic stream on the temperature
Dimensionless length profiles in endothermic and exothermic sides along the
c 520 520 reactor length for thermally coupled two-membrane reactor.
Temperature of gas phase in inner permeation side (K)
Temperature of gas phase in outer permeation side (K)

TCTMR These are the cases where the cold spot is not observed which
TCMR
are due to suitable temperature driving force for transferred
heat from the solid wall. Here the inlet temperature of the
515 515

520
Endothermic side
510 510 Exothermic side

515

505 505 510

Temperature (K)

505

500 500
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Dimensionless length 500

Fig. 6 e Variation of temperature for CR and thermally

coupled membrane and two-membrane reactors in (a) 495
exothermic side, (b) endothermic side, (c) outer and inner
permeation sides along the reactor axis.
490
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Dimensionless length

reactions. The efficient coupling of exothermic and endo- Fig. 8 e Influence of inlet temperature of endothermic
thermic reaction in a single vessel reduces the thermal losses stream on the temperature profiles in endothermic and
associated with the supply of heat for the energy intensive exothermic sides along the reactor length for thermally
endothermic process. coupled two-membrane reactors.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5 7321

Fig. 9 e Influence of molar flow rate of endothermic stream on (a) axial temperature profile in exothermic side, (b) in
endothermic side, (c) methanol yield, (d) hydrogen recovery yield and (e) cyclohexane conversion along the reactor length for
thermally coupled two-membrane reactor.
7322 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5
endothermic stream (T 490 K) is lower than the exothermic
stream. This arrangement requires the pre-heating of the
exothermic stream and that can be carried out by utilizing the
sensible heat of the exothermic stream leaving the reactor.
Decreasing the inlet temperature of endothermic stream from
503 to 490 K, can decrease the methanol yield from 0.3822 to
0.3773, hydrogen recovery yield from 2.6976 to 2.6123 and
cyclohexane conversion from 93.26% to 89.91%, which is due
to lower temperature at first parts of reactor and then lower
kinetics constants of reactions.
6.5. Influence of molar flow rate of endothermic stream
When reactor geometry, inlet operating conditions and
catalyst loading are fixed, variations of flow rates result in
corresponding variations of fluid velocities and residence
times. Fig. 9(a) and (b) shows the influence of molar flow rate
of endothermic stream on the temperature profiles of
exothermic and endothermic sides along the reactor length,
respectively. With increasing the flow rate of endothermic
stream, axial temperature variation of exothermic and
endothermic sides becomes lower which is due to higher
transferred heat from the solid wall. Fig. 9(c) and (d) illus-
trates how the methanol yield and hydrogen recovery yield
behave along the reactor axis when the flow rate of endo-
thermic stream increases from 0.1 to 0.2 mol s1. Decreasing
of methanol yield is due to lower axial temperature profile
(see Fig. 9(a)) and consequently lower rate of reaction. As it
can be seen in Fig. 9(d), increasing of molar flow rate of
endothermic stream results in hydrogen recovery yield
reduction from 2.69 to 1.83 which is due to lower cyclohexane
conversion. Cyclohexane conversion significantly decreases
from 93.26% to 46.12% (see Fig. 9(e)). Decreasing of cyclo-
hexane conversion is an obvious consequence of the fact that
the amount of catalyst on endothermic side is not enough for
these higher flow rates. Besides, lower axial temperature
profile of endothermic side (see Fig. 9(b)) can result in
cyclohexane conversion which is an endothermic reversible
reaction.
Fig. 10 e Influence of molar flow rate of outer permeation stream on (a) hydrogen recovery yield and (b) hydrogen
permeation rate in outer permeation side for thermally coupled two-membrane reactor.
6.6. Influence of molar flow rate of outer permeation
stream
The effect of the outer sweep gas flow rate on reactor perfor-
mance for the co-current mode is shown in Fig. 10. With
increase in the sweep gas flow rate, the partial pressure of
hydrogen in the separation side decreases, leading to increase
driving force for the permeation of hydrogen through the Pd/
Ag membrane. As a result, hydrogen recovery yield increases.
Fig. 10(b) presents the profiles of permeation rate of hydrogen
thorough the membrane versus dimensionless length and
inlet flow rate of outer permeation side. As shown in this
figure, increasing inlet flow rate of the outer permeation side
enhances hydrogen permeability along the reactor; hydrogen
permeation depends on the hydrogen partial pressure square
root difference between the reaction zone and the permeation
zone. Consequently, permeation rate of hydrogen enhances
when partial pressure square root difference increases.
6.7. Influence of Pd/Ag membrane thickness
To enhance the hydrogen recovery yield in thermally coupled
membrane reactor, thickness of the membrane should be
reduced. Pd-based membranes have a high selectivity for
hydrogen but the rate of hydrogen permeation in Pd
membrane is low. To overcome this problem many efforts
have been made to reduce the thickness of the Pd-based
membrane reactor by producing a thin layer of palladium on
a support like alumina and stainless steel. Larger pores and
the high selectivity of the Pd-based membrane to hydrogen
make it possible to obtain both high permeability and selec-
tivity. Fig. 11 illustrates the effect of membrane thickness on
the hydrogen recovery yield. As can be seen in this figure, the
reduction of membrane thickness from 200 mm to 6 mm can
enhance 254% of hydrogen recovery yield according to the
increase in the hydrogen permeation rate at the basic condi-
tions. Also Fig. 11 shows thickness of layer thinner than
100 mm has the better efficiency. Decreasing of membrane
thickness has a little effect on methanol yield and cyclo-
hexane conversion.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5 7323

3 6.8. Production rate

Fig. 12(a) and (b) presents the comparison of methanol and

2.5
hydrogen production in CR, TCMR and TCTMR. As demon-
strated, the methanol production of TCTMR increases about 9
Hydrogen recovery yield

2 and 7.18% relative to that of CR and TCMR, respectively.

