3496 Ind. Eng. Chem. Res.

2006, 45, 3496-3502

Ethylene and Acetaldehyde Production by Selective Oxidation of Ethanol Using

Mesoporous V-MCM-41 Catalysts
Yesim Gucbilmez and Timur Dogu*
Department of Chemical Engineering, Middle East Technical UniVersity, 06531Ankara, Turkey

Suna Balci
Department of Chemical Engineering, Gazi UniVersity, 06570 Ankara, Turkey

Vanadium-incorporated MCM-41 type catalytic materials, which were synthesized by a direct hydrothermal
synthesis procedure, showed very high activity and high selectivity in the production of ethylene from ethanol
in an oxidative process. Ethylene selectivity showed a significant increase with an increase in temperature
over 300 °C, while relatively high acetaldehyde selectivities were observed at lower temperatures. An ethylene
yield value of 0.66 obtained at 400 °C with an O2/ethanol feed ratio of 0.5 was beneficial from the point of
view that these results might open a new pathway for the production of ethylene from a nonpetroleum
environmentally friendly feedstock, namely, bioethanol. The optimum V/Si ratio of the catalyst, which gave
the maximum ethylene yield, was found to be around 0.04. Experimental results showing the formation of
acetaldehyde and not showing the formation of ethylene in the absence of gas-phase oxygen and the catalyst
deactivation observed in such conditions suggested a redox mechanism involving the surface lattice oxygen
of the catalyst in acetaldehyde production, while the involvement of adsorbed oxygen was concluded to take
place in the formation of ethylene.

Introduction aldehyde and diethyl ether, by selective oxidation of ethanol

Ethylene is one of the main intermediate chemicals used as
a raw material in the petrochemical industry. Polyethylene,
ethylbenzene-styrene, ethylene dichloride, and ethylene oxide-
glycol are some of the major petrochemicals which are produced
from ethylene. Ethylene is commercially produced by the
thermal cracking of saturated hydrocarbons, such as ethane and
propane. Due to thermodynamic limitations, thermal cracking
reactors operate at temperatures as high as 850 °C, to maintain
the desired conversion levels. Typical ethylene yields in the
thermal ethane dehydrogenation plants are about 0.55. Finding
new pathways to produce ethylene from different starting
materials and using more efficient processes has been a
challenging research area in the past decade.1
In the literature, catalytic oxidative dehydrogenation of ethane
was proposed as an alternative method to produce ethylene at
much lower temperatures, without any equilibrium limitations.2-4
The success of oxidative dehydrogenation of ethane strongly
depends on the development of selective catalysts with high
activity.5-9 Bodke et al.10 proposed a high temperature-short
contact time catalytic process to achieve a high selectivity of
ethylene by the oxidative dehydrogenation of ethane.
Developments in the use of ethanol and ethanol-based
oxygenates as alternative motor vehicle fuels, fuel additives,11-13
or as a feedstock to produce hydrogen14,15 attracted significant
attention of researchers and fuel producers. Ethanol might be
produced by the fermentation of sugar and crop wastes. Recent
studies on selective catalytic oxidation of ethanol are focused
on the production of acetaldehyde using vanadium-based oxide
catalysts.16-22 However, in some of these studies formation of
small amounts of ethylene was also indicated. Kannan et al.23
also indicated the formation of ethylene, together with acet-
* To whom correspondence should be addressed. E-mail: tdogu@
metu.edu.tr.
10.1021/ie050952j CCC: $33.50 © 2006 American Chemical Society
Published on Web 04/11/2006
over microporous vanadium silicate molecular sieves.
Vanadium-based mixed oxide catalysts show high activity
for the oxidative dehydrogenation of saturated hydro-
carbons.2-8,16-19 A redox mechanism, involving the lattice
oxygen of V2O5, is generally accepted to be responsible in the
selective oxidation reactions. Our recent diffuse reflectance
Fourier transform spectroscopy (DRIFTS) studies also proved
the formation of ethoxy species on the catalyst surface and the
involvement of the surface lattice oxygen through a redox
mechanism, in the oxidative dehydrogenation of ethane over a
V-Mo-Nb mixed oxide catalyst.8
Here, we propose a new process for the production of ethylene
from an environmentally friendly nonpetroleum feedstock,
namely, from ethanol, by oxidative catalytic dehydrogenation
using vanadium-incorporated MCM-41 type mesoporous cata-
lysts. MCM-41-based catalysts are mesoporous high surface area
silicate-structured materials with narrow pore size distri-
butions.24-26 These materials may be activated by the incorpora-
tion of metals or metal oxides into the MCM-41 structure by
direct synthesis27-29 or postsynthesis methods, including im-
pregnation,30,31 ion exchange,28 grafting,29 and chemical vapor
deposition. Vanadium-incorporated MCM-41 type catalytic
materials are reported as attractive catalysts for the partial
oxidation of alkanes to alkenes.28-30 In the present study, high
surface area vanadium-incorporated MCM-41 type catalytic
materials are synthesized and tested in the selective oxidation
of ethanol.
V-MCM-41 Catalyst Preparation and Characterization
V-MCM-41 catalysts used in this work are synthesized
following a direct hydrothermal synthesis procedure. In the
preparation of the catalysts, an aqueous solution containing
27 wt % SiO2 was used as the silica source, cetyltrimethyl-
ammonium bromide as the surfactant, and vanadyl sulfate

