Catalysis Communications 6 (2005) 147–152

www.elsevier.com/locate/catcom

Catalytic dehydration of methanol to dimethyl ether (DME)

over solid-acid catalysts
a,* *,a,
F. Yaripour , F. Baghaei I. Schmidt b, J. Perregaard b

a
Catalysis Research Group, Arak Center, Petrochemical Research & Technology Company NPC, P.O. Box 1435, Arak, Iran
b
Haldor Topsøe A/S Research Laboratories, Nymøllevej 55, DK-2800, Lyngby, Denmark

Received 14 June 2004; accepted 30 November 2004

Available online 5 January 2005

Abstract

A series of solid-acid catalysts with different components contents were prepared by coprecipitation (sol–gel) method. These sam-
ples comprised c-alumina and modified c-Al2O3 with silica. The effects of silica various contents have been investigated on purpose
to determine an optimum one. Dehydration of methanol to dimethyl ether (DME) on solid-acid catalysts was studied in a fixed-bed
flow reactor at a temperature of 300 °C under atmospheric pressure and a GHSV of 15,600 h
1. The catalysts have been character-
ized using BET, TGA, XRD, NH3–TPD and elemental analysis techniques and also the results are reported. According to the exper-
imental results, the pure c-Al2O3 catalyst shown a good catalytic activity, but this sample undergoes a fairly rapid and irreversible
deactivation. Silica-modified catalysts have shown better performance compared to the untreated c-Al2O3. It was found that surface
areas increase with increasing in the silica loading at aluminosilicate catalysts. Also, by modifying alumina with silica, it was
observed that the surface acidity of aluminosilicate catalysts increased with increasing in silica loading. The sample with 6 wt% silica
loading has exhibited the best conversion without any by-product.
Ó 2004 Elsevier B.V. All rights reserved.

Keywords: Methanol; Dehydration; Dimethyl ether; Solid-acid catalysts

1. Introduction rofluorocarbons (CFC), has received attention as an

Air pollution is one of the most serious environ-
mental problems all over the world. Since, onboard
diesel engines of buses and trucks exhaust a huge
amount of NOx and particulates, a clean alternative
fuel is desired [1]. In recent years, dimethyl ether
(DME), which is now used as a raw material for mak-
ing chemicals and aerosol propellant such as hair
spray, shaving cream to replace ozone-destroying chlo-
*
Corresponding author. Tel.: +98 861 228 7701 4; fax: +98 861 228
7705.
E-mail addresses: f.yaripour@npc-rt.ir, f_yaripour@chemist.com
(F. Yaripour).
LPG alternative, transportation fuel in substitution
to diesel and power generation [2–5].
Catalytic dehydration of methanol over solid-acid
catalysts offers a potential process for dimethyl ether
synthesis. Several catalysts having activity and selectiv-
ity for the catalytic conversion of methanol into DME
are known, the so called acidic dehydration catalysts
[6,7]. From the literature, it can be concluded that the
reaction takes place on different solid-acid catalysts such
as c-alumina, modified-alumina with silica and phos-
phorus, Al2O3–B2O3 and molecular sieves materials
(chabazites, mordenites, SAPOs, . . .), in a temperature
range of 250–400 °C and pressures up to 18 bar [6–10].
Extensive research has been made especially in order

