CATALYSIS, KINETICS AND REACTORS

Chinese Journal of Chemical Engineering, 17(4) 630ü634 (2009)

Experimental Study and Modeling of an Adiabatic Fixed-bed Reactor

for Methanol Dehydration to Dimethyl Ether

M. Fazlollahnejad1, M. Taghizadeh1,*, A. Eliassi2 and G. Bakeri3

1
Department of Chemical Engineering, Babol University of Technology, 4714871167 Babol, Iran
2
Chemical Industries Research Department, Iranian Research Organization for Science and Technology (IROST),
Tehran, Iran
3
Catalyst Research Group, Petrochemical Research and Technology Company, National Petrochemical Company,
Tehran, Iran

Abstract One-dimensional heterogeneous plug flow model was employed to model an adiabatic fixed-bed reactor
for the catalytic dehydration of methanol to dimethyl ether. Longitudinal temperature and conversion profiles pre-
dicted by this model were compared to those experimentally measured in a bench scale reactor. The reactor was
packed with 1.5 mm Ȗ-Al2O3 pellets as dehydration catalyst and operated in a temperature range of 543603 K at an
atmospheric pressure. Also, the effects of weight hourly space velocity (WHSV) and temperature on methanol con-
version were investigated. According to the results, the maximum conversion is obtained at 603.15 K with WHSV
of 72.87 hˉ1.
Keywords methanol, dimethyl ether, modeling, fixed-bed reactor

1 INTRODUCTION In our previous work, the effects of temperature

Dimethyl ether (DME), as a multi-source and
multi-purpose product, has received growing attention
considering global environment pollution and energy
supply problem today. DME can be produced from
syngas, which is from natural gas, coal or biomass.
DME has wide applications, such as liquefied petro-
leum gas (LPG) substitute, transportation fuel, pro-
pellant, chemical feedstock and fuel cell fuel [1]. It has
been identified as a potential diesel and cooking fuel
due to its many excellent characteristics. It has an
oxygen concentration of 34.78% and can be burned
without soot emission, while for traditional diesel fu-
els the simultaneous control of NOx and soot emis-
sions cannot be expected. It has a boiling point of
 25°C, which is 20°C higher than LPG and can be
liquified at 0.54 MPa (20°C). Therefore, based on the
matured technology of LPG application, there is no
any problem for the storage, transportation and usage
of DME [2].
Two processes are used for DME production, in-
direct [38] and direct processes [911]. In indirect
process, methanol is converted to DME in a catalytic
dehydration reactor over a solid-acid catalyst by the
following reaction:
2CH3OH o CH3OCH3  H 2 O
In the second process (direct process), a synthesis gas
(a mixture of H2 and CO gases) is used as the feed of
the process. In this process, the synthesis gas is pri-
marily converted to methanol and then it is followed
by methanol dehydration to DME. The net reaction is
as follows:
3CO  3H 2 o CH3OCH3  CO2
and feed composition on catalytic dehydration of
methanol to dimethyl ether over gamma-alumina were
studied and the results showed that the conversion of
methanol strongly depended on the operating tem-
perature in the reactor. Also, conversion of pure
methanol and mixture of methanol and water versus
time were studied and the effect of water on deactiva-
tion of the catalyst was investigated [12]. In this work,
acidic gamma-alumina has been used as the catalyst
for the dehydration of methanol to DME. Also, we
reached the optimum WHSV that gives us maximum
conversion of methanol in three inlet temperatures of
methanol gas.
2 EXPERIMENTAL
2.1 Apparatus
The schematic diagram of the used set up is
shown in Fig. 1. Pure methanol was pumped from
methanol storage tank at different rates from 44 g·h 1
ˉ
ˉ1
up to 1021 g·h to an evaporator and then to a supper
heater before entering the reactor. The superheated
methanol was sent to an adiabatic fixed-bed reactor.
The axial reactor temperature at any point of the cata-
lyst bed was measurable via a thermo-well using a
thermocouple. The reactor outlet products were passed
through an air cooler and a double pipe heat exchanger
to cool down to the ambient temperature. The cooled
products were sent to a gas-liquid separator. A back
pressure regulator (BP-LF690, pressure Tech2000, Eng-
land) was placed on this separator to regulate the system
pressure. Reaction products were analyzed by a gas
chromatograph (Varian CP-3800) equipped with ther-
mal conductivity detector (TCD) and flame ionization

Received 2009-01-30, accepted 2009-05-25.

