Chemical Engineering Journal xxx (2012) xxxxxx

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

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

Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric
acid based mesoporous catalysts
Aysegul Ciftci a, Dilek Varisli b, Kenan Cem Tokay a, N. Asl Sezgi a, Timur Dogu a,
a
Chemical Engineering Department, Middle East Technical University, 06800 Ankara, Turkey
b
Advanced Technologies, Gazi University, Teknikokullar-Ankara, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: Tungstophosphoric acid (TPA) incorporated silicate structured new mesoporous catalysts were synthe-
Available online xxxx sized following one-pot hydrothermal and impregnation procedures. Surface area of TPA@MCM-41,
which was prepared by impregnating TPA into MCM-41, was two orders of magnitude higher than the
Keywords: surface area of pure TPA and this catalyst showed very high activity in dehydration reactions of both
Tungstophosphoric acid ethanol and methanol. Ethanol fractional conversion values reaching to 1.0 was obtained at 300 C at a
Mesoporous catalyst space time of 0.27 s.g/cm3, over TPA@MCM-41. Diethyl ether selectivity showed a decreasing trend by
Dehydration
increasing temperature from 180 to 400 C in ethanol dehydration reaction. Ethylene yield values
Ethylene
Diethyl ether
approaching to 100% were obtained at temperatures over 250 C. DME yield passed through a maximum
Dimethyl ether at about 200 C with this catalyst, over which coke formation caused catalyst deactivation. One-pot
Fuel hydrothermal synthesis procedure was very successful to synthesize a catalyst (TRC-W40) which did
not lose any activity after repeated washing steps. This catalyst gave highly stable catalytic performance
in dehydration of both ethanol and methanol. Well dispersed WOx clusters were formed within the mes-
oporous silicate matrix of this material. This catalyst showed very good activity in dehydration reactions
of alcohols, giving 100% conversion in ethanol dehydration at 400 C and 100% DME selectivity in meth-
anol dehydration at temperatures less than 300 C.
2012 Elsevier B.V. All rights reserved.

1. Introduction Mesoporous silicate structures (M41S family) having ordered

Heteropolyacid (HPA) compounds have very strong Bronsted
acidity, with very high proton mobility. They also have good redox
properties. These properties make them suitable catalysts for acid
catalyzed and selective oxidation reactions [13]. Recent research
on etherication reactions to produce gasoline blending oxygen-
ates [47] and on dehydration of alcohols [814] showed high
activity of HPAs in these reactions. Some ethanol dehydration
reaction results obtained using pure silicotungstic acid (STA),
tungstophosphoric acid (TPA) and molybdophosphoric acid
(MPA) catalysts, were reported in our recent publication [10]. Re-
sults of that work showed that ethylene was the main product at
high temperatures while diethyl ether (DEE) was formed at lower
temperatures. Although HPAs are considered to have good poten-
tial as solid acid catalysts, their very low surface area (<1 m2/g) and
high solubility in polar solvents limit their use as catalysts in prac-
tical applications. In order to improve these limitations of HPAs,
recent studies were focused on the synthesis of supported catalysts
and/or on the production of their water insoluble salts [4,5,1517].
Corresponding author. Tel.: +90 312 2102631; fax: +90 312 2102600.
E-mail address: tdogu@metu.edu.tr (T. Dogu).
pore structures, have been considered as highly promising catalyst
supports, due to their high surface area and larger pore diameters
than zeolites, which allow easy penetration of the reacting mole-
cules to the active sites [18]. However, these materials are quite
inert and have low catalytic activity in pure form, for most catalytic
applications. For the enhancement of catalytic activity of these
materials, metals or metal oxides were incorporated into their
structure by direct (one-pot) hydrothermal procedures or by post
synthesis methods [1922]. For the improvement of the acidic
characteristics of such silicate structured materials, heteropolyac-
ids were incorporated into these materials and their catalytic per-
formances were tested in different reactions [16,17,2326]. In a
recent study of our research group, acidic characteristics of such
silicate structured mesoporous materials were improved by the
impregnation of silicotungstic acid (STA) into these materials and
their catalytic performances were tested in ethanol dehydration
reaction [11]. That study showed that, STA impregnated MCM-41
was very active in ethanol dehydration to produce ethylene and
diethyl ether. Characterization studies of STA incorporated silicate
structured mesoporous materials had also indicated the formation
of well dispersed WOx nano-rods within the mesoporous silicate
matrix of the synthesized materials [30,12].