1566-7367/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2004.11.012
148 F. Yaripour et al. / Catalysis Communications 6 (2005) 147–152
to find catalysts having higher selectivity for the ether
formation and less tendency to coke formation [7]. It
has recent been found that if the reaction of methanol
dehydration take place on the modified-alumina cata-
lysts with silica, can be caused to reduce the amounts
of coking and by-products [5,7].
In the present work, the catalytic dehydration of
methanol to DME has been studied over c-Al2O3 and
modified-alumina with silica catalysts. The effect of sil-
ica on the catalytic activity of c-Al2O3 have been inves-
tigated. In addition, we have investigated the correlation
of the activity results with surface acid properties of
these catalysts. So, we have attempted to characterize
the properties of catalysts by surface area measure-
ments, XRD, etc. This work is part of a long-range ef-
fort to develop a new know–how for the conversion of
methanol to DME at Haldor Topsøe A/S.
2. Experimental
2.1. Material
The starting materials were aluminium nitrate nano-
hydrate [ANN; Al(NO3)3 Æ 9H2O], tetraethyl orthosili-
cate [TEOS; Si(OC2H5)4], ethanol [C2H5OH] and
ammonia solution [max. 33% NH3].
2.2. Catalysts preparation
2.2.1. c-Al2O3
c-Al2O3 (DME-SCAT2) was obtained by the thermal
decomposition of the boehmite (c-AlOOH, DME-
SCAT1) precursor at 550 °C for 6 h at heating rate of
2 °C/min. A commercially available catalyst (it has been
developed by Haldor Topsøe A/S, DME-FCAT) was
used as a reference solid-acid catalyst for the methanol
dehydration catalyst.
2.2.2. Aluminosilicates
A series of aluminosilicate catalysts were prepared
by varying amount of silica loading (1, 3, 6, 9 and
15 wt%) by co-precipitation (sol–gel) method. All of
the samples were prepared at 50 °C. According to pre-
vious study on the aluminosilicate catalysts [11,12], in
all these experiments the standard preparation condi-
tions were as follows: co-precipitation by the ammonia
solution, the precipitant solution was added slowly at
a rate of 4 ml/min, the concentration of ANN and
TEOS in ethanol is 2 mole/l, H2O/TEOS = 10, mixing
time 1440 min and NH4OH/C2H5OH ratio = 1/3. The
mixture was allowed to react in a glass beaker using
a magnetic stirrer (IKA, cylindrical shape, 30 mm
length) at about 500 rpm at 50 °C for 24 h. After pre-
cipitation, the product dried at 110 °C overnight and
calcined in air at 650 °C for 6 h at heating rate of
2 °C/min to remove the residual water, ammonia,
ammonium nitrate and organic substances. In more
detail aluminosilicate catalysts with 1, 3, 6, 9 and
15 wt% silica loading, were applied DME-AlS1,
DME-AlS2, DME-AlS3, DME-AlS4 and DME-AlS5,
respectively.
2.3. Characterization of the catalysts
BET surface area, pore volume and pore diameter
were measured by N2 adsorption–desorption isotherm
at liquid nitrogen temperature using Autosorb-3B
(Quantachrome, USA). Prior to the adsorption–desorp-
tion measurements, all the samples were degassed at
300 °C in N2 flow for 16 h.
The XRD pattern of all the calcined samples were
recorded on an X-ray diffractometer (X
Pert PRO,
Model PW3040/60 console) using Cu Ka monochroma-
tized radiation source and Ni filter in the range
2h = 5–90°.
Ammonia temperature programmed desorption
(NH3–TPD) experiments in the temperature range 90–
850 °C were conducted using a 0.2 g of catalyst (in a
fixed-bed quartz microreactor: i.d., 4 mm and length,
200 mm) under 2% NH3/He gas mixture stream
(100 N ml/min) from room temperature up to 500 °C
at a heating rate of 10 °C/min. Before all experiments,
catalyst sample (0.2 g) were treated in situ for 2 h in a
He flow rate of 100 N ml/min while the temperature
was raised from room temperature up to 500 °C at a
heating rate of 10 °C/min.
TGA pattern was detected by a Haldor Topsøe TGA-
HT thermogravimetric analyzer in order to determine
proper calcination and phase transformation conditions.
The sample was heated from 25 to 950 °C at heating rate
5 °C/min, in flow of 100 N ml/min of helium.
The chemical compositions of catalysts (Al, Si) were
determined by an inductively coupled plasma-optical
emission spectrometer (ICP-OES, Perkin–Elmer, model
Optima 3000) and using Ar as plasmogene.
2.4. Catalytic activity
Catalytic activity of all samples for dehydration of
methanol to DME were studied at a steady state in a
fixed-bed quartz reactor (i.d., 10 mm and length
650 mm) with an on-line GC. All of the experiments
were performed at atmospheric pressure, and tempera-
ture of 300 °C. Prior to catalytic testing the samples
were crushed and then sieved. For each experiment,
0.5 g of the catalyst (grain size 25–50 mesh or 300–
710 lm) was loaded to the reactor by packing quartz
wool pads at both of ends of catalyst bed. Nitrogen
saturated by pure methanol (11% MeOH in N2) was
used as feed, and the gas hourly space velocity
(GHSV) was monitored to 15,600 h
1 (feed flow rate
 F. Yaripour et al. / Catalysis Communications 6 (2005) 147–152
of 130 ml/min). The temperature is used for saturating
the N2 stream with methanol was 15 to 18 °C. Before
the test, the catalyst sample was activated in situ at
atmospheric pressure from 25 to 200 °C at heating
rate 5 °C/min, in a flow of nitrogen 150 ml/min. Then
the feed was sent into fixed-bed reactor and the reac-
tor temperature increase up to 300 °C simultaneously.
In order to survey the activity of the various solid-
acid catalysts, feed was sent for 70 h. After 70 h, anal-
ysis of the outlet gas stream was performed using GC.
2.5. Product analysis
The reaction products were analysed by an on-line
gas chromatograph (Hewlett–Packard, Model: HP-
5890 series II) using CP-PorPlot Q-HT column (con-
nected to FIDA) for separating DME and MeOH and
Al2O3/NaOH column (connected to FIDB) for separat-
ing C1 –Cþ6 hydrocarbons. The product lines were heated
electrically where necessary in order to avoid unwanted
condensation of methanol and water. Several types of
different methanol dehydration catalysts were prepared
and tested. As measures of the catalytic activity, and
for purpose of quantitative comparison with commercial
ones, the conversion of the feed methanol (X%) and
turnover frequency (TOF) were used. These were de-
fined as follows:
 
