Fuel 87 (2008) 29672971

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Fuel
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Effects of temperature and feed composition on catalytic dehydration of methanol

to dimethyl ether over c-alumina
Freshteh Raoof a, Majid Taghizadeh a, Ali Eliassi b,*, Fereydoon Yaripour c
a

Chemical Engineering Department, Babol University of Technology, Babol, Iran

Chemical Industries Research Department, Iranian Research Organization for Science and Technology (IROST), No. 71, Forsat Street, Enghelab Avenue, Tehran, Iran
c
Catalysis Research Group, Petrochemical Research & Technology Company NPC, Tehran, Iran
b

a r t i c l e

i n f o

Article history:
Received 29 September 2007
Received in revised form 17 March 2008
Accepted 18 March 2008
Available online 22 April 2008
Keywords:
Clean fuel
Dimethyl ether
Methanol dehydration
Catalyst deactivation

a b s t r a c t
Catalytic dehydration of methanol to dimethyl ether (DME) is performed in an adiabatic xed bed heterogeneous reactor by using acidic c-alumina. By changing the mean average temperature of the catalyst
bed (or operating temperature of the reactor) from 233 up to 303 C, changes in methanol conversion
were monitored. The results showed that the conversion of methanol strongly depended on the reactor
operating temperature. Also, conversion of pure methanol and mixture of methanol and water versus
time were studied and the effect of water on deactivation of the catalyst was investigated. The results
revealed that when pure methanol was used as the process feed, the catalyst deactivation occurred very
slowly. But, by adding water to the feed methanol, the deactivation of the c-alumina was increased very
rapidly; so much that, by increasing water content to 20 weight percent by weight, the catalyst lost its
activity by about 12.5 folds more than in the process with pure methanol. Finally, a temperature dependent model developed to predict pure methanol conversion to DME correlates reasonably well with
experimental data.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Dimethyl ether (DME) with the chemical formula of CH3OCH3
is the simplest ether for preparation of some chemicals such as dimethyl sulfate and high-value oxygenated compounds. In addition,
it has been used as an aerosol propellant to replace chlorouoro
carbons which can destroy the ozone layer of the upper atmosphere. It is a colorless gaseous with an ethereal smell. Unlike
methane, DME does not require an odorant because it has a sweet
ether-like odor. Dimethyl ether is also a clean fuel alternative to
liquied petroleum gas (LPG), liquied natural gas (LNG), diesel
and gasoline [1,2].
DME can be made from natural gas, coal, or biomass. This fuel
burns with a visible blue ame and is non-peroxide forming in
the pure state or in aerosol formulations. DME is a volatile organic
compound, but is non-carcinogenic, non-teratogenic, non-mutagenic, and non-toxic [1]. Its physical and chemical properties in
comparison with diesel can be summarized as follows:
 The low heat value of DME is only 64.7% of that of diesel, therefore a larger amount of fuel supply is needed to deliver the same
power output for the engine.
* Corresponding author. Tel./fax: +98 21 88838324.
E-mail address: alieliassi@yahoo.com (A. Eliassi).
0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.03.025

 Cetane number of DME is higher and its auto ignition temperature is lower than that of diesel.
 DME has only got CH and CO bonds, but no CC bond and it
contains about 34.8% oxygen, therefore the combustion products such as carbon monoxide and unburned hydrocarbon emissions are lower than those of natural gas.
 The latent heat of evaporation of DME is much higher than that
of diesel, so it will be benecial to the NOx reduction due to the
larger temperature drop of the mixture in the cylinder.
 DMEs boiling point is 24.9 C and it must be pressurized to
keep it in liquid state under ambient conditions.
Two processes are used for DME production, indirect [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
2CH3 OH $ CH3 OCH3 H2 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 primarily converted to methanol and
then it is followed by methanol dehydration to DME. The net reaction is as follows:
3CO 3H2 $ CH3 OCH3 CO2

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F. Raoof et al. / Fuel 87 (2008) 29672971

2. Experimental

son to the entrance methanol, the methanol conversion was

estimated. BET surface area, pore volume and pore radius of the
catalysts were measured by N2 adsorptiondesorption isotherm
at liquid nitrogen temperature using Autosorb-3B (Quantachrome,
USA). Experiments were carried out at average reactor bed temperature (operating temperatures) ranging from 233 to 303 C at constant atmospheric pressure. The operating conditions as well as
some of the characteristic of the system are reported in Table 1.
For study of the adiabatic status of the applied reactor, an
experiment was performed as a blank run (without any reaction)
and the temperature prole of the bed was measured by using
thermocouple and thermowell. The result of this experiment is
shown in Fig. 2. According to this gure, the performance of the
reactor as an adiabatic reactor is reasonable. Therefore, the adiabatic assumption for the used reactor is reasonable. This experiment was performed by passing air through to the catalyst bed.

