June 2011, Volume 2, No.

3
International Journal of Chemical and Environmental Engineering
175



Enhancement of methanol synthesis in a
Water vapor-perm selective membrane reactor

M. Farsi
a
, A. Jahanmiri
a
*
a
School of Chemical and Petroleum Engineering, Department of Chemical Engineering,
Shiraz University, Shiraz, Iran * jahanmir@shirazu.ac.ir

Abstract
In this work a membrane reactor is proposed for water vapor removal from reaction zone in the methanol production process to
overcome thermodynamic equilibrium limitations of the methanol synthesis reactions. A steady state heterogeneous one-dimensional
mathematical model is developed for simulation of the proposed catalytic fixed bed membrane reactor. To verify the accuracy of the
considered model and assumptions, simulation results of the conventional reactor is compared with the available industrial plant data.
The membrane reactor benefits are the higher methanol production rate, higher quality of outlet product and consequently lower cost
in the product purification stage. This configuration has enhanced the methanol yield about 5.7% than industrial reactor. Experimental
proof-of-concept is needed to establish the safe operation of the proposed configuration.
Keywords: Methanol, Composite membrane, Heterogeneous model, Membrane reactor.
1. Introduction
Methanol as the simplest aliphatic alcohols is one of
the most important industrial petrochemical products that
used as solvent and produce chemical intermediate. It is
an alternate fuel for internal combustion and other
engines, either in combination with gasoline or directly.
Methanol is a colorless liquid, completely miscible with
water that is very hydroscopic. Liquid methanol has a
higher energy density than gas fuels. It can be produced
from different sources like natural gas, coal, biomass and
petroleum. Commercially, it is produced from syngas in a
tubular packed bed reactor. A conventional type of
methanol reactor includes many tubes that have been
surrounded with circulating boiling water as coolant to
remove the heat of reactions from reaction zone. Due to
the thermodynamic equilibrium limitations of the
methanol synthesis reactions, methanol conversion in the
conventional methanol reactors is low. Thus, most of the
syngas should be circulated in the process. There are
several researches on methanol process in the literature.
Lange presented a good review of methanol synthesis
technologies [1]. Jahanmiri and Eslamloueyan modeled a
conventional methanol reactor and showed that the
difference between one and two-dimensional simulation
is negligible [2]. Graaf et al. modeled a low pressure
methanol synthesis reactor [3]. They showed that
commercial size of the catalyst particles exhibit
intraparticle diffusion limitations. Kordabadi and
Jahanmiri optimized methanol synthesis reactor to
enhance overall production at steady state and dynamic
conditions [4]. This optimization approach enhanced a
2.9% additional yield in methanol reactor. Shahrokhi and
Baghmisheh investigated dynamic behavior and
controllability of the low pressure methanol synthesis
reactor [5]. To increase the reactor yield, they developed
an optimizer which can be coupled with the control
system. Recently, a dual-type reactor system instead of a
conventional methanol reactor was proposed by
Rahimpour et al. [6, 7]. The dual-type methanol reactor is
an advanced technology for converting natural gas to
methanol at low cost and large quantities. The main
factors in the production rate of industrial methanol
reactor are thermodynamic equilibrium limitations and
catalyst deactivation. Many efforts have been considered
to increase methanol conversion by removal of products
over a permselective membrane. The application of
membrane reactors has attracted much attention in the
recent year [8, 9]. Simultaneous occurrence of reaction
and separation leads to lower cost of the separation
system compared to conventional reactors. In addition, by
removing some product components from reaction zone
and transfer of some reactant to the reaction zone in a
membrane reactor, thermodynamic equilibrium
limitations can be overcome towards higher conversion.
Rahimpour et al. improved methanol production in an
industrial methanol reactor by applying a Pd based
hydrogen-permselective membrane to the conventional
reactor [10]. In this configuration, hydrogen permeates
from membrane tubes to the reaction zone.
The main objective of this work is modeling and
simulation of the proposed membrane reactor for
methanol synthesis and performance comparison of the
proposed reactor with a conventional reactor at steady
Enhancement of methanol synthesis in a water vapor-perm selective membrane reactor




state condition. The proposed reactor is modeled
heterogeneously and numerical simulation utilized to
compare the results of the membrane reactor with
conventional reactor at the same process conditions. The
steady state simulation results show that this novel
configuration in the industrial single type methanol
reactor improves methanol production rate.

2. Process description
2.1 Conventional methanol reactor
Figure 1 shows the schematic of a conventional
methanol synthesis reactor. The conventional methanol
reactor is basically a vertical shell and tube heat
exchanger that tubes are packed with catalyst particles
and surrounded by the boiling water. The heat of
reactions is transferred to the boiling water and steam is
produced.


Figure 1, Schematic of a conventional methanol reactor

Typical operating conditions of the methanol reactor
are 543 K and 80 bar. The base case specifications of
studied reactor, catalyst and feed are tabulated in Table 1.

