Journal of Natural Gas Science and Engineering 3 (2011) 484e495

Contents lists available at ScienceDirect

Journal of Natural Gas Science and Engineering

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

A comparative study between a uidized-bed and a xed-bed

water perm-selective membrane reactor with in situ H2O removal
for FischereTropsch synthesis of GTL technology
M.R. Rahimpour a, *, A. Mirvakili a, K. Paymooni a, B. Moghtaderi b
a
b

Chemical Engineering Department, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran
Discipline of Chemical Engineering, Faculty of Engineering and Built Environment, The University of Newcastle, University Drive, 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:
Received 17 January 2011
Received in revised form
25 May 2011
Accepted 26 May 2011
Available online 28 June 2011

In order to eliminate the pressure drop problem and mal distribution of the temperature prole along the
reactors, uidized-bed membrane reactors are proposed as an alternative for FischereTropsch synthesis
(FTS) in gas-to-liquid (GTL) technology. Regarding this, a novel cascading uidized-bed membrane reactor
(CFMR) is proposed in this study and compared with a xed-bed membrane cascading with uidized-bed
membrane reactor (FMFMR). The CFMR conguration consists of a uidized-bed water perm-selective
membrane reactor followed by a uidized-bed hydrogen perm-selective membrane reactor. The performance of CFMR is compared with FMFMR in order to investigate the effect of uidization concept on the
reactor performance. Unlike CFMR where a uidized-bed concept is applied in the rst reactor, a xed-bed
concept is used in the rst reactor of FMFMR. The modeling results show 5.3% increase in the gasoline yield
and 12% decrease in CO2 yield in CFMR in comparison with FMFMR owing to applying a uidized-bed
concept instead of a xed-bed concept in which more effective temperature management is achieved.
According to the modeling results, CFMR is superior to FMFMR for FTS in GTL technology owing to
achieving excellent temperature control and a small pressure drop and consequently higher gasoline yield
and lower CO2 yield.
2011 Elsevier B.V. All rights reserved.

Keywords:
FischereTropsch synthesis
Water perm-selective membrane layer
Fluidized-bed membrane reactor
FT reactor combination
In situ water removal
GTL technology

1. Introduction

1.1. Process and model

The conversion of natural gas to hydrocarbons (Gas-To-Liquids

route) is currently one of the most promising topics in the energy
industry due to economic utilization of remote natural gas to
environmentally clean fuels. For FT to be competitive with crude oil,
while the latter is still available, the cost of coal or methane needs
to be low (Dry Mark, 1999). FT products are of high quality, being
free of sulfur, nitrogen, aromatics, and other contaminants typically
found in petroleum products, which is especially true for
FT-gasoline with a very high octane number. However, drawbacks
also exist for the FT process: the capital costs of FT conversion
plants are relatively higher and the energy efciency of producing
FT liquids is relatively lower than the one for other alternative fuels
such as hydrogen, methanol, dimethyl ether (DME) and conventional biofuels (Takayuki and Kenji, 2008).

In order to realize more comprehensive description of FTS

process and model, the kinetics model and a few mathematical
modeling studies on FTS are provided as follows:
The kinetics of the gasesolid FTS over a commercial
FeeCueKeSiO2 catalyst was studied in a continuous spinning
basket reactor (van der Laan, 1999). Schulz et al. (1999) extended
their existing kinetic model by taking into account olen hydrogenation, isomerization (double bond shift) and incorporation and
in particular chain length dependent product solubilities. The validity of their model was checked with experimental data obtained
from FTS runs in a slurry reactor with cobalt and iron catalysts.
Eliason et al. obtained rate data for FTS on unsupported Fe and Fe/K
catalysts at total pressure, temperature, and H2 and CO partial
pressures of 10 atm, 200e240
C, 0.9e1.4 and 0.4e0.9, respectively
(Eliason and Bartholomew, 1999). Nowicki et al. (2001) developed
a new hydrocarbon product distribution model for FTS reaction.
The model was based on the assumption that there are two types of
active sites on the catalyst surface: type-1, where growth of
hydrocarbon intermediates occurs, and type-2, where reversible re

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

E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).
1875-5100/$ e see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jngse.2011.05.003

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

adsorption of 1-ole00 ns occur. Nakhaei Pour et al. (2011) investigated

the kinetic modeling of the water-gas-shift (WGS) reaction over
a Fe/Cu/La/Si catalyst under FTS reaction condition. A new GTL
process based on a single stage xed-bed FTS was developed in the
Research Institute of Petroleum Industry (RIPI) to produce high
octane and low sulfur gasoline (RIPI-NIOC, 2004). Ahmadi Marvast
et al. considered a water-cooled xed-bed reactor with a length of
12 m (Marvast et al., 2005). Rahimpour et al. optimized a uidizedbed hydrogen perm-selective membrane reactor for FTS
(Rahimpour and Alizadehhesari, 2008). Rahimpour and Elekaei
compared the performance of uidized-bed membrane dual-type
reactor (FMDR) with CR for FTS (Rahimpour, 2008). Moreover,
several investigations are performed by Rahimpour et al. to apply
membranes in dual-type reactors (Rahimpour and Elekaei,
2009a,b; Forghani et al., 2009; Rahimpour et al., 2010).
1.2. Hydroxy sodalite (H-SOD) membrane
H-SOD membrane has been used as highly water perm-selective
membrane for water permeation. H-SOD is a zeolite-like material
which consists of sodalite cages exclusively (Fernandes and Soares,
2006; Gielens et al., 2007). H-SOD membrane shows excellently
ideal selectivity (near to absolute) of water to hydrogen. It can be
considered as a capable candidate for water separation in FTS
which requires a high H2O/H2 perm-selectivity (Rohde et al., 2008).
The exceptional property of H-SOD membrane in comparison with
the other widely studied membranes (Rohde et al., 2008; Peters
et al., 2008; Dittmeyer et al., 2001) is its 100% selectivity of water
on the basis of molecular sieving in hybrid processes (Rohde et al.,
2008; Breck, 1974). No traces of the other components are detected
in permeate (water selectivity w 1,000,000). Thus, H-SOD is
a promising candidate for in situ H2O removal during FTS (Breck,
1974).
1.3. Effect of in situ H2O removal
Water is a primary product of FT reactions and CO2 can only be
produced by WGS reaction which is a reversible paralleleconsecutive reaction in respect to CO (Rohde et al., 2008;
Khajavi et al., 2010). In case of Fe catalysts, oxidation and hydrothermal sintering lead to formation of an inactive magnetite core
and losing the active surface area, respectively (David et al., 1991).
The WGS reaction can be displaced selectively in favor of CO by in
situ H2O removal (Rohde et al., 2008). Since in situ H2O removal
accelerates the reverse WGS of CO2 with H2 toward CO, CO2 can be
utilized as a constituent in the synthesis gas which reacts in
a subsequent step toward long-chain hydrocarbons (Rohde et al.,
2008). The effect of the in situ water removal is extensively discussed in the previous publication (Rahimpour et al., 2011).