1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.04.016

Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
2 A. Ciftci et al. / Chemical Engineering Journal xxx (2012) xxxxxx
Alcohols have been considered as being among the best alter-
nates to petroleum for the production of environmentally benign
transportation fuels, fuel additives and petrochemicals [27]. Ethyl-
ene, which is one of the main feed stocks of petrochemical industry
and diethyl ether (DEE), which has excellent transportation fuel
properties (cetane number > 125) may be produced by dehydration
of ethanol over solid acid catalysts [28,10]. Good burning properties
of DEE make it a promising alternative fuel or fuel additive for diesel
fuel [27,29]. Also, blending of DEE with ethanol was reported to im-
prove the cold start problem of ethanol fueled cars. STA incorpo-
rated silicate structured mesoporous materials, which were
synthesized by a one-pot hydrothermal method and containing
various W/Si ratios, were also shown to give very good catalytic
performance in dehydration reaction of ethanol to produce
ethylene and DEE [29,30].
Another highly attractive environmentally clean diesel fuel
alternate is dimethyl ether (DME), which is commercially produced
by dehydration of methanol. DME has higher cetane number and
much lower NOx emissions than conventional diesel fuel. Also,
near-zero smoke formation was reported in DME derived engines.
Our recent studies showed that mesoporous aluminosilicate, nano-
composite Naon-silica and STA incorporated mesoporous silicate
structured catalysts were highly active and selective for the syn-
thesis of DME by dehydration of methanol [12,13,32,33].
Most of our earlier studies with heteropolyacid catalysts were
performed with silicotungstic acid (STA) based materials. The main
objectives of the present study were the synthesis of new water
insoluble and high surface area tungstophosphoric acid (TPA)
incorporated silicate structured mesoporous catalysts, following a
new one-pot hydrothermal procedure, and comparison of catalytic
performance of such materials with the performance of TPA
impregnated MCM-41 type catalytic materials, in dehydration
reactions of methanol and ethanol, to produce DME, DEE and eth-
ylene, respectively.
2. Experimental
In this study, TPA incorporated silicate structured mesoporous
catalytic materials were synthesized following two different
routes, namely by a new one-pot hydrothermal synthesis route
and by impregnation of TPA into MCM-41. The catalysts prepared
by these two procedures were denoted as TRC-W40 and
TPA@MCM-41, respectively. Details of the synthesis procedures
of these materials are given in the following sections.
2.1. Synthesis of mesoporous TRC-W40 catalyst by one-pot
hydrothermal procedure
Tungstophosphoric acid (TPA) incorporated mesoporous TRC-
W40 catalyst was synthesized following a one-pot hydrothermal
route. Synthesis mixture was prepared using tetraethylorthosilicate
(TEOS) (Merck) as the silica source and cetyltrimethylammonium
bromide (CTMABr), (99% pure, Merck) as the surfactant. TPA, which
was obtained from Acros Organics, was used as the active compo-
nent. The W/Si molar ratio in the synthesis solution was adjusted
to 0.40 [34]. The pH of the clear solution, which contained TEOS,
CTMABr and TPA, was below 0.5. This solution was continuously
mixed and transferred into a Teon-lined stainless steel autoclave,
in which hydrothermal synthesis was performed at 120 C for a per-
iod of 96 h. Solid product obtained by this procedure was crushed
and then thoroughly washed with deionized water, until the pH of
the wash water was close to neutral. Then, it was dried at 40 C
and calcined in a tubular furnace.
Calcination temperature of MCM-41-like materials was gener-
ally selected as being over 500 C, for the removal of the surfactant
Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
from their lattice [11,1822]. However, in the case of synthesis of
temperature sensitive materials, lower calcination temperatures
or use of supercritical or alcohol-acid extraction procedures should
be applied [10,11,31,35]. Heteropolyacids are known to be highly
temperature sensitive, as far as their acidity and catalytic perfor-
mances are considered [5,6,31,36] As it was reported in our earlier
publication, calcination temperature caused signicant variation
on the catalytic performance of STA incorporated materials and
some activity loss was observed in the materials calcined at tem-
peratures over 400 C [31]. Loss of acidity of TPA was reported to
take place at lower temperatures than STA [36]. Consequently, a
set of TGA-DTA experiments were made to decide about the calci-
nation temperature of the novel TPA incorporated material, which
was synthesized in this work following the one-pot procedure.
2.2. Synthesis of TPA@MCM-41 by impregnation
TPA@MCM-41 catalyst was synthesized following an impregna-
tion procedure. In the synthesis of TPA@MCM-41, rst MCM-41
was synthesized following a hydrothermal synthesis procedure.
Sodium silicate and cetyltrimethylammonium bromide (CTMABr)
were used as the silica source and the surfactant, respectively.
After the hydrothermal synthesis step, the synthesized material
was calcined at 550 C, before the application of the impregnation
process. Details of the MCM-41 synthesis procedure are available
in the literature [18,22]. Predetermined amount of tungstophos-
phoric acid (TPA) (Acros Organics) was then dissolved in deionized
water and MCM-41 was added to this solution. The resulting mix-
ture was stirred at 30 C for 65 h. Evaporation of excess water was
achieved at 70 C. Then, the temperature of the oven was in-
creased, rst to 96 C and later to 120 C, for completion of the dry-
ing process.
2.3. Characterization of the synthesized catalysts
TPA@MCM-41 and TRC-W40 catalysts were characterized by
nitrogen adsorptiondesorption (Quantachrome Autosorb-1-C/MS
instrument), X-ray diffraction (Rigaku D/MAX2200 diffractometer
with a CuK radiation source with a 2h scanning range between 1
and 50), SEM-EDS (JSM-6400 (JEOL) equipped with NORAN sys-
tem Six), FTIR (Bruker FTIR-IFS66/S instrument), pyridine adsorp-
tion-DRIFTS (Perkin Elmer Spectrum One instrument) and
transmission electron microscopy (JEOL Model JEM 1010 TEM)
techniques. TEM analysis of the synthesized materials was per-
formed at the Electron Microscopy Center of Babes-Bolyai Univer-
sity, in Romania.
Calcined materials were further degassed at 100 C for 16 h in
vacuum before nitrogen adsorptiondesorption analysis. Degas-
sing procedure was decided basing on our earlier tests for com-
plete removal of moisture from heteropolyacid incorporated
silicate structured mesoporous materials. Catalysts were also dried
at 110 C before the SEM-EDS and diffuse reectance FT-IR
(DRIFTS) analyses. For the SEM-EDS analyses, samples were cov-
ered with a very thin layer of gold. DRIFTS analysis of the pyridine
adsorbed catalysts gave information about the relative strengths of
Bronsted and Lewis acid sites of the synthesized materials. DRIFTS
analysis, was made at room temperature in a wave number inter-
val of 4004500 cm 1. Difference of the DRIFT spectra of pyridine
adsorbed and fresh catalysts was analyzed for the acidity measure-
ments. FTIR analysis of the synthesized materials (mixed with KBr)
was also performed at a spectral resolution of 4 cm 1.
2.4. Activity tests of the synthesized catalysts
Catalytic activities of TPA@MCM-41 and TRC-W40 catalysts
were tested in vapor phase dehydration of ethanol and methanol.
 A. Ciftci et al. / Chemical Engineering Journal xxx (2012) xxxxxx 3