Figure 1. X-ray diffraction pattern of the catalyst V4b-MCM-41.
hydrate as the vanadium source. Hydrothermal synthesis was
performed in a Teflon-lined stainless steel autoclave at 120 °C
for 96 h. The product of the hydrothermal synthesis was washed
until the pH of the filtrate was about 7, dried in a vacuum, and
calcined in contact with a flow of dry air. In the calcination
step, the furnace temperature was increased from room tem-
perature to 550 °C, at a heating rate of 1 °C/min and the sample
was kept at 550 °C for 6 h. Further details of the preparation
procedure were reported in our recent publication.27
The V/Si ratios of the synthesized catalysts were determined
by the energy-dispersive spectrometry (EDS), X-ray photoelec-
tron spectroscopy (XPS), and atomic absorption spectroscopy
techniques. Among the different V-MCM-41 type catalytic
materials synthesized with different V/Si ratios, the catalyst
having a V/Si molar ratio of 0.04 showed the highest activity
in the selective oxidation of ethanol to ethylene. The X-ray
diffraction (XRD) pattern of this catalyst (Figure 1) showed
the characteristic Bragg peaks of the MCM-41 strucure at 2θ
values of 2.40, 4.06, 4.65, and 6.02. The Brunauer-Emmett-
Teller (BET) surface area of this catalyst (V4b-MCM-41) was
found as 1062 m2/g. XRD and BET results for this catalyst
clearly indicated that the MCM-41 structure was not distorted
by the incorporation of vanadium into the structure. However,
a significant decrease of the surface area and some distortions
of the XRD patterns were observed for the catalysts having
higher V/Si ratios. For insance, the BET surface areas of the
two V-MCM-41 catalysts prepared with the V/Si molar ratios
of 0.133 and 0.159 were 813 and 481 m2/g, respectively. Some
physical and structural properties of the catalysts used in the
ethanol oxidation experiments are reported in Table 1. The
characteristic lattice parameter a (the repeating distance between
two pore centers) was calculated32,33 from a ) 2d(100)(3)-1/2.
The pore wall thickness δ was then estimated27 from the lattice
parameter a and the average pore diameter dp using δ ) a -
0.95dp. Some decrease of the surface area, together with an
increase in the pore wall thickness, was observed by the
incorporation of small amounts of vanadium into the MCM-41
structure. Narrow pore size distributions and typical type IV
nitrogen adsorption isotherms of these V-MCM-41 catalysts
were also reported in our previous publication.27 For the catalysts
containing high amounts of vanadium (for instance for the
catalyst containing a V/Si molar ratio of 0.133), pore size
distributions were wider and some distortions were observed
from the MCM-41 structure. Consequently, the values of the
characteristic lattice parameter and the pore wall thickness were
not reported for this catalyst in Table 1.
Ind. Eng. Chem. Res., Vol. 45, No. 10, 2006 3497
Ethanol Selective Oxidation Experiments
Selective oxidation of ethanol (EtOH) was carried out in a
stainless steel fixed bed flow reactor packed with 0.2 g of
catalyst. The catalyst was supported from both ends by quartz
wool. Ethanol, which was introduced into the reaction system
using a syringe pump, was mixed with O2 or with an O2 + He
mixture of desired composition in an evaporator which was
heated to 150 °C. The gaseous mixture was then passed through
the fixed bed reactor, which was placed into a tubular furnace.
All the flow lines were heated to eliminate condensation of
ethanol. Chemical composition of the reactor effluent stream
was continuously analyzed using a Varian CP 3800 gas
chromatograph. High-purity oxygen and helium gases and high-
purity liquid ethanol (over 99%) were used in the experiments.
Selective oxidation experiments were carried out at different
temperatures between 150 and 400 °C with O2/EtOH molar
ratios changing between 0.0 and 2.0 in the feed stream. In most
of the experiments, the total flow rate of the gas mixture was
kept at 31.6 cm3/min. At each reaction condition, a sufficient
amount of time was allowed for the system to reach steady state.
At least three successive steady-state data points were obtained
at each reaction condition, and the average of these data points
was used in the analysis. The results of the succesive chemical
analysis of the reactor exit stream compositions were found to
be highly reproducible. Also, a set of preliminary experiments
carried out in the same system with no catalyst in the reactor
proved that the contribution of the gas-phase reactions were
negligible.
Results and Discussions
Results of the selective oxidation experiments carried out with
the V4b-MCM-41 catalyst showed that the major products
obtained were ethylene and acetaldehyde (AA). Besides these
two major products, formation of carbon dioxide, methane,
diethyl ether, acetic acid, ethyl acetate, and diethylacetal were
also observed at some reaction conditions. Fractional conversion
of ethanol (XEtOH) and product selectivities (Si), which are
defined as the ratio of moles of ethanol converted to product i
to the total moles of ethanol converted, are calculated from the
chemical composition of the reactor exit stream.
For a reactant gas mixture containing an O2/EtOH molar ratio
of 0.5, the fractional conversion of ethanol showed a sharp
increase with an increase in temperature, reaching 0.96 at 375
°C (Figure 2a). This fractional conversion of ethanol became
0.99 at 400 °C. As it is shown in Figure 2b, an increase in the
O2/EtOH ratio also caused a further increase in the fractional
conversion of ethanol. For instance, the fractional conversion
values of ethanol obtained at 300 °C with gas mixtures
containing O2/EtOH molar ratios of 0.5 and 1.2 were 0.24 and
0.98, respectively (Figure 2a,b).
At temperatures lower than 300 °C, the fractional conversion
of ethanol is quite low and the major product is acetaldehyde.
For an O2/EtOH feed ratio of 0.5, acetaldehyde selectivity
showed a decrease from 1.0 to 0.26 with an increase of
temperature from 200 to 400 °C. The oxygen conversion values
were also evaluated from the chemical analysis of the product
stream. Parallel to the decrease of the acetaldehyde yield values,
the ratio of the moles of oxygen reacted to the moles of ethanol
reacted was found to decrease from about 0.45 to 0.23 by
increasing the temperature from 250 to 400 °C.
The increase of the ethylene selectivity from zero to 0.67
with an increse of temperature from 200 to 400 °C was exciting
(Figure 2a). The highest ethylene yield was obtained as 0.66 at
3498 Ind. Eng. Chem. Res., Vol. 45, No. 10, 2006