485

a uidized-bed reactor instead of a xed-bed reactor (Rahimpour

and Elekaei, 2009a,b; Forghani et al., 2009; Rahimpour et al.,
2010, 2011).
1.5. Objectives
The underlying goal of this study is to investigate the effect of
applying a uidization concept in the rst reactor of CFMR instead
of a xed-bed concept in FMFMR on the reactors performance.
Altering the rst reactor from a xed-bed in FMFMR to a uidizedbed in CFMR is comprehensively investigated in this study.
Modeling results of CFMR are compared with the results of FMFMR
and the CR plant data. Some criteria such as the gasoline yield, the
CO2 yield and temperature prole are considered for recognizing
the best conguration. Moreover, the simultaneous effects of the in
situ water removal and uidization are investigated on CFMR and
FMFMR performances. Owing to simultaneously applying a uidized-bed concept and H-SOD membrane layer in CFMR, the products yield increase considerably in CFMR compared with FMFMR as
demonstrated further.
2. Process description
CFMR, FMFMR and CR are packed by a bi-functional Fe-HZSM5
catalyst (metal part: 100 Fe/5.4 Cu/7K2O/21SiO2, acidic part: SiO2/
Al2O3 28).
2.1. Conventional xed-bed FTS reactor (CR)
A schematic process diagram of CR is depicted in Fig. 1 (RIPI-NIOC,
2004; Marvast et al., 2005). CR is extensively discussed in the
previous publication (Rahimpour and Elekaei, 2009a).
2.2. Membrane dual-type reactors (FMFMR and CFMR)
A schematic diagram of CFMR conguration is depicted in
Fig. 2(a). A schematic diagram of FMFMR is depicted in Fig. 2(b).
Unlike FMFMR where the rst reactor is a xed-bed water permselective membrane reactor, a uidized-bed water perm-selective
membrane reactor is fabricated in the rst reactor of CFMR. The

Steam
Reforming

Steam Drum

1.4. Fluidized-bed reactor

One of the new possibilities for improving the efciency of
a conventional xed-bed reactor is the application of a uidizedbed technology. Fluidized-bed reactors are particularly attractive
for highly exothermic reactions because of their superior heat
management ability, proper mixing and excellent temperature
control, a small pressure drop and elimination of diffusion limitations (van der Laan and Beenackers, 2000). Other advantages of
uidized-bed membrane reactors include the possibility of using
inexpensive metal alloys as well as continuous/periodic catalyst
replacement (Dry, 1990). Despite such obvious advantages,
uidized-bed membrane reactors have not been widely exploited
by industry (Dry, 1990; Unruh et al., 2004). Rahimpour et al.
improved methanol synthesis reactor and FTS reactor by using

Product

Fig. 1. Schematic diagram of a conventional xed-bed reactor (CR).

486

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

a
Steam
Reformer

N2
Reaction Gas

Steam Drum

Pd-Ag
membrane
GTL
Product
H-SOD
membrane

Catalyst

Second Reactor
Gas-cooled reactor

Synthesis Gas

First Reactor
Water-cooled reactor

N2 + H2O

b
N2 & H2O
Steam
reformer

Steam drum
Synthesis gas
Pd-Ag
membrane

H-SOD
membrane

Product

Reaction gas
N2
Fluidized-bed membrane reactor
(the second reactor)

Fixed-bed membrane reactor

( the first reactor)

Fig. 2. Schematic diagram of (a) cascading uidized-bed membrane dual-type FTS reactor (CFMR), (b) FMFMR.

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495
Table 1
Specications of FMFMR.
Parameter

Catalyst density [kg$m3]

Catalyst equivalent diameter [m]
Molar ratio of H2/CO in feed
Flow rate per tube [gmol$s1]
Feed temperature [K]
Reactor pressure [kPa]
Cooling temperature [K]
Bulk density [kg$m3]
Tube length [m]
Tube size [mm]
Number of tubes
Bed voidage
Catalyst thermal conductivity
[kJ$m1 s1 K1]

487

Table 3
Kinetic parameters data (RIPI-NIOC, 2004).
Water-cooled
reactor
(rst reactor)

Gas-cooled
reactor
(second reactor)

1290
3.83  103
0.96
0.0335
565
1700
566
730
7.2
21.2  4.2
180
0.488
0.00625

1290
0.2  103
e
0.377
e
2200
e
e
4.8
21.2  4.2
16
0.56 (min uidization)
0.00625

CFMR conguration consists of a uidized-bed water permselective membrane reactor (the rst reactor) followed by a uidized-bed hydrogen perm-selective membrane reactor (the second
reactor). The structure of the rst reactor (water-cooled reactor) is
such that the primary and secondary shell sides are fabricated
where a coolant stream ows in the former one and the latter one is
packed by catalyst particles. The walls of the tubes in both
uidized-bed membrane reactors of CFMR are coated by H-SOD on
a-Al2O3 support and PdeAg membrane layers. In the rst reactor of
CFMR, water permeates through the H-SOD membrane layer to the
tube side owing to a water partial pressure difference between both
sides of the membrane layer. The inert gas (i.e., N2) is directed to the
tube side and carries the permeated water. In the second reactor,
a cold feed synthesis gas is preheated in the tube side and subsequently fed into the secondary shell side of the rst reactor where
the chemical reaction is initiated by catalysts. The partially reacted
gas leaves the rst reactor and it is subsequently fed to the bottom
of the second reactor. It is directed to the shell side of the second
reactor in a counter-current mode with synthesis gas owing
through the tube side and it uidizes the catalyst particles in the
shell side. Hydrogen permeates through the PdeAg membrane
layer to the reaction side due to a hydrogen partial pressure driving
force in the second reactor. The reaction is completed in the second
reactor. Specications of the FMFMR conguration are presented in
Table 1. Specications of the rst reactor (uidized-bed reactor) in
CFMR conguration are presented in Table 2.