DrTGA TGA TRC-W40 Uncalcined DTA

mg/min % uV
378.88C
1.00 100.0 Weight Loss -5.367m
Weight Loss -3.840mg -48.583 40.00
-34.761%
80.0
Weight Loss -0.481mg
-4.354%
20.00
493.64 C
60.0
0.00

40.0 349.64C 505.10 C

110.12 C Weight Loss -0.861mg 0.00
-7.794%
236.20 C
20.0
-20.00
-1.00 0.0 233.06C

0.0 100.0 200.0 300.0 400.0 500.0 600.0

Temp[C]

Fig. 1. TGADTA analysis of uncalcined form of TRC-W40.

For each experiment 0.2 g of fresh catalyst was placed into the
xed bed ow reactor and supported by quartz wool from both
ends. Liquid ethanol (99.98% purity, Sigma Aldrich) was pumped
at a ow rate of 2.9 ml/h, into the evaporator by a syringe pump.
Evaporator was placed before the reactor and its temperature
was kept at 150 C. In the evaporator, vaporized alcohol was mixed
with helium at a ratio of 1:1. Total ow rate of the gas mixture fed
to the reactor was 44 ml/min. In order to control the reaction zone
temperature, reactor was placed into a temperature controlled
tubular furnace. All the lines, before and after the reactor, were
heated to 150 C, to avoid condensation of any chemicals in the
experimental system. Composition of the reactor exit system was
analyzed by a gas chromatograph (Varian 3800), which was con-
nected on-line to the reactor. Gas chromatograph was equipped
with a Porapak T column and a TCD detector.
3. Results and discussions
3.1. Results of catalyst characterization tests
Thermal analysis (TGA-DTA) of the uncalcined material, which
was synthesized by the one-pot procedure, was performed by a
Dupont 951 thermal analysis system, at a heating rate of 10 C/
min, under the ow of dry air. The weight loss (about 18%), which
was observed between 200270 C (Fig. 1), corresponds to the re-
moval of most of the surfactant from the synthesized material. The
minimum of the corresponding endothermic DTA peak was at
236 C. This result indicated that calcination temperature should
be over 250 C. As shown in Fig. 1, there are two other DTA peaks
at about 380 C and 495 C. Both of these peaks correspond to the
exothermic processes, indicating the removal of some oxidized
species from the synthesized material. Basing on the TGA/DTA
results, synthesized materials were calcined either at 270 C
(denoted as TRC-W40(L)) or at 400 C (denoted as TRC-W40(H)),
and the characterization results of these materials were compared.
Basing on the literature results, which indicated loss of acidity of
TPA at higher temperatures, calcination temperature was not se-
lected over 400 C. Further discussion about the effects of calcina-
tion temperature on the catalyst structure will be given in the
following sections.
Chemical compositions of the TPA incorporated mesoporous
materials were evaluated by EDS analysis and W/Si ratio in the so-
lid products was compared with the W/Si ratio in the synthesis
solution. EDS analyses made at different locations of the materials
were highly consistent, indicating well dispersion of TPA in the
synthesized material. For TPA@MCM-41 catalyst, the molar ratio
of W/Si was found as 0.18. This result was consistent with the ratio
in the synthesis solution, indicating that TPA was successfully
impregnated into the mesoporous MCM-41 support. The material
synthesized by the one-pot hydrothermal synthesis procedure,
namely TRC-W40, was prepared by adjusting the W/Si molar ratio
as 0.40 in the synthesis solution. This ratio was found as 0.52 from
EDS analysis of the synthesized material. This result indicated suc-
cessful incorporation of TPA into the catalyst structure and loss of
some silica during the hydrothermal synthesis and washing steps
of the synthesis procedure. As it was mentioned in Section 2.1, this
material was repeatedly washed with deionized water after the
hydrothermal synthesis step. As it was found by the EDS analysis,
W/Si ratio of the nal product was even higher than the W/Si ratio
in the synthesis solution, indicating no leaching of the incorporated
tungstophosphoric acid from the lattice of the synthesized material
as a result of washing steps.
Physical and chemical properties of the synthesized materials
are summarized in Table 1. According to the nitrogen physisorp-
tion analysis, TRC-W40(L) has multipoint BET surface area, pore
volume and average pore diameter values of 143 m2/g, 0.23 cm3/
g and 5.6 nm, respectively. This material was calcined at 270 C.
Corresponding values of the material, which was calcined at
400 C (TRC-W40(H)), showed signicantly higher surface area

Table 1
Physical and chemical properties of the synthesized materials.