Outlet partial pressure of MeOH
X ¼ 1
 100%;
Inlet partial pressure of MeOH
 
2  Number of mole of DME produced per second
TOF ¼
Number of mole of acid site on the catalyst
Fig. 1. TGA curves of boehmite sample (in a flow of 100 N ml/min of helium, heating rate 5 °C/min).
149
3. Results and discussion
3.1. Catalyst characterization
Suitable temperature of calcination for phase trans-
formation of boehmite to c-alumina was determined
by the TGA method. Fig. 1 shows the TGA profile of
boehmite. According to this figure, it is clear that
boehmite transformed to c-Al2O3 at higher temperature
of 425 °C. Calcination of boehmite under conditions
(550 °C, 6 h) has shown good results because boehmite
does not show any weight loss at higher temperature
of 550 °C.
Table 1 summarizes the specific BET surface areas,
pore volumes and pore diameters of the catalysts em-
ployed in this study. The phase transformations of
Al2O3 (boehmite) to c-Al2O3 become significant at high-
er temperature of 425 °C and remarkably decrease the
surface area of the c-Al2O3 catalyst. This variation in
the porous properties; is likely due to change in the pri-
mary particle size and/or crystal growth of either the
bulk material or the active phase (sintering phenomena).
Surface area of the aluminosilicate samples monoto-
nously increased with increasing the silica content, and
all the samples had surface areas higher than 250 m2/g,
indicating that they had well-developed pore structures.
The chemical compositions of the solid-acid catalysts
used in the present study are also given in Table 1. In all
cases, the real content was very similar to the nominal one.
The XRD patterns (not shown) of all the calcined
catalysts exhibited different diffraction lines. The XRD
analyses of the DME-SCAT1 catalyst determined the
presence of the orthorhombic (JCPDS No. 83-2384)
150 F. Yaripour et al. / Catalysis Communications 6 (2005) 147–152

Table 1
Compositions, acidity contents and some characterization data of the calcined catalysts
Properties Surface Pore Pore Surface area of Amount of Acidity Components
area (m2/g) volume (cm3/g) diameter the used catalyst NH3 (mmole) (mmole/g dry sample)
Al (%) Si (%) P (%)
(nm) (m2/g)
Catalyst
DME-SCAT1 338.7 0.65 7.69 – 0.0397 0.437 44.9 – –
DME-SCAT2 268.2 0.68 10.18 295 0.0402 0.442 52.8 – –
DME-FCAT 168.1 0.50 11.65 184 0.0261 0.287 29.6 6.91 4.26
DME-AlS1 252.4 0.43 6.75 224 0.0276 0.301 43.1 0.767 –
DME-AlS2 286.7 0.46 6.48 274 0.0269 0.295 41.4 2.044 –
DME-AlS3 333.8 0.56 6.75 305 0.0283 0.311 37.6 3.72 –
DME-AlS4 363.5 0.48 5.32 294 0.0324 0.362 35.6 5.83 –
DME-AlS5 383.2 0.54 5.63 359 0.0347 0.398 32.6 9.28 –