2.1. Apparatus

2.2. Chemicals

A schematic diagram of the laboratory-scaled system employed

in this study is shown in Fig. 1. Pure methanol was pumped from
methanol storage tank at a rate of 0.121 L/h to an evaporator and
then to a supperheater before entering the reactor. The superheated methanol was sent to an adiabatic xed bed reactor. The
length of catalyst bed could be adjusted for a given experiment.
The axial reactor temperature at any point of the catalyst 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.
Cooled products were sent to a gasliquid separator. A back pressure regulator (BP-LF690, pressure Tech2000, England) was placed
on this separator to regulate the system pressure. Before any
experiments all of set up was swept by using nitrogen gas. Reaction
products were analyzed by a gas chromatograph (Varian CP-3800)
equipped with TCD and FID detectors. Also, the remaining methanol in the exit reactor products was measured and with compari-

Acidic c-alumina, 12 mm in particle size, was obtained from

BASF (Kat.D10-10 S4). Physical and chemical properties of the
catalyst are reported in Table 2. Methanol was obtained from Iran

In this work, we have considered the conversion of methanol to

DME by dehydrating process. This process is moderately exothermic and usually is conducted in an adiabatic xed bed reactor.
One of the most important problems related to the operation of
heterogeneous catalysts is the loss of catalyst activity with timeon-stream. In the indirect process to produce DME using acidic
c-alumina, water has the most important effect on catalyst deactivation [11].
In this work, acidic c-alumina has been used as the catalyst for
the dehydration of methanol to DME. Methanol conversion to DME
and the deactivation of the catalyst have been studied in a laboratory-scale system at various operating temperatures. A temperature dependent model has been developed to predict methanol
conversion to DME at various temperatures.

Table 1
Operating conditions and some characteristics of the laboratory-scale apparatus and
the catalyst used in this study
Set up characteristics
Absolute pressure (atm)
Average temperature of the catalyst bed (C)
Liquid methanol ow rate (L/h)
Reactor inside diameter (mm)
Thermowell outside diameter (mm)

1
233303
0.121
18
6.35

Catalyst
Catalyst weight (g)
Catalyst volume (cm3)
Liquid hourly space velocity (h1)

8.2
14.2
8.5

Fig. 1. A schematic diagram of the experimental apparatus for catalytic production of DME from methanol: (1) nitrogen cylinder, (2) methanol feed tank, (3) dosing pump, (4)
ow meter (5) mixer, (6) evaporator, (7) preheater, (8) adiabatic xed bed reactor, (9) air cooler, (10) condenser, (11) liquidgas separator, (12) back pressure regulator.

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F. Raoof et al. / Fuel 87 (2008) 29672971

300

330
310

Temperature (C)

Temperature (C)

280

260

240

220

290
270
250
230
210

200
0

10

15

20
190

Reactor length (cm)

Catalyst
Catalyst particle sizes (a)
Knife edge hardness (KG)
Inner surface (m2/g)
Tapped density (g/L)
L. o. attrition (%)
L. o. Ignition (%)
Main component
Na2O (%)
Fe2O3 (%)

1 mm < a < 2 mm
Min 4
200
650
Max 3.5
Max 6
Al2O3
Max 0.10
Max 0.15

Methanol
Purity (%)
H2O (%)
Acetone (%)

99.85
0.1
0.003

Petrochemical Company (IPC) as the feed to the reactor. Its composition is given in Table 2.

3. Results and discussion

217 C

230 C

240 C

250 C

259 C

280 C

242 C

245 C

310

290

270

250

230

210
210

230

250

270

290

Inlet temperature (C)

3.1. The temperature effect on methanol conversion

The rst series of experiments were conducted to investigate
the effect of operating temperature of the reactor on methanol conversion. Since the reactor was adiabatic and the reaction exothermic, the temperature of catalyst bed increased from the feed
inlet temperature to a maximum value, as illustrated in Fig. 3.
The change in catalyst bed average temperature, or reactor operating temperature, versus inlet feed temperature is shown in Fig. 4.
According to this Figure, there seem to be a relatively linear
correlation between the change in the reactor operating temperature and the feed inlet temperature.
Fig. 5 shows the variations of conversion at different inlet feed
temperatures versus time on stream. This Figure demonstrates that
methanol conversion was not substantial below 230 C and increased with temperature to the equilibrium amount of 85% at
250 C. Beyond this temperature the conversion remained nearly
constant. It should be noted that methanol conversion did not
change substantially with time at a set feed inlet temperature
meaning that the activity of the catalyst used remained nearly constant throughout the 30 h of experiment.

Fig. 3. Temperature prole along the catalyst bed at various inlet feed temperatures. Solid lines show the trend of these variations.

Bed average temperature (C)

Table 2
Physical and chemical properties of the catalyst and methanol composition

Catalyst bed length (cm)

Fig. 2. Performance of the adiabatic reactor in a blank experiment (without any

reaction).