Sample ID W/Si (atomic) from EDS Surface area (m2/g) BET Pore volume (cm3/g) BJH des. Average pore diameter (nm) BJH des.
MCM-41 1000 1.00 2.9
TRC-W40(L) 0.52 143 0.23 5.6
TRC-W40(H) 0.52 263 0.51 5.6
TPA@MCM-41 0.18 183 0.15 1.4

Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
4 A. Ciftci et al. / Chemical Engineering Journal xxx (2012) xxxxxx

Fig. 4. Pore size distributions of TRC-W40(L) and TRC-W40(H).

Fig. 2. Pore size distribution of TPA@MCM-41.

desorption branches and the closure of the hysteresis loops was

and pore volume values (Table 1). By increasing the calcination
at a relative pressure of nitrogen, as high as 0.85. Such a hysteresis
temperature from 270 C to 400 C, surface area of the material in-
loop is generally considered to indicate signicant interconnectivi-
creased from 143 m2/g to 263 m2/g. Similarly, pore volume in-
ty in the mesoporous network [13]. Major difference of the adsorp-
creased from 0.23 cm3/g to 0.51 cm3/g, by increasing the
tiondesorption isotherms of TRC-W40(L) and TRC-W40(H) is the
calcination temperature. These results showed that 270 C was
higher quantity of adsorbed nitrogen in the material calcined at
not sufcient for the removal of all of the surfactant from the struc-
higher temperature (TRC-W40(H)). This is consistent with the high-
ture of the synthesized material. These results also indicated that
er pore volume of this material than the pore volume of TRC-
the second TGA-DTA peak (Fig. 1), observed in the temperature
W40(L) (Table 1). Pore size distributions of TRC-W40(L) and TRC-
range of 350380 C, is probably due to the removal of carbon
W40(H) showed the presence of mesopores, mostly in the range
containing surfactant remains from the catalyst pores through an
of 210 nm (Fig. 4). In fact, the average pore diameter of both of
exothermic oxidation process.
these materials was 5.6 nm, which is about twice the average pore
Results of nitrogen physisorption analysis of TPA impregnated
diameter of MCM-41.
material (TPA@MCM-41) showed that surface area evaluated by
XRD pattern of the synthesized material, which was calcined at
the BET method was 183 m2/g. Its pore volume and average pore
270 C (TRC-W40(L)), indicated an amorphous structure (Fig. 5a).
diameter values were 0.15 cm3/g and 1.4 nm, respectively. Pore
Typical XRD peaks of the Keggin structure of TPA were not ob-
size distribution of this material indicated the presence of pores
served in this XRD spectrum. In the case of the material calcined
in the range of 110 nm (Fig. 2). Surface area and pore volume val-
at 400 C (TRC-W40(H)), XRD pattern indicated the presence of
ues of this supported catalyst were much lower than that of MCM-
broad diffraction peaks at 2h values of 23.2 and 33, which were
41 support itself, which were 1000 m2/g and 1.0 cm3/g, respec-
tively. These results indicated plugging of signicant fraction of
the pores present in the support material (MCM-41), with the
impregnated TPA. The average pore diameter of the TPA impreg-
nated material (1.4 nm) was also lower than the support material
MCM-41 (Table 1).
The nitrogen adsorptiondesorption isotherms of TRC-W40(L)
and TRC-W40(H) (Fig. 3) were both Type IV, according to the IUPAC
classication, with H2-like hysteresis loops. These isotherms indi-
cated the formation of the ordered mesoporous structures. For
MCM-41-like materials having long range ordered mesopores,
sharp hysteresis loops with parallel adsorption and desorption
branches were expected. The desorption branches of the isotherms
of TRC-W40(L) and TRC-W40(H) were quite sharp. However, the
adsorption branches of these isotherms were not as sharp as the

Fig. 3. Nitrogen adsorptiondesorption isotherms of TRC-W40(L) and TRC-W40(H). Fig. 5. XRD patterns of the synthesized materials.

Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
 A. Ciftci et al. / Chemical Engineering Journal xxx (2012) xxxxxx
Fig. 6. SEM photographs of TPA@MCM-41 catalyst.
assigned to WOx clusters (Fig. 5b). Similar results were reported in
our earlier study with STA incorporated mesoporous materials
[30,31]. A small but a rather sharp peak observed at a 2h value of
25.8 is consistent with the main XRD peak of Keggin structure
of TPA. These results indicated that Keggin structure was mostly
destroyed and WOx clusters were formed within the matrix of
the silicate structured mesoporous material prepared by the one-
pot hydrothermal procedure, which was calcined at 400 C. Cluster
size of WOx was estimated from the Scherrer equation as 5.4 nm.
Main peaks corresponding to pure TPA, which were observed at
2H = 25.88 and 2H = 34.72, were also seen in the X-ray diffraction
patterns of the TPA impregnated MCM-41 (TPA@MCM-41). As it
can be seen in Fig. 5a, peaks observed at 2H values of 29.52 and
37.92 also correspond to the Keggin structure of TPA. These results
indicated that, in the case of TPA impregnated MCM-41 catalyst,
Keggin structure was essentially conserved. MCM-41 is a mesopor-
ous material having a narrow ordered pore size distribution. The
characteristic peaks of the ordered pore structure of MCM-41 were
expected at 2h values of about 2.5, 4.2, 4.8 and 6.2 [22]. Among
these peaks, only the main peak corresponding to d100 was ob-
served in the low angle range of XRD patterns of TPA@MCM-41
(Fig. 5a). Also, the intensity of this peak was quite low. These
results are consistent with the nitrogen adsorptiondesorption
results, which indicated closure of signicant fraction of mesop-
ores of MCM-41 with the impregnated TPA.
SEM photographs of TPA@MCM-41 indicated the presence of
agglomerated particles, in a particle-size range of 38 lm
(Fig. 6). However, in the case of the material synthesized by the
one-pot procedure, the resulting solid product was not in powder
form. After the synthesis, the solid product was crushed to the de-
sired size. SEM images of TRC-W40 showed that the average size of
the crushed catalyst particles was about 110 lm (Fig. 7).
TEM images showed well dispersed nanoballs of about 15 nm
in size, which were due to the incorporated TPA within the amor-
phous silicate matrix of the synthesized material (Fig. 8). These re-
sults were consistent with the predicted WOx cluster size from the
XRD analysis.
In order to get some information about the relative strengths of
Bronsted and Lewis acid sites of the synthesized catalyst, diffuse
reectance FT-IR spectroscopic (DRIFTS) analysis of pyridine ad-
sorbed samples was performed. By taking the difference of the
spectra of fresh and pyridine adsorbed samples, relative signi-
cance of Lewis and Bronsted acid sites on the surface of these cat-
alysts was determined. Bands observed at 1540 and 1640 cm 1 in
the DRIFT spectra of pure TPA and TPA@MCM-41 (Fig. 9) corre-
spond to the pyridinium ion adsorbed on Bronsted acid sites. Very
strong bands corresponding to Bronsted acid sites were observed
Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
5
for pure TPA and TPA@MCM-41. However, in the case of TPA
impregnated MCM-41 (TPA@MCM-41), intensity of the bands cor-
responding to Bronsted acid sites was somewhat less. Heteropoly-
acids are known to have very high Bronsted acidity. In fact, the
Hammet acidity function of TPA (Ho = 13.2) is even higher than
the Hammet acidity function of 100% sufuric acid. While TPA and
TPA@MCM-41 have high Bronsted acidity, bands observed at
1447 cm 1 and at about 1600 cm 1 in the spectra also indicated
the presence of some Lewis acid sites. However, intensity of the
bands corresponding to the Lewis acid sites was much lower than
the intensity of the bands corresponding to the Bronsted acid sites.
DRIFT spectra of the pyridine adsorbed catalysts prepared by the
one-pot hydrothermal procedure (TRC-W40(L) and TRC-W40(H))
have three distinct IR absorption bands at 1640, 1537 and
1488 cm 1 (Fig. 10). The bands at 1537 cm 1 and 1640 cm 1 corre-
spond to Bronsted acid sites, indicating strong acidity of the synthe-
sized materials. The broad band at 1442 cm 1, which belonged to
the Lewis acid sites, was observed to be quite low in intensity.
The band observed at about 1488 cm 1 is due to adsorbed pyridine
on both Bronsted and Lewis acid sites [11].
FTIR spectra of pure TPA, TRC-W40(L) and TRC-W40(H) catalyst
are given in Fig. 11. Pure TPA showed IR peaks at 1080, 981, 889,
796, 594, 522 cm 1. First ve of these bands are due to the stretch-
ing vibrations POa, WOd, WObW, WOcW, and to the bending
vibration OaPOa, respectively [8]. The subscripts signify oxygen
bridging the W and the heteroatom (a), corner-sharing (b) and
edge-sharing oxygen (c), belonging to octahedral WO6 and terminal
oxygen (d). Most of the peaks belonging to pure TPA were also ob-
served in the case of TRC-W40(L), but there was a decrease in their
intensities. This is partly due to small quantity of TPA in
TRC-W40(L) and also due to some distortion of the TPA phase in
the lattice of the synthesized material. It seems that the highest
deformation was observed in the band corresponding to PO at
1080 cm 1. In the case of TRC-W40(H), which was calcined at
400 C, characteristic peaks of the Keggin structure were mostly de-
formed. This is consistent with the XRD results of this material,
which had indicated deformation of TPA and the formation of
WOx clusters within the mesoporous silicate lattice of the synthe-
sized material after calcination.
3.2. Results of dehydration reaction experiments
Catalytic performances of TPA incorporated mesoporous cata-
lysts synthesized in this study were tested in dehydration reac-
tions of ethanol and methanol. Ethylene, which is a an important
feedstock of petrochemical industry and DEE (diethyl ether), which
is an environmentally clean transportation fuel alternate, are the
6 A. Ciftci et al. / Chemical Engineering Journal xxx (2012) xxxxxx

Fig. 7. SEM photographs of TRC-W40. Fig. 8. TEM images of TRC-W40.