Reaction No.

1
2
3
4
5
6
7
8

1.0889
0.7622
0.5645
0.4051
0.4728
0.8204
0.5850
0.5742

1.5662
0.0728
1.3155
0.6635
1.1389
0.5026
0.5982
0.710

142583.8
51.556
24.717
0.4632
0.00474
0.00832
0.02316
410.667

83423.9
65018
49782
34885.5
27728.9
25730.1
23564.3
58826.3

3.1. Reaction network

The FT components consist of H2, CO, CO2, H2O, CH4, C2H6, C3H8,
i-C4H10, n-C4H10, and C
5 . The principal FTS reactions are as follows
(RIPI-NIOC, 2004):
R1

CO 3H2 /CH4 H2 O

(1)

R2

2CO 4H2 /C2 H2 2H2 O

(2)

R3

2CO 5H2 /C2 H6 2H2 O

(3)

R4

3CO 7H2 /C3 H8 3H2 O

(4)

R5

4CO 9H2 /n-C4 H10 4H2 O

(5)

R6

4CO 9H2 /i-C4 H10 4H2 O

(6)


R7
6:05 CO 12:23 H2 /C6:05 H12:36 C5 6:05 H2 O

(7)

R8

CO H2 O 4 CO2 H2 WGS reaction

(8)

H-SOD membrane
N2 + H2O

3. Mathematical model
A heterogeneous one-dimensional model including a set of
coupled energy and mass balances as well as kinetics equations are
taken into consideration.
Table 2
Specications of the rst reactor in the CFMR.

coolant

H2O

Parameter

Water-cooled reactor
(rst reactor)

Flow rate per tube [gmol$s1]

Flow rate per shell [gmol$s1]
Catalyst equivalent diameter [m]
Tube pressure [Kpa]
Shell pressure [kPa]
Cooling temperature [K]
Bulk density [kg$m3]
Tube length [m]
Tube size [mm]
Shell side size [mm]
Number of tubes

0.05
0.06
3.83  104
1700
1700
566
730
7.2
21.2  4.2
50.8  4.2
180

H2O

Catalyst
N2
Fig. 3. Schematic diagram of an elemental volume in the rst reactor of CFMR.

488

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

Kinetic parameters are presented in Table 3 and the reaction rate

equation is as follows:



Ei m n
PCO $PH2
RT

h
i
mol$kg1
cat $s

Ri 0:278 ki exp

(9)

The kinetic model is valid in the temperature, the pressure and

the H2/CO molar ratio range of 290e310
C, 15e23 bar and
0.76e1.82, respectively (RIPI-NIOC, 2004).

Table 5
Hydrodynamic parameter (Kunii and Levenspiel, 1991; Deshmukh et al., 2005).
Parameter

Equation

Supercial velocity at minimum

uidization

Umf 0:01

Archimedes number

m
27:22 0:0408Ar0:5 27:2
rgdp
d3p rg rp  rg g
Ar
m2

db dbm  dbm  dbo exp0:3z=D

Bubble diameter

dbm 411:38AU0  Umf 0:4

dbo 0:376U0  Umf 2

3.2. Mathematical model of FMFMR

The mathematical model of FMFMR was extensively developed
in the previous publication (Rahimpour et al., 2011).

Volume fraction of bubble phase d U0  Umf =Ub

to overall bed
Bubble rising velocity
Ub U0  Umf gdb 0:5
 0:021
rg
Bed voidage at minimum velocity 3mf 0:5861=Ar0:029

rp

Overall mass transfer coefcient

Kbe

Umf
4Djm $3mf $Ub =pdb 0:5
3

3.3. Mathematical model of CFMR

3.3.1. Fluidized-bed water perm-selective membrane reactor
(the rst reactor)
The walls of the tubes in the rst reactor and the second reactor
of CFMR conguration are coated by the H-SOD and PdeAg
membrane layer, respectively. The following assumptions are made
in the mathematical modeling of the rst reactor in CFMR:
1) Due to rapid mixing, the operation is assumed to be isothermal
which means that the bubble and the emulsion phases have the
same temperature.
2) Both phases have the plug ow regimes.
3) Hydrogen is only added to the emulsion phase and water is
only removed from the emulsion phase.
4) Axial diffusion of water and hydrogen through the membrane
is negligible in comparison with radial diffusion.
5) Catalyst particles can be found in the bubble phase and
therefore components can react well in rising bubbles. The

Equation

Component heat capacity

Cp a bT cT 2 dT 3
C1 T C2
m
C
C
1 3 42
T
T
Based on the Chung et al. method

Mass transfer coefcient

between gas and solid phases

kgi 1:17Re0:42 Sc0:67

ug  103
i
2Rp ug
Re

Sci

Dij

rDim  104

q
107 T 3=2 1=Mi 1=Mj



3=2
2=3 2
P vci vcj

Effectiveness factor for reaction

k (pore diffusion resistance)

1
1 Ai lnDo =Di Ai 1

U
hi
2pLKw
Ao ho



2=3
Cp m
h
0:458 rudp 0:407

3B
m
Cp rm K
R RP
r dr
hk 0 ks
RP rk

Water permeation rate

JH2 O

Hydrogen permeation rate

(Sieverts law)

JH

Heat transfer coefcient between

gas phase and reactor wall

11)

As seen in Fig. 3, the element with the length of Dz is taken into

consideration. The differential equations describing mass and
energy balances in the axial direction of CFMR are discussed in the
following subsections.
Mass balance equation for the bubble phase:

ft
Ashell

8
X
dyib
rbij 0 ;
d$kbei $ct $ab $yie  yib d$g$rp $
dz
j1

(10)

Table 6
A comparison between the modeling results of FMFMR and CFMR congurations
and plant data.
Parameter

Pilot
plant

1y
Dim P y i
i
i j Dij

Overall heat transfer coefcient

10)

i 1; 2; .; N  1

Parameter

Mixture thermal conductivity

7)
8)
9)

d

Table 4
Mass and heat transfer coefcients.