Fig. 4. Catalyst bed average temperature (or operating temperature) versus inlet
feed temperature. Solid circles are experimental data and solid line shows the trend
of changes.

3.2. Catalyst deactivation

Fig. 6 shows the change in methanol conversion with time for
pure methanol feed (solid circles) and methanolwater mixture
feed (solid triangles; 80 wt% methanol and 20 wt% water) at the inlet feed temperature of 250 C. The slops of the trend lines in Fig. 6
show the catalyst activity loss with time on stream. This Figure
indicates that conversion of methanol rapidly decreased with time
when the mixture of methanolwater was used as the reactor feed.
For the latter feed, the catalyst activity loss was about 12.5 times
larger than that of the pure methanol feed. This phenomenon is
due to the negative effect of water on c-Al2O3 acidic sites. A drop
in methanol conversion due to the presence of water decreased
the heat of reaction released, hence, lowering the reactor temperature as can be seen in Fig. 7.

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F. Raoof et al. / Fuel 87 (2008) 29672971

Operational temperature (C)

300

0.9

Methanol conversion

0.8
0.7
0.6
0.5
0.4
0.3

290
280
270
260
250
240
0

0.2

Catalyst bed length (cm)

0.1
0

10

20

Fig. 7. Catalyst bed temperature prole for pure methanol (solid circle) and methanolwater mixture (80 wt% methanol and 20 wt% H2O; solid triangle) at 250 C
inlet feed temperature. Solid lines show the trends of the results.

30

Time on stream (hr)

217 C

240 C

250 C

230 C

245 C

259 C

280 C
Table 3
Some characterization data of the used catalysts

Fig. 5. Methanol conversions versus time on stream at different inlet feed

temperatures.

Catalyst sample

Surface area (m2/g)

Pore volume (cm3/g)

Pore radius (nm)

1
2

191.55
184.93

0.450
0.433

470.14
468.81

Catalyst 1 is used in the process with pure methanol and catalyst 2 is used with
methanol + water as feed process.

Methanol conversion

0.9
0.8

ln

0.7

 x  13669

 0:1523T 93:171
1x
T

where, x is fractional methanol conversion and T is the operating

reactor temperature (C). Fig. 8 presents a comparison between
the proposed model results and the experimental data. This Figure
demonstrates a good consistency between the calculated and
experimental results. The average relative error of this model in
predicting the results of this study is less than 3%. The cross plot
of estimated versus experimental values for methanol conversion
is presented in Fig. 9. As expected, this Figure demonstrates a good

0.6
0.5
0.4
0.3
0.2
0.1
0
0

10

15

20

25

30

35
1

Time on stream (hr)

Table 3 shows some characterization data of the used catalysts

for two different experiments, namely pure methanol and methanol with water as the process feed. According to this table, the
catalyst characterization data had no considerable changes after
the experiments. As a result, decreasing of catalyst activity in
methanol + water feed, is not related to the changes of catalyst surface area. Water is believed to block the active sites of the catalyst
for methanol consumption through competitive adsorption with
methanol on the catalyst surface [6,11].

0.9
0.8

Methanol conversion

Fig. 6. Methanol conversion variations with catalyst time on stream for pure methanol (solid circle) and methanolwater mixture (80 wt% methanol and 20 wt%
H2O; solid triangle) at 250 C inlet feed temperature. Solid lines show the trends of
the results.

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

3.3. The mathematical model for methanol conversion

A mathematical model has been developed to relate pure methanol conversion to the reactor operating temperature. This model
is presented by the following equation:

190

210

230

250

270

290

310

330

Operational temperature (C)

Fig. 8. A comparison between the calculated conversions of pure methanol using
the proposed model (dashed lines) and the experimental data (circles).

F. Raoof et al. / Fuel 87 (2008) 29672971

2971

different reactor operating temperatures. The obtained results also

showed that water presence in the feed led to a visible reduction in
methanol conversion due to catalyst deactivation.

0.8

Acknowledgments
This work was partially supported by Iran Petrochemical
Research and Technology Company. 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.

xcal

0.6

0.4

References

0.2

0
0

0.2

0.4

0.6

0.8

xexp
Fig. 9. A comparison between calculated conversions (xcal) using the proposed
model and the experimental conversions (xexp).

consistency between the proposed model and the experimental

results.
4. Conclusion
Methanol dehydration over acidic c-alumina in an adiabatic
packed bed reactor to produce DME has been studied over inlet
feed temperature ranging from 217 to 280 C. This study showed
that the methanol conversion to DME was not substantial at feed
temperatures below 230 C and increased to the limit of about
85% at 250 C where it remained unchanged with further increase
in feed temperature. A mathematical model was developed and
successfully tested for pure methanol conversion to DME at

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