Table 1. Some Properties of V-MCM-41 Type Catalysts Used in Selective Oxidation of Ethanol
surface area, m2/g
adsorption lattice pore wall
catalyst V/Si in MCM-41 BET BJH pore vol, cm3/g dpore, nm d(100 ) param a, nm thickness, nm
MCM-41a - 1400 1489 1.00 2.69 3.02 3.49 0.94
V1-MCM-41 0.006 1315 1362 0.92 2.71 3.14 3.63 1.06
V4b-MCM -41b 0.040 1062 1340 1.09 3.20 3.76 4.34 1.30
V3-MCM-41a 0.133 813 526 0.44 2.85 3.14
a Properties reported by Gucbilmez et al.27 b Prepared in this study.

Figure 2. Ethanol conversion (XEtOH) and product selectivity (Si) values

obtained with V4b-MCM-41 with O2/EtOH feed ratios of (a) 0.5 and (b)
1.2.

400 °C with an O2/EtOH feed ratio of 0.5. This yield value is

significantly higher than the ethylene yield in a conventional
plant producing ethylene by the thermal dehydrogenation of
ethane. Besides, the feedstock used in this work is a nonpetro-
leum environmentally friendly chemical, namely, ethanol, which
might be produced by the fermentation of sugar beat and/or
crop wastes.
The feed composition of the reactor also has a significant
effect on the product distribution. Especially at high tempera-
tures, increase of the O2/EtOH ratio in the feed stream caused
a significant reduction in the acetaldehyde selectivity together
with an increase in the carbon dioxide selectivity (Figure 2a,b).
For instance at 400 °C, the increase of the O2/EtOH ratio from
0.28 to 2.0 caused a reduction in the acetaldehyde selectivity
from 0.64 to 0.06. This effect is more clearly seen in Figure
3a-c, in which the variations of ethanol conversion, acetalde-
hyde, and ethylene yields were plotted as a function of the O2/
EtOH feed ratio, at 400, 375, and 300 °C, respectively. For T
g 375 °C, the increase of the O2/EtOH ratio in the feed stream
to a value of about 0.5 caused a sharp increase in the ethylene
yield. Further increase in this ratio caused a slight decrease in
the ethylene yield. The acetaldehyde yield showed a maximum
at an O2/EtOH ratio of about 0.28, at 400 °C. Reduction of the
AA yield and a corresponding increase in the carbon dioxide
yield with a further increase in the O2/EtOH ratio indicated a
Figure 3. Ethanol conversion (XEtOH) and product yield (Yi) values at
different O2/EtOH feed compositions using V4b-MCM-41: (a) 400, (b)
375, and (c) 300 °C.
consecutive reaction of further oxidation of AA in the presence
of excess oxygen. This effect became less at lower temperatures.
For instance, at 375 °C, the maximum observed in the
acetaldehyde yield became wider and shifted to higher O2/EtOH
ratios (Figure 3b). At even lower temperatures, this maximum
disappeared. For instance, at 300 °C, ethylene and acetaldehyde
yields showed a similar increasing trend with an increase in
the O2/EtOH ratio and reached to about the same value of 0.39
at excess oxygen conditions (Figure 3c).
Besides the formation of ethylene, acetaldehyde, and carbon
dioxide, small amounts of methane, diethyl ether (DEE),
diethylacetal (DEA), acetic acid (AAc), ethyl acetate (EAc), and
even some ethane were observed, especially at low O2/EtOH
 Ind. Eng. Chem. Res., Vol. 45, No. 10, 2006 3499

Table 2. Product Distributions at Different Temperatures and Feed Compositions with V4b-MCM-41
selectivities
O2/EtOH conversion EtOH SAA Sethylene SCO2 SCH4 SDEE SDEA SAAc SEAc Sethane
400 °C
2.00 0.99 0.06 0.61 0.27 0.06
0.50 0.99 0.26 0.67 0.03 0.01 0.02 0.01 Trace
0.28 0.49 0.64 0.14 0.03 0.07 0.02 0.02 Trace 0.05 0.03
375 °C
2.00 0.99 0.08 0.59 0.22 0.09 0.02
0.50 0.96 0.28 0.64 0.03 0.01 0.02 0.01 0.01
0.28 0.42 0.72 0.07 0.04 0.05 0.02 0.02 0.06 0.02
300 °C
2.00 0.95 0.40 0.41 0.06 0.02 0.06 0.04 0.01
0.50 0.24 0.49 0.28 0.01 0.09 0.07 0.01 0.05