Viscosity of reaction mixtures

6)

extension of chemical reactions in the bubble phase, however,

is less than the emulsion phase.
Gas ow through the emulsion phase remains constant at the
minimum uidization velocity.
Gases are assumed to be ideal.
Steady state condition exists.
Ideal condition is assumed for H-SOD membrane (Ideal selectivity of water to hydrogen) (Rohde et al., 2008).
The variation of water concentration in the tube side is
negligible.
The temperature of the inert gas is constant.

As
P t
 P sh
$Q
Vr H2 O  H2 O  H2 O
Ep
q q
2pLp0 :exp
RT
t 
sh
PH
PH

Ro
ln
Ri

Xco (%)
XH2 (%)
C5 Selectivity
(g/Nm3 (CO
CO2 Selectivity
(g/Nm3 (CO
CH4 Selectivity
(g/Nm3 (CO
H2O Selectivity
(g/Nm3 (CO
C2H4 Selectivity
(g/Nm3 (CO
C2H6 Selectivity
(g/Nm3 (CO
C3H8 Selectivity
(g/Nm3 (CO
n-C4 Selectivity
(g/Nm3 (CO
i-C4 Selectivity
(g/Nm3 (CO

Model
predicted
(CFMR)

Relative
error (%)

Model
predicted
(FMFMR)

Relative
error (%)

77.94
93.83
42.55

92
99.8
54.46

18
6.36
27.99

86
99.4
51.99

14
5.93
22.18

339.77

248.87

26.75

305.15

10.01

44.15

38.26

13.34

41.5

6.00

120.67

146.18

21.14

112.8

6.5

3.95

4.5

13.92

5.5

11.78

11.9

1.02

12.4

9.33

6.8

27.11

11.07

10.24

14.45

12.82

H2))
H2))
H2))
H2))
39

H2))
5.26

H2))
7

24.97

7.49

9.5

14.18

11.28

12.22

15.43

H2))
H2))
H2))

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

489

a
10

Gasoline yield( gr/gr feed *100)

Gasoline yield (gr/gr feed *100)

12

4
CFMR
CR
FMFMR

10
8
6
4
2
0
560
559
558

6
Length (m)

10

Feed Temperatur (K) 557

12

12

Length (m)

Gasoline yield (gr/gr feed *100)

Gasoline yield (gr/gr feed *100)

d
15

10

0
555
550

15

10

0
22

12

21

545

540

Temperature (K)

12

19

3
535

20

Pressure (bar)

Length (m)

3
18

Length (m)

Fig. 4. Comparison of (a) Gasoline yield in three types of reactors: CR, CFMR and FMFMR congurations (b) Yield of gasoline as a function of pressure and FMFMR length (c) Yield of
gasoline as a function of pressure and CFMR length (d) Gasoline yield as a function of inlet temperature and CFMR length.

Mass balance equation for the emulsion phase:

8
X
dy
 1  d$
$ ie 1  d$re $h$
rij d$kbei $ab $ct $yib  yie
Ashell dz
j1

ft

 1  d$s$JH2 O 1  d$U$

JH2
0
As

11

The energy balance of the reaction side in the rst reactor is as

follows:

1  d$h$re $

8

 p$D




X
i
rj$ DHfj g$rB $d$h$
rbj $ DHfj
A
shell
j1
j1

8
X

 $Ushell $Tshell  T s$1  d$JH2 O  U$1  d$

JH2
0
As

JH2 , are reported in Table 4. As is the equivalent area around each

tube, Ashell is the equivalent cross sectional area of the shell around
each tube.
Boundary conditions for the bulk phase are expressed as:

at

z 0;

yi yi; in

T Tin

(13)

3.3.2. Fluidized-bed hydrogen perm-selective membrane reactor

(the second reactor)
The mathematical modeling of the second reactor in CFMR is
similar to the one of FMFMR (Rahimpour et al., 2011).
3.4. Auxiliary correlations

12

s and U equal 0 and 1 for the rst reactor and 1 and 0 for the second
reactor, respectively. Water, JH2 O , and hydrogen permeation rates,

In order to simulate the reactor, heat and mass transfers

between solid and uid phases have been taken into consideration.
Physical properties of the components are also important for the

490

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

calculations. Therefore, some other correlations are used to cover

these issues. The correlations of physical properties, mass and heat
transfer coefcients are listed in Table 4 and also hydrodynamic
properties are presented in Table 5.
4. Numerical solution
The CFMR model consists of a set of differential-algebraic
equations (DAE) including mass and energy balances for bubble
and emulsion phases in the rst and the second reactors. Moreover,
these equations are coupled with non-linear algebraic equations of
the kinetic model, uidized-bed hydrodynamic and transport
property correlations and other auxiliary correlations. In order to
solve the set of equations, a backward nite difference approximation is applied.
5. Model validation
Model validation is carried out by comparison of model results
of xed-bed FT reactor with the RIPI pilot plant data (Marvast et al.,
2005) under the design specications and input data. The CFMR
modeling results and the corresponding observed data of the pilot
plant is presented in Table 6. A good agreement is observed
between the estimated results and the pilot plant data.
6. Result and discussion
The performance of CFMR conguration is investigated and
compared with the FMFMR and CR performances in the following
gures:

4
3
2

CFMR
CR
FMFMR

0.6
0.5
0.4
0.3
0.2

6
8
Length (m)

10

12

CFMR
CR
FMFMR

0.1
0

Normal-butane yield (gr/gr feed *100)

Ethylene yield (gr/gr feed *100)

6
8
Length (m)

10

12

d
Propane yield (gr/gr feed *100)