Table 1, The base case specifications of reactor, catalyst and feed
Feed composition
H
2
65.9
CO 4.6
CO
2
9.4
N
2
9.3
H
2
O 0.009
CH3OH 0.5
CH
4
10.26
Total molar flow per tube [mol s
-1
] 0.64
Inlet temperature [K] 503
Inlet pressure [bar] 76.98
Reactor characteristics
Tube number 2962
Length of reactor [m] 7.022
Tube inner diameter [m] 3.810
-2

Tube outer diameter [m] 4.310
-2

Bed void fraction 0.39
2.2 Membrane reactor
As a solution to overcome the thermodynamic
limitations, methanol reactor can be devised by
permselective membrane layer for H
2
O removal that
shifts the equilibrium in the favorable direction. Figure 2
shows the schematic diagram of the proposed membrane
reactor for methanol synthesis. This system consists of
two concentric pipes that the inner tube wall is water
vapor-permselective membrane. Between the second and
inner tube, the methanol synthesis reactions take place.
The second tube has been surrounded by the boiling water
and the heat of reactions is transferred to the water and
steam produced.













Figure 2, Schematic diagram of a the proposed membrane reactor

Iliuta et al. studied H
2
O removal during DME
synthesis using a composite membrane from a gaseous
mixture contains of methanol, H
2
, CO, CO
2
and DME in a
packed bed catalytic reactor [11]. In the proposed
configuration, the wall of tubes are constructed from a
water vapor-permselective membrane. Partial pressure
difference of water vapor between inner tube and and
reaction zone permits diffusion of water through the
composite based membrane tubes.

3. Process modeling
The reactions of methanol synthesis are mainly, CO
and CO
2
hydrogenation and reverse watergas shift
reaction.

CO + 2H
2
CH
3
OH (1)
CO
2
+ 3H
2
CH
3
OH + H
2
O (2)
CO
2
+ H
2
CO + H
2
O (3)

In this work, rate expressions have been selected from
Graaf et al. work [12]. The rate equations combined with
the equilibrium rate constants and provide enough
information about kinetics of methanol synthesis. A one
dimensional steady state heterogeneous model, based on
mass and energy conservation laws, has been developed
for simulation of the proposed membrane reactor. In this
model the following assumptions has been considered:
- Radial dispersion of mass and energy is negligible.
- The gas mixture is an ideal gas.
- Due to high gas velocity, axial diffusion of mass and
heat are negligible.
- Plug flow pattern in reaction tube is considered.
- The chemical reactions are assumed to take place only
on the catalyst surface.

MeOH
Water
Vapor
To Distillation
Feed
H
2
O permselective side
Saturated water
Reaction zone

Feed
Energy stream
Mass stream
176
Enhancement of methanol synthesis in a water vapor-perm selective membrane reactor




Subject to these assumptions, mass and energy balances
for the gas phase in the reaction zone are expressed by:

( )
( ) 0 ) (
1 , 2 ,
, 2
= +
i i
c
i w g
i
s
i gi t v
g
i
c
P P
A
y y k c a
dz
y F d
A
1
t
(1)
( )
0 ) (
) ( ) (
1
0
1 3 2 3 2
2
1 2 2 1
1
2 2
2 2
=
+

dT C F T T U
A
D
T T U
A
D
T T h a
dz
T F d
A
C
T
T
p
out g
c
g g
c
g s
f v
g
c
g
p
t
t
(2)

Lee and et al. proposed a composite membrane with
permeability of 1.1410
-7
mol m
-2
s
-1
Pa
-1
and a water-
methanol selectivity of 8.4 at a permeation temperature of
250C [14]. Mass and energy balances for the solid phase
are expressed by:

0 ) (
2 , 2 ,
= +
b i
s
i
g
i gi t v
r y y k c a p n
(3)
0 ) ( ) (
1
, 2 2
= A +

N
i
i f i b
s g
f v
H r T T h a n p

(4)

The pressure drop through the catalytic bed is
calculated based on the Ergun equation [13]. The related
equation for tubular reactors is:

( ) ( )
2
c
2
3
p s c
3
2
2
p
2
s
A
Q

1
d
1.75
A
Q

1
d
150
dz
dP
+

=





(5)

Mass and energy balance equations for water vapor
permselective side (inner tube) are as follows:

( )
( )
1 , 2 , ,
1

i i i w
g
i
P P
dz
y F d
= t

(6)
( )
( ) dT C F T T U D
dz
T F d
C
T
T
p
out g g
g
g
p

+ =

2
0
) (
1 1 2 2 1 1
1 1
t
(7)

To complete the simulation, auxiliary correlations
should be added to the model. In the heterogeneous
model, heat and mass transfer coefficients between gas
and solid phases, physical properties of chemical species
and overall heat transfer coefficient should be estimated
from proper correlations.