feed compositions and at lower temperatures. A summary of
the product selectivities and the ethanol conversion values
obtained in the 300-400 °C temperature range is given in Table
2.
To have more insight about the mechanisms of ethylene and
acetaldehyde formation reactions, the activity of the V4b-
MCM-41 catalyst was also tested in the absence of oxygen gas.
Before these experiments, the catalyst bed was swept with
helium at the reaction temperature. In an experiment carried
out with a feed stream containing only ethanol and helium (with
a He/EtOH ratio of 0.5) and using the same amount of catalyst
and the same total flow rate of the gas mixture as in Figure 2,
formation of some acetaldehyde was observed at 400 °C, at the
initial times (Figure 4). The total conversion of ethanol showed
a decreasing trend from 0.36 to 0.08 within about 200 min, in
the absence of oxygen gas. Parallel to this decrease of total
conversion, acetaldehyde yield values also decreased from 0.31
to 0.05. At the initial times, no ethylene formation was observed
in the absence of oxygen gas. Although some increase of
ethylene selectivity was observed with time, ethylene yield
values remained lower than 0.02 throughout these experiments.
These results indicated the involvement of the surface lattice
oxygen of the catalyst in the formation of acetaldehyde during
the oxidative dehydrogenation of ethanol. It is generally believed
that redox sites produce acetaldehyde in the presence of oxygen.
Involvement of the surface vanadyl (VdO) species of the
vanadium silicate molecular sieves in the formation of acet-
aldehyde during the selective oxidation of ethanol was also
demonstrated in the work of Kannan et al.23 Elimination of an
hydrogen atom from the adsorbed ethoxy species (hydrogen
atom connected to the carbon atom of the ethoxy species which
was bonded to the catalyst site) by a lattice oxygen of the
catalyst may be responsible for the formation of acetaldehyde
Figure 4. Ethanol conversion (XEtOH) and yield values (Yi) obtained as a
function of time on the catalyst V4b-MCM-41 in oxygen-free medium at
400 °C (He/EtOH ) 0.5).
on the catalyst surface. A similar mechanism, involving the
removal of the R-hydrogen from the adsorbed ethoxy species
in the formation of acetaldehyde was also reported by Tesser
et al.16 The reduction of the catalytic activity and the corre-
sponding decrease in the acetaldehyde yield in the absence of
gas-phase oxygen, indicated the consumption of the surface
lattice oxygen of the catalyst. Formation of water together with
acetaldehyde showed the involvement of oxygen during the
dehydrogenation of ethanol (reaction 1). Our results supported
the literature results suggesting the involvement of the lattice
oxygen in such oxidative dehydrogenation processes.
C2H5OH + 1/2O2 f CH3COH + H2O (1)
In the presence of oxygen gas, the catalyst is expected to be
reoxidized. In fact, the experiments carried out after reoxidizing
the deactivated catalyst at 500 °C showed that the activity of
the catalyst was majorly restored. Chemical analysis of the
reactor exit stream during these catalyst reoxidation runs showed
the formation of trace amounts of CO2. These results indicated
the formation of small amounts of coke during the experiments
carried out in the absence of oxygen gas. Formation of such
trace amout of coke might also have contributed to the
deactivation of the catalyst in the absence of oxygen gas.
Formation of no or very small amounts of ethylene in the
absence of oxygen gas is a strong indication of the involvement
of the adsorbed oxygen in the formation of ethylene over this
catalyst. In the conventional dehydration reaction of ethanol,