4
3.5
3
2.5
2
1.5
CFMR
CR
FMFMR

1
0.5
0

6
8
Length (m)

10

12

0.7
0.6
0.5
0.4
0.3
CFMR
CR
FMFMR

0.2
0.1
0
2

6
8
Length (m)

10

12

f
1.6

4.5

0.8

Iso-butane yield (gr/gr feed *100)

Methane yield (gr/gr feed *100)

e
0.7

Ethane yield (gr/gr feed *100)

Fig. 4(a) illustrates the gasoline yield in three different congurations. As seen, the performances of both dual-type reactors (i.e.,
CFMR, FMFMR) are superior to CR owing to achieving remarkably
higher gasoline yield in dual-type reactors. The in situ water
removal shifts the FTS reactions to the products side according to
the thermodynamic equilibrium which enhances the yields of
heavy hydrocarbons such as gasoline. The highest gasoline yield is
achieved in CFMR as a consequence of the in situ water removal
from the secondary shell side (reaction side) of the rst reactor and
applying the uidization concept. Since a uidized-bed reactor has
some superiorities such as better heat management ability, excellent temperature control and a small pressure drop to the xed-bed
reactor, the gasoline yield in CFMR is higher than FMFMR. Moreover, the reaction side temperature prole in CFMR is lower than
FMFMR owing to good controlling of heat transfer in the uidizedbed reactor. Therefore, gasoline and other heavier components are
produced in CFMR more than the ones in FMFMR owing to their
lower temperature. Also, the effect of the in situ water removal on
the enhancement of the gasoline yield in CFMR is more considerable than the one in FMFMR owing to a slight pressure drop in
a uidized-bed reactor. Thus, lower temperature and pressure
drops in uidized-bed reactor enhance the gasoline yield in CFMR
compared with FMFMR.
Fig. 4(bec) illustrates the 3D plot of gasoline yield as a function
of feed temperature and reactor length in CFMR and FMFMR
congurations. As seen, the gasoline yield increases along CFMR
and FMFMR and rises slightly by temperature ascending however
the gasoline yield in CFMR is higher than the one in FMFMR. Higher
gasoline yield is achieved at higher feed temperatures. Fig. 4(d)
illustrates the 3D plot of gasoline yield as a function of pressure and
CFMR length. The water permeation rate increases with increasing

6
5
4
3
2

CFMR
CR
FMFMR

1
0

6
8
Length (m)

10

12

1.4
1.2
1
0.8
0.6
CFMR
CR
FMFMR

0.4
0.2
0

6
8
Length (m)

Fig. 5. Comparison of components yield along different reactors for (a) CH4, (b) C2H6, (c) C2H4, (d) C3H8, (e) n-C4H10 and (f) i-C4H10.

10

12

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

a
45

H2O yield (gr/gr feed *100)

35
30
25
20
15

CO yield (gr/gr feed *100)

18
16

40

5
0

10

14
12
10
8
6

CFMR
CR

FMFMR

CFMR
CR
FMFMR

10

491

2
0

10

12

Length (m)

12

Length (m)

b
b

-6

2.6

x 10

H2O Permeation rate

40

30

20

10

CO yield (gr/gr feed *100)

2.4

0
22

2.2
2
1.8
1.6
1.4
CFMR

21

12

FMFMR

20

19

Pressure (bar)

1.2

3
18

Length(m)

Fig. 6. (a) Comparison of CO2 yield along CR, CFMR and FMFMR (b) CO2 yield as
a function of pressure and CFMR length.

the pressure of the secondary shell side according to Fig. 7(b).

Moreover, the in situ water removal increases the reaction rates of
heavy hydrocarbons. Therefore, the production rate of gasoline
increases along CFMR.
Fig. 5 illustrates the production yields of hydrocarbons such as
methane, ethane, ethylene, propane, normal butane and isobutane. Fig. 5(a) shows the production yield of methane. The
least methane yield is achieved in CFMR conguration. Methane is
an undesired product. The methane production rate is highly
temperature dependent. Therefore, the methane production rate
increases at higher temperatures. Since the temperature of CFMR is
lower than FMFMR and CR (mainly due to applying a uidization
concept in the rst reactor), the methane production rate in CFMR
is considerably lower than the one in FMFMR and CR. According to
the fact that the production rates of light hydrocarbons are higher
at elevated temperatures, the ethane, ethylene, and propane yield
in CFMR are lower than the ones in FMFMR and CR. As shown in

Length (m)
Fig. 7. Comparison of (a) yield of water in CR, CFMR and FMFMR congurations (b) the
water permeation rate in the rst reactor of CFMR and FMFMR.

Fig. 5(bed), the ethane, ethylene and propane yield in CFMR are
5.6%, 4.8% and 4.6% lower than the ones in FMFMR. The in situ water
removal has a little effect on the production rates of light
hydrocarbons.
The normal butane yield is compared with the iso-butane yield
in Fig. 5(eef). The normal butane and iso-butane yields in CFMR
increase 3.2% and 2.8% more than the ones in FMFMR, respectively.
Since the production rate of butane increases with temperature
decreasing, the butane production rate increases in CFMR
compared with the other hydrocarbon products. Moreover, the
effect of the in situ water removal on the increasing of heavier
components is more considerable than lighter one. Therefore, the
in situ water removal via the H-SOD membrane layer increases the
production rates of normal and iso-butane components.
Fig. 6(a) illustrates the CO2 yield along CR, FMFMR and CFMR.
The decrease in CO2 yield in CFMR and FMFMR is more considerable
than the one in CR. The in situ water removal in the rst reactor of

492

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

590

100

Temperature of Gas Phase (K)

FMFMR

CO conversion(%)

80

60

40
FMFMR

20

CFMR
CR

6
Length (m)

10

12

CR
CFMR

570
560
550
540
530
520

10

12

Length (m)
Fig. 9. Comparison of reacting gas temperature proles along three different FT
congurations.

100

80

H2 conversion(%)

580

60

40
CFMR
FMFMR
CR

20

6
Length (m)

10

12

Fig. 8. Comparison of (a) CO conversion and (b) H2 conversion proles along the three
different FT congurations.