Additionally, an increment about 8.22% in hydrogen produc-
tion is achieved for TCTMR in comparison with TCMR. This
1.5
considerable improvement in the methanol and hydrogen
production rate of TCTMR is due to utilizing simultaneous
1 hydrogen and water permselective membranes in endo-
thermic and exothermic sides, respectively and also
extremely favorable profile of temperature in both sides of
0.5
TCTMR.

0
20 40 60 80 100 120 140 160 180
Pd/Ag memberane thickness (m) 7. Conclusion

Fig. 11 e Influence of membrane thickness on hydrogen The methanol forming reactions are strongly exothermic and
recovery yield. limited by the thermodynamic equilibrium. Therefore, the
development of a membrane-based process could open the
way to increasing the methanol production in the methanol
synthesis process. In this work, thermally coupled two-
membrane system (TCTMR) was compared with a thermally
coupled membrane reactor (TCMR) and conventional reactor
(CR) for simultaneous pure hydrogen production and meth-
anol synthesis. This recuperative configuration as same as
TCMR represents some important improvement in compar-
ison to conventional methanol reactor as follows: reduction
reactors sizes; production pure hydrogen in the permeation
side; increasing rate of methanol synthesis and shifting
thermodynamics equilibrium; production of benzene as an
additional valuable product; and autothermal conditions are
achieved within the reactors. The potential possibilities of the
TCTMR were analyzed using a one-dimensional heteroge-
neous model to obtain the necessary comparative estimates.
The simulation results show that there is extremely favorable
profile of temperature in exothermic side and represent 6.03
and 7.56% enhancement in the methanol yield in comparison
with TCMR and CR, respectively. Also, 8.2284 and 12.521%
enhancements in the hydrogen and benzene production
relative to TCMR are seen, respectively. Finally, these
preliminary simulation results demonstrate that the fixed-bed
membrane reactor technology with in situ H2O removal is
more efficient for methanol synthesis than a fixed-bed reactor
without H2O removal.

Nomenclature

av specific surface area of catalyst pellet, m2 m3

Ac cross section area of each tube, m2
Ai inside area of inner tube, m2
Ao outside area of inner tube, m2
C total concentration, mol m3
Fig. 12 e The comparison of (a) methanol production in CR, Cp specific heat of the gas at constant pressure, J mol1
TCMR and TCTMR and (b) pure hydrogen production in dp particle diameter, m
TCMR and TCTMR. Di tube inside diameter, m
7324 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 7 3 1 0 e7 3 2 5

Dij binary diffusion coefficient of component i in j, u superficial velocity of fluid phase, m s1
m2 s1 ug linear velocity of fluid phase, m s1
Dim diffusion coefficient of component i in the mixture, U overall heat transfer coefficient between exothermic
m2 s1 and endothermic sides, W m2 K1
Do tube outside diameter, m vci critical volume of component i, cm3 mol1
Dsh shell inside diameter, m yi mole fraction of component i, mol mol1
fi partial fugacity of component i, bar z axial reactor coordinate, m
F total molar flow rate, mol s1
G mass velocity, kg m2 s1 Greek letters
hf gasesolid heat transfer coefficient, W m2 K1 m viscosity of fluid phase, kg m1 s1
hi heat transfer coefficient between fluid phase and r density of fluid phase, kg m3
reactor wall in exothermic side, W m2 K1 rb density of catalytic bed, kg m3
ho heat transfer coefficient between fluid phase and s tortuosity of catalyst
reactor wall in endothermic side, W m2 K1
DHf,i enthalpy of formation of component i, J mol1 Superscripts
JH permeation rate of hydrogen through the PdeAg g in bulk gas phase
membrane, mol m1 s1 s at surface catalyst
JH2 O permeation rate of water through the H-SOD
membrane, mol m3 s1 Subscripts
k rate constant of dehydrogenation reaction, 0 inlet conditions
mol m3 Pa1 s1 B benzene
k1 rate constant for the 1st rate equation of methanol C cyclohexane
synthesis reaction, mol kg1 s1 bar1/2 i chemical species
k2 rate constant for the 2nd rate equation of methanol j reactor side
synthesis reaction, mol kg1 s1 bar1/2 k reaction number index
k3 rate constant for the 3rd rate equation of methanol
synthesis reaction, mol kg1 s1 bar1/2
kg mass transfer coefficient for component i, m s1 references
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