oxygen gas does not seem to be involved.
C2H5OH f C2H4 + H2O (2)
However, our results showed that this reaction did not take place
on the V-MCM-41 catalyst in the absence of gas-phase oxygen.
Ethylene is expected to be formed on the catalyst surface majorly
as a result of an oxidative dehydrogenation reaction step.
Adsorbed oxygen atoms seem to catalyze reaction 2. With an
increase in temperature and in oxygen concentration, a bridged
structure involving two different sites and an oxygen atom may
form on the surface, which may then give ethylene and water.
As reported in the theoretical study of Shinohara et al.,35 shift
of a β hydrogen of the adsorbed ethoxide to a neighboring base
site (oxide ion) may explain the formation of ethylene. The
oxygen atom which should remain on the surface as a result of
this surface reaction step, was probably used in the further
oxidation of surface species in the formation of CO2 and the
other oxygenated reaction products. However, this explanation
requires further justification by future mechanistic studies (such
as DRIFTS studies) involving the detection of the surface
intermediates during the reaction. Formation of acetaldehyde
through reaction 1 and the formation of the other reaction
3500 Ind. Eng. Chem. Res., Vol. 45, No. 10, 2006
products such as carbon dioxide, acetic acid, diethyl ether,
diethylacetal, and ethyl acetate, etc., cause reduction in ethylene
selectivity. For high O2/EtOH feed ratios (for instance at an
O2/EtOH feed ratio of 2.0), further oxidation of the reaction
products was expected, and this caused further increase in the
amount of CO2 formed. For the O2/EtOH feed ratios much less
than 0.5, formation of the other side products became quite
significant and ethanol conversions also became much less than
unity.
Small amounts of diethyl ether observed at low O2/EtOH feed
ratios and at lower temperatures are formed by a dehydration
reaction of ethanol on the acid sites.
2C2H5OH f C2H5-O-C2H5 + H2O (3)
By increasing the temperature over 300 °C, decomposition of
diethyl ether may also contribute to the formation of ethylene.
C2H5-O-C2H5 f 2C2H4 + H2O (4)
Among the other products, acetic acid is expected to be
formed as a result of a consecutive reaction involving acet-
aldehyde.
CH3CHO + /2O2 f CH3COOH
1
(5)
Diethylacetal (DEA) observed at low O2/EtOH feed ratios
indicated a surface reaction between two adsorbed ethoxy
species and acetaldehyde. The overall reaction for DEA forma-
tion is due to the following reaction:
2C2H5OH + CH3CHO f CH3CH(OCH2CH3)2 + H2O (6)
As reported in our previous publication,27 the XPS peak of
V 2p3/2 at 517.2 eV showed that the oxidation state of vanadium
in the fresh V-MCM-41 catalyst synthesized in this work was
+5. The pale yellow color of the V-MCM-41 type catalysts
synthesized in this work turned to pale gray-white during the
selective oxidation experiments. A similar color change was
observed in the work of Le Bars et al.5 in oxidative dehydro-
genation of ethane over V2O5/SiO2 catalysts prepared by the
impregnation and grafting techniques, this color change was
attributed to the desorption of water molecules and to the change
in the coordination number of the surface vanadia species from
octahedral to tetrahedral, and it was stated by these authors that
such a change in the coordination number might contribute to
the enhancement of selectivity of the catalyst. Formation of
tetrahedrally coordinated vanadium in the silica framework was
also reported by Lim and Haller.40 The color change observed
in our work may also be an indication of a change in the
oxidation state of vanadium during the selective oxidation
reaction. The oxidation state of vanadium at the surface of the