4. Numerical solution
The governing equations combined with the kinetic
expressions and auxiliary correlations form a set of
nonlinear ordinary differential equations as an initial
value problem. This set of equations has been solved with
4th order Runge-Kutta method. The results of node k are
to be used as inlet conditions for the next node (k+1). At
the end of this procedure it is possible to plot the
concentration of components and temperature profiles
versus the length of reactor.
5. Result and discussion
In this section the effect of membrane on key
parameters of methanol reactor such as methanol, CO,
CO
2
and H
2
O mole flow rates has been considered. The
model of methanol synthesis side is validated against
industrial methanol reactor for tabulated design
specifications in Table 1 [15]. The comparison between
simulation results and plant data for industrial case is
shown in Table 3. It is shown that the observed plant data
has a good agreement with simulation data.

Table 3, Comparison between simulation results and plant data
Inlet Reactor Outlet
Composition Simulation Plant date
CO
2
2.048 1.055 1.032
CO 3.118 0.978 0.932
H
2
77.87 75.8 75.12
H
2
O 0.008 1.151 1.249
CH
3
OH 0.407 4.17 4.008

CO
2
and CO mole flow rate profiles are shown in
Figure 3(a) and (b). This figure shows that in the second
half of the conventional reactor, the rate of CO
2

hydrogeneation reaction approaches to its equilibrium. It
is observed from synthesis methanol reactions that water
vapor removal from reaction zone shifts CO
2

hydrogenation reaction to the higher CO
2
consumption
which results an greater equilibrium shift and methanol
production. Also, Water vapor removal shifts reverse
water gas shift reaction to the right side and higher CO
can be produced. Increasing CO concentration shifts CO
hydrogenation reaction to the right side and higher
methanol production is attainable. Thus, one of the main
advantages of proposed structure is higher CO
2

conversion to methanol.
0 1 2 3 4 5 6 7
0.04
0.045
0.05
0.055
0.06
Length (m)

C
O
2

m
o
l
e

f
l
o
w

r
a
t
e

(
m
o
l

s
-
1
)


Conventional reactor
Membrane reactor
(a)

Figure 3(a), CO
2
mole flow rate profiles
The outlet CO
2
mole flow rate from proposed and
conventional reactor for base case are 0.041 and 0.045
mol s
-1
, respectively. The CO
2
conversion in the
membrane reactor has been improved about 9% than
177
Enhancement of methanol synthesis in a water vapor-perm selective membrane reactor




conventional reactor. Simultaneous occurrence of CO
production and consumption results a same mole flow
rate profile for CO in the proposed and conventional
reactors.
0 1 2 3 4 5 6 7
0.01
0.015
0.02
0.025
0.03
Length (m)

C
O

m
o
l

f
l
o
w

r
a
t
e

(
m
o
l

s
-
1
)


Conventional reactor
Membrane reactor

Figure 3(b), CO mole flow rate profiles

In Figure 4, methanol mole flow rate in the
conventional reactor and proposed configuration are
shown. It is observed that the methanol mole flow rate in
the proposed configuration is higher than conventional
reactor. This figure shows that in the second half of the
conventional reactor, the rate of methanol synthesis
reactions has approached to equilibrium point and the
membrane layer in this section is useful. The outlet
methanol mole flow rate from proposed configuration and
conventional reactor for base case obtained about 0.37
and 0.35 mol s
-1
, respectively.

0 1 2 3 4 5 6 7
0
0.01
0.02
0.03
0.04
Length (m)

M
e
t
h
a
n
o
l

m
o
l
e

f
l
o
w

r
a
t
e

(
m
o
l

s
-
1
)


Conventional reactor
Membrane reactor

Figure 4, MeOH mole flow rate profiles

The water vapor mole flow rate in the reaction zone of
the proposed and conventional reactors are shown in
Figure 5. According to Le Chtelier's principle,
decreasing water vapor concentration in the methanol
synthesis reactions leads to shift the CO
2
hydrogenation
and reverse water gas shift reactions to the right direction
and higher methanol is produced. This figure shows that
the water vapor mole flow rate in the second half of the
membrane reactor decreases due to higher water vapor
removal than water vapor production. While there is a
difference between water vapor partial pressure in the
exothermic and permeation side, vapor can penetrate from
reaction zone into the permeation side through composite
membrane layer.
0 1 2 3 4 5 6 7
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
Length (m)

H
2
O

m
o
l

f
l
o
w

r
a
t
e

(
m
o
l

s
-
1
)


Conventional reactor
Membrane reactor

Figure 5, Water vapor mole flow rate profiles

4. Conclusion
In this study, a novel composite membrane reactor for
mrthanol production were proposed and molded
heterogeneously at steady state condition. The results of
mathematical simulation for an industrial case were
compared with the plant data and the accuracy of the
model and considered assumptions was proved. The
results of the steady state simulation showed that
proposed membrane reactor enhances outlet methanol
mole flow rate about 5.7% than conventional reactor.
Methanol production could be promoted beyond
thermodynamic equilibrium by permeation of water vapor
from reaction side as a product. In general, the
performance of methanol reactor system improved when a
membrane were used in a conventional-type methanol
reactor and the obtained results suggest that this
configuration could be feasible and beneficial.


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