* To whom correspondence should be addressed. E-mail: taghizadehfr@yahoo.com
 Chin. J. Chem. Eng., Vol. 17, No. 4, August 2009 631

d p / d tube 0.0015 / 0.0127  0.1 , and the second

Ltube / d tube 0.25 / 0.0127  50 [13]. The mass and
energy balance equations for the bulk gas phase can
be written as follows:
dC b
u i K0 vi rM T b , Cib  U B (1)
dz
dT b
Figure 1 A schematic diagram of the experimental appa-
ratus for catalytic production of DME from methanol
uUcp K0 rM T b , Cib   'H r  U B (2)
dz
Where, Ci is concentration in fluid phase, u is superfi-
cial velocity, ǻHr is heat of reaction, vi is stoichiomet-
ric coefficient, ȡ is gas phase density, ȡB is catalyst
bed density, cp is specific heat of fluid, and z is reactor
longitudinal coordinate. In these equations the reac-
1ünitrogen cylinder; 2ümethanol feed tank; 3üdosing pump;
4üflow meter; 5ümixer; 6üevaporator; 7üpreheater; 8ü
adiabatic fixed-bed reactor; 9üair cooler; 10ücondenser;
11üliquid-gas separator; 12üback pressure regulator
tion rate equation rM T b , Cib  and its kinetic parame-
ters that expressed by following equations were got
from Bercic and Levec [3]:

rM T , Ci 
2
ks K M  CM2  CW CE / K  (3)
1  2 
4
detector (FID). Also, the remaining methanol in the exit K M CM  K W C W
products was measured and the methanol conversion
was estimated with comparison to the entrance methanol. ks 5.35 u 1013 exp  17280 / T  (4)

2.2 Chemicals KM 5.39 u 104 exp  8487 / T  (5)

Acidic gamma-alumina as dehydration catalyst
was prepared from Engelhard (Netherland). Methanol
was obtained from Iran Petrochemical Company (IPC).
Characterization of the used catalyst and methanol and
the operational conditions are reported in Table 1.
3 DEVELOPMENT OF REACTOR MODEL
KW 8.47 u 102 exp  5070 / T  (6)
Where, Ș0 (effectiveness factor) that is expressed by
Eq. (7) is supposed to be 1, because catalyst particles
are so small that concentration and temperature varia-
tions in particles can be neglected. Thus, this factor
does not have any important effect on temperature of
reactor and conversion of methanol.
V 1 ³ rM T , Ci  dV
3.1 Model assumptions K0 v
(7)
rM T b , Cib 
The mathematical model for adiabatic fixed-bed Equations (1) and (2) are subject to the initial conditions
reactor is based on the following assumptions: (1) The that specify the feed composition and temperature:
feed current in reactor is plug flow and the gas phase
is assumed to behave ideally; (2) The reactor is oper- Cib Cib,0 at z 0
ated at steady state conditions; (3) Heat transfer from b
(8)
reactor to environment is negligible; (4) The reactor is T T0b at z 0
in isobaric operation; (5) Diffusion limitation in cata-
lyst pores is negligible; (6) Radial gradients of con- 3.3 Numerical method
centration and temperature are absent.
The numerical integration of the reactor mass and
3.2 Mathematical model heat balances [Eqs. (1) and (2)] was performed by
using a fourth-order Runge Kutta while the surface
A one-dimensional and heterogeneous ideal plug conditions (CS, TS) in the heterogeneous model were
model is chosen in this work to simulate the adiabatic determined by a Newton iteration method. In these
fixed-bed reactor. The dispersion model in this work calculations, ȡ, ǻHr, u, and cp were considered as a
cannot be used because of two reasons: firstly function of inlet temperature.

Table 1 Properties of catalyst and operating conditions

Catalyst particle Catalyst bed Catalyst bed Catalyst bed Reactor Reactor Inlet Absolute
Catalyst
diameter/mm height/cm porosity density/ kg·m 3 diameter/m height/cm temperature/K pressure/Pa
ˉ

engelhard Ȗ-Al2O3 1.5 25 0.6 693.96 0.01905 90 543.15603.15 101325

632 Chin. J. Chem. Eng., Vol. 17, No. 4, August 2009
4 RESULTS AND DISCUSSION
4.1 Model validation, prediction and experiments
Model results and the obtained experimental data
are shown in Figs. 27. In Figs. 24 variations of
temperature versus reactor length are shown. When
the inlet temperature of the feed is increased from 543
to 603 K, the reaction rate is increased; therefore, the
reaction is reached to its equilibrium state faster. Ac-
cording to Figs. 24 the experimental data are well
predicted by the model. In Figs. 57 conversion
versus reactor length are shown. It can be observed
that conversion is increased by increasing the inlet
feed temperature.
Figure 2 The simulated reactor temperature versus reac-
tor length (p 101325 Pa and WHSV 45.33 hˉ1)
üü Eq. (2);Ƶexp. data
Figure 3 The simulated reactor temperature versus reac-
tor length (p 101325 Pa and WHSV 63.47 hˉ1)
üü Eq. (2);Ƶexp. data
Figure 4 The simulated reactor temperature versus reac-
tor length (p 101325 Pa and WHSV 79.8 hˉ1)
üü Eq. (2);Ƶexp. data
Figure 5 Methanol conversion versus reactor length (Inlet
feed temperature is 543 K, p 101325 Pa and WHSV 45.3 hˉ1)
üü Eq. (1);Ƶexp.
Figure 6 Methanol conversion versus reactor length (Inlet
feed temperature is 573 K, p 101325 Pa and WHSV 63.5 hˉ1)
üü Eq. (1);Ƶexp.
Figure 7 Methanol conversion versus reactor length (Inlet
feed temperature is 603 K, p 101325 Pa and WHSV 79.8 hˉ1)
üü Eq. (1);Ƶexp.
According to the obtained results, the best inlet
feed temperature is 573 K. The maximum conversion
at this condition was 95% with WHSV of 48.85 h 1.
ˉ
Our experiments showed that at higher temperatures,
methanol conversion increases negligibly, but the se-
lectivity respect to DME decreases.
4.2 Effect of WHSV on methanol conversion
The influence of WHSV on the conversion of
methanol at three different inlet feed temperatures
(543603 K) is shown in Fig. 8. At a constant inlet
temperature, methanol conversion increases with de-
creasing WHSV, however, when the WHSV is less than
36.4 h 1, the methanol conversion does not increase
ˉ
with decreasing WHSV. For instance, XMeOH increases
from 48.9% to 93.00% at 543 K when WHSV de-
creases from 100.4 h 1 to 36.4 h 1. Increasing the
ˉ ˉ
 Chin. J. Chem. Eng., Vol. 17, No. 4, August 2009 633