catalyst is expected to change during the selective oxidation
reaction, following a redox mechanism. Partially reduced
catalysts containing more V4+ are generally accepted to be more
selective in the selective oxidation reactions.33
High ethylene selectivity of the V-MCM-41 catalyst syn-
thesized in this work is expected to be strongly related to the
coordination of the V, Si, and O atoms in the catalyst structure.
As it was also reported by Kannan et al.,23 diethyl ether and
ethylene production was probably due to the simultaneous
involvement of vanadyl (VdO) and V-O-Si groups in the
lattice structure of the catalyst, while VdO was responsible for
the formation of acetaldehyde. Critical functionality of the
V-O-Si bridging bonds in the selective oxidation reactions
and oxygen liberation of the surface redox sites of mixed metal
Figure 5. Ethanol fractional conversion, acetaldehyde, and ethylene yield
values obtained with catalysts containing different V/Si mole ratios. (T )
400 °C; O2/EtOH ) 0.5 in the feed stream).
oxide catalysts were also demonstrated by Wachs and co-
workers,38,39 in methanol oxidation reaction. Active site distribu-
tion of V-MCM-41 type catalysts which were measured by
titration were reported in the recent work of Yang et al.43 This
work suggested that most of the vanadium species were
incorporated into the silica framework in their catalysts. The
significance of the V-O-Si bond angle on the stability of the
catalyst was also demonstrated in that work.
In the present study, another set of experiments was carried
out using catalysts having different V/Si ratios between 0 and
0.133, with a O2/EtOH molar feed ratio of 0.5. Our results
obtained at 400 °C proved that there is an optimum V/Si ratio
of the V-MCM-41 type catalytic materials which maximized
the ethylene yield (Figure 5). Among the catalysts sudied in
this work, V4b-MCM-41, which contained a V/Si molar ratio
of 0.04, gave the highest ethanol conversion and also the highest
ethylene yield. Ethanol conversion showed an increasing trend
with an increase in the V/Si ratio of the catalyst, up to a V/Si
ratio of 0.04. For instance, experiments carried out with the
V-MCM-41 catalyst containing a V/Si ratio of 0.006 (V1-
MCM-41) gave an ethanol fractional conversion value of 0.81
at an O2/EtOH feed ratio of 0.5, at 400 °C. The corresponding
ethanol fractional conversion was 0.99 with the V4b-MCM-
41, which contained a V/Si ratio of 0.04. By the incorporation
of higher amounts of vanadium into the catalyst structure (over
0.04), a reduction was observed in the surface area of the catalyst
and the characteristic MCM-41 structure of the synthesized
catalysts was also somewhat distorted. For instance, a catalyst
containing a V/Si ratio of 0.133 had a BET surface area of 813
m2/g (BJH surface area being 526 m2/g) (Table 1). The decrease
in the surface area of the catalyst with an increase in vanadia
content (V/Si ratios being over 0.04) may be attributed to the
incomplete formation of the MCM-41 structure and/or to
plugging of mesopores. The increase of the V/Si ratio over 0.04
caused a significant increase in acetaldehyde selectivity, with a
corresponding decrease in ethylene selectivity. Also, a decrease
in the overall conversion of ethanol was observed with an
increase in the V/Si ratio, over 0.04. For instance, for the catalyst
containing a V/Si ratio of 0.133, the acetaldehyde selectivity
reached a value of 0.70 at 400 °C. The decrease of the fractional
conversion of ethanol with a significant increase in the V/Si
ratio of the catalyst (over 0.04) is partly due to the reduction of
the surface area of the catalyst. The pore structures of the