boehmite (c-AlOOH) crystal phase. However, XRD
analyses of DME-SCAT2 confirmed presence of two
crystalline phase, namely cubic c-Al2O3 (JCPDS No.
79–1558) and some amorphous phase. It was confirmed
that the DME-FCAT sample has an c-Al2O3 crystalline
phase on an amorphous background. All the aluminosil-
icate calcined catalysts exhibited diffraction line of c-
Al2O3. However, aluminosilicate containing more than
6 wt% silica are almost amorphous c-Al2O3 and show
a shoulder by 2h = 28° could be Al2(SiO4)O/kyanite tri-
clinic crystalline phase.
The results of ammonia TPD-titration (Boric acid
procedure) that contain the amount of desorbed ammo-
nia and acidity content of the prepared catalysts are
summarized in Table 1. It is well known that the acidic
sites on the surface solid-acid catalysts are two type;
Brønsted and Lewis acid sites. So, it is well known that
Brønsted acid sites are able to catalyze the dehydration
of methanol [13]. The prepared c-Al2O3 has higher acid-
ity than commercial one. By modifying c-Al2O3 with sil-
ica it was observed that the surface acidity improved.
Also, by modifying alumina with silica, it is observed
that the surface acidity of aluminosilicate catalysts in-
creased with increasing in silica loading. The NH3–
TPD profiles of DME-FCAT, DME-SCAT2 and
DME-AlS3 (DME-S) catalysts are shown in Fig. 2,
while the temperature of desorption maxima (Tdi) and
the amount of desorbed ammonia and water are sum-
marized in Table 2. The peak temperatures for all the
catalyst samples were approximately identical (260–
275 °C), indicating that acid strength was not changed
by the silica content. TPD results shown that all the acid
sites on the surface catalysts are a medium type. The
amounts of desorbed water decreased with addition
the silica to pure c-Al2O3 catalyst.
3.2. Catalytic activity
Table 3 show the catalytic performance at steady
state in methanol dehydration over reference and pre-
pared catalysts at the atmospheric pressure. As indicated
by the results of Table 3, c-Al2O3 catalyst is active and

Fig. 2. NH3–TPD profiles of: (a) DME-SCAT2, (b) DME-FCAT and (c) DME-S catalysts.
 F. Yaripour et al. / Catalysis Communications 6 (2005) 147–152 151

Table 2
NH3–TPD: temperature of desorption maxima (Tdi) and amounts desorbed
Catalysts DME-SCAT2 DME-FCAT DME-S
Parameters
Amount of NH3 (mmole) 0.0402 0.0261 0.0283
Amount of H2O (mmole) 0.538 0.400 0.514
Acidity (mmole/g dry sample) 0.442 0.287 0.311
Tdi (°C), ammonia peak 261 270 262
Tdi (°C), water peak 657.5 705 660
Temperature range of NH3 desorbed (°C) 171–793 176–729 158–770
Temperature range of H2O desorbed (°C) 385–854 437–853 434–854

Table 3
Methanol dehydration over reference and modified c-alumina catalysts
Catalysts DME-AlS1 DME-AlS2 DME-AlS3 DME-AlS4 DME-AlS5 DME-SCAT2 (c-Al2O3) DME-FCAT
Parameters
DME (wt%) 75.6 73.4 71.3 64.7 58.6 63.23 67.24
MeOH (wt%) 24.4 26.6 28.7 35.3 41.6 38.77 32.76
CH4 (wt%) 0.0326 0.0128 – – – – –
Conversion (X%) 86.4 84.5 85.0 83.5 73.6 77.15 82.13
TOF (103/s) 121.9 158.2 164.5 178.9 457.4 131.7 333.7
Rate (10
7 mol g
1 s
1) 2.20 2.84 1.88 3.22 8.25 3.77 3.79
Rate/surface area 0.87 0.99 0.56 0.89 21.5 2.24 1.41
(10
6 kmole/h m2)