Table 2 Experimental data for conversion of methanol at different inlet temperatures and atmospheric pressure

Experiment mMeOH/ T 543.15 K T 573.15 K T 603.15 K

No. g·h 1
ˉ Mass of used WHSV/ MeOH Mass of used WHSV/ MeOH Mass of used WHSV/ MeOH
catalyst/g h 1 Conv./% catalyst/g h 1 Conv./% catalyst/g h 1 Conv./%
ˉ ˉ ˉ

1 44.042 1.16 27.35 64 0.805 54.71 85.8 0.805 54.71 70

2 75.6966 3.22 31.34 66 1.16 94.03 73.8 0.805 94.03 80
3 163.58 3.22 50.8 52 2.415 67.74 75 1.61 67.74 92.2
4 275.2616 12.88 34.2 85 9.66 42.74 89 4.83 56.99 83.4
5 469.298 12.88 36.44 93 9.66 48.58 95 6.44 72.87 95.8
6 485.2068 4.83 100.45 48.9 4.03 120.55 73 3.22 150.68 76
7 1021.832 25.76 43.6 82 16.1 63.47 83 12.88 79.83 84

with WHSV of 48.58 h 1, and 95.8% at 603.15 K with

ˉ

WHSV of 72.87 h 1. Therefore, according to the ob-

ˉ

tained results, the maximum conversion is obtained at

603.15 K with WHSV of 72.87 h 1.
ˉ

ACKNOWLEDGEMENTS

This work was partially supported by National

Figure 8 Experimental data of methanol conversion versus
WHSV at three different inlet feed temperatures (Dashed
lines are trend of changes)
Tinlet/K:ƽ543;Ƶ573;Ʒ603.15
WHSV will cause an increase in the gas velocity,
which promotes mass transfer but leads to a decrease
in the contact time of reactant species [14]. As a result,
the conversion of methanol increases with decreasing
Petrochemical Research and Technology Company of
Iran, NPC-RT. The authors specially thank to the
Chemical Industries Research Department of Iranian
Research Organization for Science and Technology
(IROST) for their generous assistance with this project.
NOMENCLATURE
Ci concentration in fluid phase, kmol·m 3
ˉ

WHSV until it reaches a maximum value. For the cp specific heat of fluid, kJ·kg 1·K 1
ˉ ˉ

lower WHSV, although the decrease in the flow rate ǻHr heat of reaction, kJ·kmol
ˉ1

causes to increase the contact time, but in this case the K thermodynamic equilibrium constant
mass of catalyst is too low to increase the conversion. Ki adsorption constant, m3·kmol 1
ˉ

Also, in higher WHSV the operative temperature reaction rate constant, kmol·kg 1·h 1
ˉ ˉ
ks
ˉ1
should be increased to have better conversion of Mi molecular weight, kg·kmol
p pressure, Pa
methanol (Table 2).
gas constant, Pa·m3·kmol 1·K 1
ˉ ˉ
R
As it is reported in Table 2, 7 runs are performed. rM rate of methanol disappearance, kmol·kg 1·h 1
ˉ ˉ

A constant mass flow rate of methanol as a feed is T temperature, K

used at three inlet temperatures for each run. The u superficial velocity, m·h 1
ˉ

maximum conversion of methanol is 93% at 543.15 K V particle volume, m 3

with WHSV of 36.44 h 1, 95% at 573.15 K with

ˉ
z reactor longitudinal coordinate, m
ˉ1
WHSV of 48.58 h , and 95.8% at 603.15 K with Ș effectiveness factor
WHSV of 72.87 h 1.
ˉ
Ȟi stoichiometric coefficient
gas-phase density, kg·m 3
ˉ
ȡ
catalyst bed density, kg·m 3
ˉ
ȡB
5 CONCLUSIONS Subscripts
b bulk conditions
A one-dimensional heterogeneous model is de- i ith component (methanol, DME, water)
M methanol
veloped to simulate the adiabatic fixed-bed reactor.
s surface conditions
The axial temperature and conversion profiles in an W water
adiabatic fixed-bed reactor for DME production are 0 inlet conditions
well predicted by the proposed model. Also, the effect
of WHSV on methanol conversion in different inlet
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