CFMR and FMFMR shifts the WGS reaction to the reactants side and
causes more CO2 consumption in both congurations. Moreover,
the CO2 yield decreases in CFMR owing to better heat transfer in
the uidized-bed reactor and the in situ water removal. The CO2
yield, as an undesired product, decreases considerably in CFMR
therefore it performs better than CR and FMFMR. CO2 is one of the
main air pollutants consequently the decrease in CO2 yield is
benecial for the environment. A considerable increase in the
gasoline yield and a remarkable decrease in the CO2 yield can be
counted as the superiority of CFMR to FMFMR. Fig. 6(b) illustrates
the 3D plot of CO2 yield as a function of pressure and reactor
length in CFMR. In CFMR, the in situ water removal shifts the WGS
reaction to the reactant side and CO2 is consumed. Furthermore,
lower temperature in the exothermic side of CFMR decreases the
reactions rates of WGS. These two factors decrease the CO2 yield
in CFMR more considerably than FMFMR and CR. Also, the CO2
yield decreases with pressure rising in CFMR. Therefore, CFMR

performs well at higher operating pressures owing to more CO2

consumption.
The water yield along three congurations is depicted in
Fig. 7(a). The highest water yield is achieved in CFMR. In CFMR and
FMFMR, the water yield increases along the rst reactor owing to
the in situ water removal via the H-SOD membrane layer which
increases the reaction rates of heavy hydrocarbons. The increase in
the reaction rates of heavy hydrocarbons leads to an increase in the
water production as a byproduct. The water permeation rate
through the H-SOD membrane layer is much lower than the water
production rate as a byproduct. It is worth mentioning that the
water yield increases along CFMR not only due to the in situ water
removal via the H-SOD membrane layer but also due to applying
the uidization concept. The water production rate in CFMR is
much higher than its permeation rate through the H-SOD
membrane layer (See Fig. 7(b)) and the in situ water removal
cannot satisfactorily decrease the water amount in the reaction
side. Fig. 7(b) illustrates the water permeation rate through the
H-SOD membrane layer along the rst reactors of CFMR and
FMFMR. The water permeation rate increases along the rst reactors of CFMR and FMFMR owing to an increase in the water partial
pressure in the reaction side. The water permeation rate along
CFMR is higher than FMFMR owing to applying the uidized-bed
reactor which enhances the FTS reactions and the water production rate (due to higher water partial pressure). The water permeation rate increases with increasing the partial pressure difference
between shell and tube sides. A partial pressure difference between
shell and tube sides of CFMR is higher than FMFMR.
Fig. 8(aeb) illustrates hydrogen and carbon monoxide conversions in CFMR in comparison with the ones in CR and FMFMR. The
CO and H2 conversions in CFMR and FMFMR are higher than the
ones in CR. Hydrogen and carbon monoxide conversions increase
owing to a water removal. The increase in H2 and CO conversions in
CFMR has the same trend as the ones in FMFMR. The rst reactors
(water-cooled reactor) of CFMR and FMFMR play the major role in
increasing the CO and H2 conversions. The highest conversion of
reactants is achieved in CFMR owing to the in situ water removal
from the rst reactor as well as the application of the uidized-bed
concept in the rst reactor. These observations can be justied by
the mentioned advantages of uidized-bed concept (SotudehGharebagh et al., 2007).

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

10

Production yield (gr/gr feed *100)

C +
5

C 3H8
6

C H
2

CH4
i-C4

C2H 4

n-C4
0

6
8
Length (m)

10

12

10

C +
Production yield (gr/gr feed *100)

C 3H8
6

C 2H 6
4

CH4
i-C

n-C
0

6
8
Length (m)

10

12

CFMR
CR

2
1.5
1
0.5
0

mole of C  atom in product

 100
mole of CO consumed

According to this gure, the CFMR conguration shows satisfying results relative to the others. CO2 declines considerably in this
conguration in conjunction with the C
5 increasing. Moreover,
methane is an undesired product which decreases considerably in
this novel conguration. The best results have been achieved by
CFMR, whether for desired products or undesired products.
7. Conclusions

FMFMR

2.5

Selectivity

3.5
3

Fig. 9 demonstrates the gas phase temperature prole along

CFMR, FMFMR and CR. Two temperature peaks are observed in the
zones close to the entrance of reactors. One peak is occurred in each
reactor owing to high exothermic reactions. One temperature jump
is clearly seen in the rst 0.5 m of the water-cooled reactor (the rst
reactor) and the second one arises in the rst 0.5 m of the gascooled reactor (the second reactor). The average temperatures in
CFMR and FMFMR are lower than the one in CR which can promote
the durability of catalyst activity. It is observed that the temperature control in the dual-type reactor is easier than the one in the
single type. The superior heat management capability and excellent
temperature control are the advantages of uidized-bed reactors.
Therefore, the average temperature in CFMR is lower than the one
in FMFMR owing to applying a uidized-bed reactor instead of
a xed-bed reactor.
There is a jump of temperature for all systems in the rst 0.5 m
of each reactor that is caused by high heat of reaction in FTS. For
simulation purposes, the maximum temperature for the Fe-HZSM5
catalyst to remain active is assumed to be 620 K (Marvast et al.,
2005). As shown in this gure, in the single xed-bed reactor
system, the risk of temperature runaway makes alert in closing to
hotspot. However, as evident in this gure, dual-type congurations have better temperature performance. Due to high
exothermic reactions, temperature jump occurs in the rst section
of reactor because the temperature runaway in most cases occurs at
a zone close to the inlet of the reactor.
Fig. 10(aeb) presents the prole of the component yield along
CFMR and FMFMR for FTS, respectively. According to Fig. 10(aeb),
the C
5 yield is the highest among hydrocarbon products. A
comparison of carbon molar selectivity of products between CR,
CFMR and FMFMR congurations is presented by Fig. 10(c). The
carbon molar selectivity of each component is dened as (Chang
et al., 2007):

C H

493

C5+

CH4

CO2

H2O

i-C4

n-C4 C2H4 C3H8 C2H6

Components
Fig. 10. (a) Components yield proles along the FMFMR conguration (b) components
yield proles along the CFMR conguration (c) comparison of components selectivity
in three reactor congurations.