selective for DME formation. In the case of commercial
catalyst, methanol conversion slightly increased. The re-
sults shown that c-Al2O3 catalyst have high initial rate
of the DME formation but slowly deactivates with time
on stream in methanol dehydration to DME.
To improve the catalytic performance, c-Al2O3 cata-
lyst was modified with Si. By modifying c-Al2O3 with sil-
ica, it has been observed that catalytic performance is
positively affected (Table 3). The rates of DME forma-
tion do not change on all the prepared catalysts. But,
the formation rate of dimethyl ether increased signifi-
cantly in DME-AlS5, in comparison with that of the
pure c-Al2O3. The significant acceleration of the dehy-
dration rates may be due to an enhancement of acid
strength by the intercalation and/or an increase in alu-
mina surface area on intercalation [14]. The methanol
partial pressure and the amount of the inlet methanol
depended to the cooling bath temperature. It should
be pointed out that the DME selectivity (SDME%) is al-
most 100% on the different catalysts. The variations of
the DME selectivity can be attributed to the methanol
partial pressure. SiO2-modified catalysts showed better
performance than the untreated c-Al2O3. By modifying
alumina with silica, it is observed that the surface acidity
of aluminosilicate catalysts increased with increasing in
silica loading. Also, it is understood that the catalytic
activity decreases after 6 wt% of silica loading. Further-
more, the surface acidity and catalytic activity of cata-
lysts with 3 wt% silica loading is low. The activity,
selectivity and stability studies showed that the
c-Al2O3 modified with 6 wt% silica is more active, noth-
ing by-product and less deactivated by the reaction con-
ditions. 15 wt% SiO2-modified catalyst showed almost
similar performances in comparison with unmodified
c-Al2O3. This subject can be explained the surface of so-
lid acid catalysts contain the Lewis and Brønsted acid
sites which it has now been found that the dehydration
reaction took place mainly on Brønsted acid sites. It is
also known that Brønsted acid sites on c-Al2O3 are very
weak. Therefore, since the acidity of the above-men-
tioned catalysts is almost similar with c-Al2O3, it can
concluded that the amount of Brønsted acid sites is
low. So, it can be concluded that the aluminosilicate cat-
alysts with mild acidity will be effective on DME 10 syn-
thesis in the long term reaction. The low conversion over
the samples having more than 6 wt% silica suggest that
the excess amount of silica creates the hindrance to the
existence of acid sites due to the accumulation on the
surface of the catalyst, which is already evidenced from
XRD and SEM spectra (not shown). Under the experi-
mental conditions, methanol was converted into DME
and methane was formed as the main by-product in cat-
alysts which contains the SiO2 amount of lower than
3 wt%. It can be concluded that the number of strong
acidic centers is high on these catalysts surfaces. This
is due to DME formation is related to sites with weak
and medium acidity whereas, selectivity to hydrocar-
bons such as methane is due to the number of strong
acidic centers.
4. Conclusions
A series of solid-acid catalysts were prepared by co-
precipitation method. c-Al2O3 and modified-alumina
152 F. Yaripour et al. / Catalysis Communications 6 (2005) 147–152
with silica catalysts were used for the synthesis of DME
through dehydration of methanol.
Methanol is dehydrated to form DME over acid sites
of solid catalysts. DME formation is mainly related to
sites with weak and medium acidity. Under the experi-
mental conditions used, methanol was converted into
DME as a main product and methane was formed as
the main by-product on the some catalysts.
SiO2-modified catalysts showed better performance
than the untreated c-Al2O3. The effect of SiO2 contents
were studied to find out the optimum SiO2 contents.
Among the SiO2-modified c-Al2O3 catalysts, 6 wt%
SiO2/c-Al2O3 (DME-AlS3) exhibited the best conversion
without any by-product. DME was selectively formed
over DME-AlS3 catalyst in the catalytic dehydration
of methanol at 300 °C and atmospheric pressure in com-
parison with other catalysts.
Acknowledgements
The financial support to this work by the National
Petrochemical Company (NPC), Iran and Haldor Top-
søe A/S (HTAS), Denmark as joint research activity
whose aid is gratefully acknowledged. The authors
would like to thank HTAS employees of Syngas/Chem-
icals Technology and Analysis Divisions for valuable
discussions and their collaboration at catalyst character-
ization by different methods.
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