main products obtained from dehydration of ethanol. On the other of TPA@MCM-41 catalyst, fractional conversion values reaching
hand, the main product of dehydration of methanol is dimethyl to 0.75 and 0.80 were obtained, respectively, in the present study.
ether, which is considered as one of the best alternatives of con- The main reason of this increase in activity of TPA is much higher
ventional diesel fuel. Fractional conversion of alcohols and the surface area of the supported TPA in comparison to its pure form.
product selectivities were calculated using the data obtained from While the surface area of pure TPA was around 1 m2/g, this new
the online analysis of the reactor exit stream. Data points reported supported catalyst had a surface area of 183 m2/g.
in this paper correspond to the averages of at least three successive The NMR study of Thomas et al. [36] had indicated the loss of
steady state experimental results obtained within a reaction period protons of TPA between 200300 C. However, the work of Obali
of 23 h. and Dogu [4], had indicated stabilization of TPA at higher temper-
atures when supported on activated carbon. In the present study,
activity of the TPA@MCM-41 catalyst was also quite stable in eth-
3.2.1. TPA@MCM-41 in ethanol and methanol dehydration reaction anol conversion, even at temperatures over 350 C, indicating sta-
Experiments were performed using 0.2 g of fresh catalyst in a bilization of TPA when supported on MCM-41.
temperature range of 200400 C and at a space time of
0.27 s.g.cm 3. TPA impregnated MCM-41 catalyst showed very
high activity in dehydration reactions of both ethanol and metha-
nol. Fractional conversion of ethanol sharply increased when reac-
tion temperature was approached to 200 C. As shown in Fig. 12,
fractional conversion of ethanol was approximately 0.75 at
200 C and an increase in activity of TPA@MCM-41 was observed
with an increase of temperature, up to 300 C. At this temperature,
ethanol conversion approached to 100%.
Heteropolyacid catalysts have very high activity in dehydration
reaction of alcohols due to their high Bronsted, acidity. However,
their activity is limited due to their very low surface area. Catalytic
activities of pure heteropolyacid catalysts had been tested in our
earlier work [10] in ethanol dehydration reaction. In that work,
ethanol fractional conversion values of 0.40 and 0.55 were re-
ported at 200 and 250 C, respectively, with pure TPA being the
catalyst. At the same reaction conditions, with the same amount Fig. 9. DRIFT spectra of pyridine adsorbed TPA and TPA@MCM-41 samples.

Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
 A. Ciftci et al. / Chemical Engineering Journal xxx (2012) xxxxxx
Fig. 10. DRIFT spectra of TRC-W40(H) and TRC-W40(L).
Fig. 11. FTIR spectra of pure TPA, TRC-W40(L) and TRC-W40(H).
Fig. 12. Ethanol fractional conversion over TPA@MCM-41 (space time 0.27 s.g/cm3).
Product distributions of ethanol dehydration reaction indicated
the formation of diethyl ether (DEE) as well as ethylene. Selectivity
of DEE was found to be higher than that of ethylene up to 220 C
(Fig. 13). Above this temperature ethylene became the main prod-
uct and its selectivity approached to 1.0 at 250 C. At temperatures
higher than 220 C, decomposition of DEE was also expected to
contribute to the formation of ethylene. As it was also discussed
in our recent publication [11], Bronsted acid sites are the main con-
tributor to DEE formation, while Lewis acid sites are also expected
to contribute to the formation of ethylene at higher temperatures.
Methanol dehydration reaction test experiments also showed a
sharp increase in methanol conversion from 0.17 to 0.79 by
increasing reaction temperature from 150 C to 200220 C
(Fig. 14). It was interesting to observe the decrease of methanol
conversion over this temperature. In the case of ethanol dehydra-
tion, only a slight decrease was observed in fractional conversion
Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
7
Fig. 13. Selectivity of products in ethanol dehydration over TPA@MCM-41 (space
time: 0.27 s.g/cm3).
Fig. 14. Methanol fractional conversion over TPA@MCM-41 (space time 0.27
s.g/cm3).
at temperatures over 300 C. Increase of temperature is expected
to increase thermodynamic limitations on conversion. However,
the decrease observed in methanol dehydration over 220 C was
much higher than it would be predicted from equilibrium consid-
erations. Some decrease of methanol conversion was also reported
at high temperatures, in our recent publication on STA incorpo-
rated mesoporous catalysts [12] and this decrease was attributed
to catalyst deactivation due to coke formation. Similarly the
decrease of catalyst activity observed in this work in methanol
dehydration is considered to be mainly due to coke formation.
Decomposition of produced DME is expected to cause coke forma-
tion at high temperatures. In the case of DME production by meth-
anol dehydration over TPA@MCM-41, operating temperatures
should be kept below 220 C.
The main product of methanol dehydration reaction was DME,
with a selectivity value of approximately 1.0, in the reaction tem-
perature range of 150300 C. Apart from DME, small amounts of
formaldehyde and methane formation was also observed as side
products (Fig. 15). Increase in the selectivity of methane was recog-
nized at temperatures higher than 300 C. This result also conrms
decomposition of produced DME at high temperatures.
3.2.2. Dehydration reaction results of alcohols with TRC-W40
Although the activity of TPA impregnated MCM-41 (TPA@MCM-
41) was very high in dehydration reactions of alcohols, TPA was
not expected to be strongly attached to the support. Through
washing of the supported catalyst with water caused leaching of
some of the impregnated TPA. Consequently, this TPA impregnated
MCM-41 catalyst was more suitable for vapor phase reactions.
However, for the TPA incorporated catalyst prepared by the one
8 A. Ciftci et al. / Chemical Engineering Journal xxx (2012) xxxxxx
Fig. 15. Variation in product selectivities in methanol dehydration over TPA@MCM-
41 (space time: 0.27 s.g/cm3).
pot procedure described in this manuscript (TRC-W40), no leach-
ing of heteropolyacid from the catalyst matrix was observed after
it was repeatedly washed with water. In fact, in the synthesis pro-
cedure of these catalysts, washing of the solid product obtained
after the hydrothermal synthesis step was continued until the pH
of the wash water was close to neutral. No loss of tungsten from
the catalyst lattice was observed during this washing step. The
W/Si ratio of the synthesized material (after the washing steps)
was found to be even greater than the W/Si ratio in the synthesis
solution. This is due to stable distribution of the WOx clusters with-
in the silicate structured mesoporous matrix of the catalyst.
Experimental results for ethanol dehydration over TRC-W40
showed that fractional conversion increased with temperature,
approaching to 1.0 at around 400 C (Fig. 16). Although the ethanol
conversion values obtained with TRC-W40 were somewhat less
than the values obtained with TPA@MCM-41, this material was
quite stable, even at temperatures as high as 400 C. Higher activity
of TPA@MCM-41 than TRC-W40 is consistent with the higher acid-
ity of this catalyst, as indicated by DRIFTS analysis of pyridine
adsorbed materials.
A similar trend was observed in methanol dehydration (Fig. 16).
Ethanol and methanol conversion values were quite close in a tem-
perature range between 200300 C. Experiments were not per-
formed at temperatures higher than 300 C, in methanol
dehydration tests. As it was observed with TPA@MCM-41, methane
formation cause a decrease in DME selectivity at higher tempera-
tures. At 180 C somewhat higher conversion was obtained with
methanol than ethanol. It was also quite promising to observe no
deactivation of TRC-W40 due to coke formation in methanol dehy-
dration, in the studied temperature range.
Product distributions obtained in ethanol dehydration experi-
ments are illustrated in Fig. 17. As shown in this gure, DEE is
Fig. 16. Ethanol and methanol fractional conversions over TRC-W40.
Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
Fig. 17. Variation in product selectivities in ethanol dehydration over TRC-W40.
the main product at temperatures lower than 250 C. DEE selectiv-
ity was close to 0.9 at 200 C. DEE selectivity decreased and ethyl-
ene selectivity increased with an increase in temperature.
Selectivity of ethylene exceeded 0.9 by increasing reaction temper-
ature over 350 C. These results are consistent with the results
obtained with TPA@MCM-41 catalyst.
In the case of methanol dehydration, main product was DME. In
fact, even at 180 C, DME selectivity was 0.97. This value further