In this study, a cascading uidized-bed membrane dual-type

reactor (CFMR) is proposed as an alternative conguration for
conventional tubular reactors for FTS in GTL technology. The
performance of CFMR is investigated and compared with the one of
FMFMR. CFMR conguration is fabricated as two subsequent
uidized-bed reactors where the PdeAg and H-SOD membrane
layers are assisted in both reactors to enhance the main products
yield. A desirable temperature prole is achieved in CFMR owing to
an excellent heat management in uidized-bed reactors. The
modeling results of CFMR conguration is compared with the
modeling results of FMFMR and CR pilot plant data. The modeling
results demonstrate that the gasoline yield increases remarkably
while the CO2 yield decreases considerably in CFMR compared with
FMFMR and CR mainly due to applying the uidization concept. The
modeling results show 5.3% increase in gasoline yield and 12%
decrease in CO2 yield in CFMR compared with the ones in FMFMR.
Therefore, the in situ water removal as well as applying the uidization concept can effectively improve the performance of CFMR
compared with FMFMR and propose it as more promising conguration for GTL technology.

494

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

Appendix

Nomenclature
Symbol

Unit

Denition

Ac
Ai
As
Ashell
ab
av
cPg
cPgt
cpH
cPs
ct
Di
Dij
Dim
Do
dp
hf
hi
ho
Ft
ft0
K
Kw
kgi
kbei
L
Mi
N
N H2 O

m2
m2
m2
m2
m2
m2$m3
J$mol1$k1
J$mol1$k1
J$mol1$k1
J$mol1$k1
mol$m3
m
m2$s1
m2$s1
m
m
W$m2$K1
W$m2$K1
W$m2$K1
mol$s1
mol$s1
W$m1$K1
W$m1$K1
m$s1
m$s1
m
g$mol1
[e]
mol s1

cross sectional area of each tube

inner area of each tube
lateral area of each tube
cross sectional area of shell
interface area between bubbles and emulsion phase
specic surface area of catalyst pellet
specic heat of the gas at constant pressure
specic heat of the gas inside the tube at constant pressure
specic heat of hydrogen at constant pressure
specic heat of the catalyst at constant pressure
total concentration
tube inside diameter
binary diffusion coefcient of component i in component j
diffusion coefcient of component i in the mixture
tube outside diameter
particle diameter
gas-catalyst heat transfer coefcient
heat transfer coefcient between uid phase and reactor wall
heat transfer coefcient between coolant stream and reactor wall
total molar ow rate in shell side
total molar ow rate in tube side
conductivity of uid phase
thermal conductivity of reactor wall
mass transfer coefcient between gas and solid phase for component i
mass transfer coefcient between bubble and emulsion phase for component i
length of reactor
molecular weight of component i
number of components
molar ow rate penetrate from membrane

t
PH

bar

tube side pressure

sh
PH

bar

shell side pressure

P
P0
QH2 O
R
Re
Ri
Ro
ri
rbi
Sci
T
Ts
Tshell
Tt
Ushell
Utube
ug
ub
Vr
yi
yis
yie
yib
z
Greek letters

mol m1$s1$Pa1/2
mol m1$s1$Pa1
mol$s1$m2$Pa1
J$mol1$K1
[e]
[m]
[m]
mol$kg1$s1
mol$kg1$s1
[e]
K
K
K
K
W$m2$K1
W$m2$K1
m$s1
m$s1
m3
mol$mol1
mol$mol1
mol$mol1
mol$mol1
m

permeability of hydrogen through PdeAg layer

pre-exponential factor of hydrogen permeability
permeance of water
universal gas constant
Reynolds number
inner radius of PdeAg layer
outer radius of PdeAg layer
reaction rate of component i
reaction rate of component i in bubble phase
Schmidt number of component i
bulk gas phase temperature
temperature of solid phase
temperature of coolant stream in rst reactor
temperature of coolant stream in second reactor
overall heat transfer coefcient between coolant and process streams
overall heat transfer coefcient between coolant and process streams
linear velocity of gas phase
rising bubble velocity
volume of reactor
mole fraction of component i in the uid phase
mole fraction of component i in the solid phase
mole fraction of component i in the emulsion phase
mole fraction of component i in the bubble phase
axial reactor coordinate

aH
DHf,i
DH298
d
3B
3s
3mf
g
m
nci
r
rB
re
rp
h

mol m1$s1$Pa0.5
J$mol1
J$mol1
[e]
[e]
[e]
[e]
[e]
kg$m1$s1
cm3$mol1
kg$m3
kg$m3
kg$m3
kg$m3
[e]

hydrogen permeation rate constant

enthalpy of formation of component i
enthalpy of reaction at 298 K
bubble phase fraction
void fraction of catalytic bed
void fraction of catalyst
void fraction of bed at minimum uidization
volume fraction of catalyst occupied by solid particles in bubble
viscosity of uid phase
critical volume of component i
density of uid phase
density of catalytic bed
density of emulsion phase
density of catalyst
catalyst effectiveness factor

M.R. Rahimpour et al. / Journal of Natural Gas Science and Engineering 3 (2011) 484e495