increased with an increase in temperature, approaching to 1.0 at
250 C. Besides DME, some formaldehyde formation was also
observed, at lower temperatures. These results proved that the
dehydration activity of the synthesized catalysts were much higher
than their dehydrogenation activity.
4. Conclusions
High surface are TPA based mesoporous catalysts were success-
fully synthesized using one-pot hydrothermal and impregnation
procedures. In the synthesis of TPA incorporated silicate structured
mesoporous catalysts by the one-pot hydrothermal route
(TRC-W40), calcination temperature was found to be quite impor-
tant on the properties of the synthesized material. Well dispersion
of WOx clusters was achieved within the silicate structured meso-
porous matrix of the catalytic material, which was calcined at
400 C. Incorporated TPA was not washed away from the structure
of these materials. This catalyst showed highly stable catalytic per-
formance both in ethanol and methanol dehydration reactions.
Highly stable ethanol dehydration results, with ethanol fraction
conversion values approaching to 1.0, were obtained with an in-
crease of temperature up to 400 C. At such high temperatures, eth-
ylene selectivity also approached to 1.0, while the main product was
DEE at temperatures lower than 250 C. Very high DME selectivity
values of about 1.0 were highly promising in the case of methanol
dehydration performed in the temperature range of 180300 C.
Very high and stable ethanol fractional conversion values,
approaching to 1.0, were obtained at 300 C with the TPA impreg-
nated MCM-41-like mesoporous catalyst (TPA@MCM-41). Pro-
duced DEE was concluded to be further dehydrated to ethylene
over 220 C. In the case of methanol dehydration, DME yield passed
through a maximum at about 220 C, above which coke formation
caused catalyst deactivation. Best operating temperature was con-
cluded as about 200 C, in DME production from methanol over
TPA@MCM-41.
MCM-41 impregnated catalyst (TPA@MCM-41), was shown to
have higher activity than pure TPA, due to its much higher surface
area. Activity of this catalyst and its Bronsted acidity was also high-
er than the material prepared by the one-pot procedure (TRC-
W40). However, the material prepared by the one-pot procedure
was more stable and did not cause any coke formation up to
300 C. Besides, TPA incorporated into this material was quite
 A. Ciftci et al. / Chemical Engineering Journal xxx (2012) xxxxxx
stable and did not leach out during the repeated washing steps
with water. Results proved that TPA incorporated silicate struc-
tured mesoporous materials prepared in this work were highly
promising solid acid catalysts for dehydration reaction of alcohols.
Acknowledgements
Financial support of TUBITAK through Project No. 107M184 and
contributions of Prof. Gulsen Dogu are gratefully acknowledged.
References
[1] M. Misono, I. Ono, G. Koyano, A. Aoshima, Pure Appl. Chem. 72 (2000) 1305
1311.
[2] T. Okuhara, N. Mizuno, M. Misono, Appl. Catal. A-Gen. 222 (2001) 6377.
[3] F. Cavani, Catal. Today 41 (1998) 7386.
[4] Z. Obali, T. Dogu, Chem. Eng. J. 138 (2008) 548555.
[5] L. Degirmenci, N. Oktar, G. Dogu, Ind. Eng. Chem. Res. 48 (2009) 25662576.
[6] L. Degirmenci, N. Oktar, G. Dogu, Fuel Process. Technol. 91 (2010) 737742.
[7] S. Shikata, T. Okuhara, M. Misono, J. Mol. Catal. A: Chem. 100 (1995) 4559.
[8] P. Vzquez, L. Pizzio, C. Cceres, M. Blanco, H. Thomas, E. Alesso, L.
Finkielsztein, B. Lantano, G. Moltrasio, J. Aguirre, J. Mol. Catal. A: Chem. 161
(2000) 223232.
[9] J. Haber, K. Pamin, L. Matachowski, B. Napruszewska, J. Poltowicz, J. Catal. 207
(2002) 296306.
[10] D. Varisli, T. Dogu, G. Dogu, Chem. Eng. Sci. 62 (2007) 53495352.
[11] D. Varisli, T. Dogu, G. Dogu, Ind. Eng. Chem. Res. 47 (2008) 40714076.
[12] A. Ciftci, D. Varisli, T. Dogu, Int. J. Chem. React. Eng. 8 (2010) A45.
[13] A. Ciftci, N.A. Sezgi, T. Dogu, Ind. Eng. Chem. Res. 49 (2010) 67536762.
[14] H. Atia, U. Armboster, A. Martin, J. Catal. 128 (2009) 307312.
Please cite this article in press as: A. Ciftci et al., Dimethyl ether, diethyl ether & ethylene from alcohols over tungstophosphoric acid based mesoporous
catalysts, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.04.016
9
[15] S. Soled, S. Miseo, G. McVicker, W.E. Gates, A. Gutierrez, J. Paes, Chem. Eng. J. 64
(1996) 235254.
[16] Y. Liu, L. Xu, B.B. Xu, Z.K. Li, L.P. Jia, W.H. Guo, J. Mol. Catal. A: Chem. 297 (2009)
8692.
[17] G. Kamalakar, K. Komura, Y. Sugi, Appl. Catal A: Gen. 310 (2006) 155163.
[18] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)
710712.
[19] X. Guo, M. Lai, Y. Kong, W. Ding, Q. Yan, Langmuir 20 (2004) 28792882.
[20] A. Taguchi, F. Schuth, Microporous Mesoporous Mater. 77 (2005) 145.
[21] O. Terasaki, Stud. Surf. Sci. Catal. 148 (2004) 241260.
[22] Y. Gucbilmez, T. Dogu, S. Balci, Ind. Eng. Chem. Res. 45 (2006) 34963502.
[23] J. Toufaily, M. Soulard, J.L. Guth, J. Patarin, L. Delmonte, T. Hamieha, M. Kodeih,
D. Naoufal, H. Hamada, Colloid. Surf. A 316 (2008) 285291.
[24] G. Karthikeyan, A. Pandurangan, J. Mol. Catal. A: Chem. 311 (2009) 3645.
[25] R. Palcheva, A. Spojakina, L. Dimitrov, K. Jiratova, Microporous Mesoporous
Mater. 122 (2009) 128134.
[26] H.J. Kim, Y.G. Shul, H. Han, Appl. Catal A: Gen. 299 (2006) 4651.
[27] T. Dogu, D. Varisli, Turk. J. Chem. 31 (2007) 551567.
[28] A. Takahara, M. Saito, M. Inaba, K. Murata, Catal. Lett. 105 (2005) 249252.
[29] T. Kito-Borsa, D.A. Pacas, S. Selim, S.W. Cowley, Ind. Eng. Chem. Res. 37 (1998)
33663374.
[30] D. Varisli, T. Dogu, G. Dogu, Ind. Eng. Chem. Res. 48 (2009) 93949401.
[31] D. Varisli, T. Dogu, G. Dogu, Chem. Eng. Sci. 65 (2010) 153159.
[32] D. Varisli, K.C. Tokay, A. Ciftci, T. Dogu, G. Dogu, Turk. J. Chem. 33 (2009) 355
366.
[33] K.C. Tokay, T. Dogu, G. Dogu, Chem. Eng. J. doi: 10.1016/j.cej.2011.12.034, in
press.
[34] A. Ciftci, Nanocomposite Naon and Heteropolyacid Incorporated Mesoporous
Catalysts for Dimethyl Ether Synthesis from Methanol, MS Thesis, Middle East
Technical University, Ankara, Turkey, 2009.
[35] M. Fujiwara, K. Shiokawa, Y.C. Zhu, J. Mol. Catal. A: Chem. 264 (2007) 153161.
[36] A. Thomas, C. Dablemont, J.M. Basset, F. Lafebre, C.R. Chimie 8 (2005) 1969
1974.