Superscripts and subscripts

f
in
out
s
sh
e
b
t
mf

References
Breck, D.W., 1974. Zeolite Molecular Sieves. John Wiley, New York.
Chang, J., Bai, L., Teng, B., Zhang, R., Yang, J., YuanYuan, H.W., Xu, X., Li, Y.W., 2007.
Kinetic modeling of FischereTropsch synthesis over Fe$Cu$K$SiO2 catalyst in
slurry phase reactor. Chem. Eng. Sci. 62, 4983e4991.
David, M.O., Gref, R., Nguyen, T.Q., Neel, J., 1991. Pervaporation-esterication
coupling: part II. Modelling of the inuence of different operation parameters.
J. Trans. Inst. Chem. Eng. 69 (A), 341e346.
Deshmukh, S.A.R.K., Laverman, J.A., Cents, A.H.G., Van Sint Annaland, M.,
Kuipers, J.A.M., 2005. Development of a membrane-assisted uidized bed
reactor. 1. Gas phase back-mixing and bubble-to-emulsion phase mass transfer
using tracer injection and ultrasound experiments. Ind. Eng. Chem. Res. 44,
5955e5959.
Dittmeyer, R., Hllein, V., Daub, K., 2001. Membrane reactors for hydrogenation and
dehydrogenation processes based on supported palladium. J. Molec. Catal. A:
Chem. 173, 135e184.
Dry, M.E., 1990. FischereTropsch synthesis over iron catalysts. Catal. Lett. 7,
241e252.
Dry Mark, E., 1999. FischereTropsch reactions and the environment. Appl. Catal. A:
Gen. 189, 185e190.
Eliason, S.A., Bartholomew, C.H., 1999. Reaction and deactivation kinetics for
FischereTropsch synthesis on unpromoted and potassium-promoted iron
catalysts. Appl. Catal. A: Gen. 186, 229e243.
FischereTropsch pilot plant of Research Institute of Petroleum Industry and
National Iranian Oil Company (RIPI-NIOC). Tehran 18745-4163. Iran, 2004.
Fernandes, F.A.N., Soares Jr., A.B., 2006. Methane steam reforming modeling in
a palladium membrane reactor. Fuel 85, 569e573.
Forghani, A.A., Elekaei, H., Rahimpour, M.R., 2009. Enhancement of gasoline
production in a novel hydrogen permselective membrane reactor in
FischereTropsch synthesis of GTL technology. Int. J. Hydrogen Energy 34,
3965e3976.
Gielens, F.C., Tong, H.D., Vorstman, M.A.G., Keurentjes, J.T.F., Keurentjes, J.T.F., 2007.
Measurement and modeling of hydrogen transport through high-ux Pd
membranes. J. Membr. Sci. 289, 15e25.
Khajavi, S., Jansen, J.C., Kapteijn, F., 2010. Application of a sodalite membrane
reactor in esterication coupling reaction and separation. Catal. Today 156,
132e139.
Kunii, D., Levenspiel, O., 1991. Fluidization Engineering. ButterwortheHeinemenn,
USA.
Marvast, M.A., Sohrabi, M., Zarrinpashneh, S., Baghmisheh, Gh, 2005. Fischere
Tropsch synthesis: modeling and performance study for Fe-HZSM5 bifunctional
catalyst. Chem. Eng. Technol. 28 (1), 78e86.

495

feed conditions
inlet conditions
outlet conditions
catalyst surface
shell side
emulsion phase
bubble phase
tube side
minimum uidization

Nakhaei Pour, A., Housaindokht, M.R., Tayyari, S.F., Zarkesh, J., Kamali Shahri, S.M.,
2011. Water-gas-shift kinetics over a Fe/Cu/La/Si catalyst in FischereTropsch
synthesis. Chem. Eng. Res. Des 89.
Nowicki, L., Ledakowicz, Sw, Bukur, D.B., 2001. Hydrocarbon selectivity model for
the slurry phase Fischer-Tropsch synthesis on precipitated iron catalysts. Chem.
Eng. Sci. 56, 1175e1180.
Peters, T.A., Stange, M., Klette, H., Bredesen, R., 2008. High pressure performance of
thin PdeAg/stainless steel composite membranes in water gas shift gas
mixtures; inuence of dilution. Mass transfer and surface effects on the
hydrogen ux. J. Membr. Sci. 316, 119e127.
Rahimpour, M.R., 2008. A two stage catalyst bed concept for conversion of carbon
dioxide into methanol. Fuel Process Technol. 89, 556e566.
Rahimpour, M.R., Alizadehhesari, K., 2008. A novel uidized-bed membrane dualtype reactor concept for methanol synthesis. Chem. Eng. Technol. 31, 1775e1789.
Rahimpour, M.R., Elekaei, H., 2009a. Optimization of a novel combination of xed
and uidizedbed hydrogen-permselective membrane reactors for Fischere
Tropsch synthesis in GTL technology. Chem. Eng. J. 152, 543e555.
Rahimpour, M.R., Elekaei, H., 2009b. A comparative study of combination of
FischereTropsch synthesis reactors with hydrogen-permselective membrane in
GTL technology. Fuel Process Technol. 90, 747e761.
Rahimpour, M.R., Bayat, M., Rahmani, F., 2010. Dynamic simulation of a cascade
uidized-bed membrane reactor in the presence of long term catalyst deactivation for methanol synthesis. Chem. Eng. Sci. 65, 4239e4249.
Rahimpour, M.R., Mirvakili, A., Paymooni, K., 2011. A novel water perm-selective
membrane dual type reactor concept for Fischer-Tropsch synthesis of GTL
technology. Energy 36 (2), 1223e1235.
Rohde, M.P., Schaub, G., Khajavi, S., Jansen, J.C., Kapteijn, F., 2008. FischereTropsch
synthesis with in situ H2O removal e directions of membrane development.
Microp. Mesop. Mat 115, 123e136.
Schulz, H., Schaub, G., Claeys, M., Riedel, T., 1999. Transient initial kinetic regimes of
FischereTropsch synthesis. Appl. Catal. A: Gen. 186, 215e227.
Sotudeh-Gharebagh, R., Chaouki, J., Sauriol, P., 2007. An experimental study of
non-premixed combustion in a turbulent uidized-bed reactor. Fuel Process.
Technol. 88, 847e858.
Takayuki, T., Kenji, Y., 2008. Important roles of Fischere Tropsch synfuels in the
global energy future. Energy Policy 36, 2773e2784.
Unruh, D., Rohde, M.P., Schaub, G., 2004. Membrane application in FischereTropsch
synthesis reactors: overview of concepts. Stud. Surf. Sci. Catal. 153, 91.
van der Laan, G.P., Kinetics, Selectivity and Scale up of the Fischer-Tropsch
Synthesis, Thesis, University of Groningen 1999.
van der Laan, G.P., Beenackers, A.A.C.M., 2000. Intrinsic kinetics of the gasesolid
FischereTropsch and water gas shift reactions over a precipitated iron catalyst.
Appl. Catal. A: Gen. 193, 39e53.