synthesized catalysts are expected to have a significant effect
on the activity and the selectivity values of these mesoporous
materials. In fact, in the recent work of Yang et al.,43 a strong
effect of pore size on the catalytic activity and the selectivity
was observed in methanol oxidation over V-MCM-41 catalysts
containing constant vanadium concentration but different pore
diameters. This effect was represented by a “volcano curve”.
As shown in Table 1, the average pore diameter of the most
active catalyst (V4b-MCM-41) was the highest among the other
catalysts used in our work in selective oxidation of ethanol.
However, the V/Si ratios (i.e. the vanadium contents) of the
catalysts synthesized in our work were not the same, and
consequently it is not possible to make a definite comment about
the effect of pore size on the activity of our catalysts, in the
selective oxidation reaction of ethanol.
Bulk V2O5 was reported to be not highly active for ethanol
oxidation.19 Also, in the case of using pure V2O5 as the catalyst,
the major product is acetaldehyde. Vanadyl species (VdO) are
generally considered the responsible species in acetaldehyde
formation. As it was reported in the literature,23 the intrinsic
activity of vanadium incorporated into the SiO2 framework was
much higher than that of nonincorporated vanadium. Our results
showing a decrease of the activity of the catalyst with an increase
in V/Si ratio over 0.04 may be partly due to the increased
amount of vanadium in extraframework positions of the catalyst.
The acetaldehyde yield values did not change much in the
catalysts having V/Si mole ratios smaller than 0.04. In fact, the
experimental results obtained with the MCM-41 catalyst con-
taining no vanadium also gave an acetaldehyde yield value of
about 0.3 (Figure 5). This result is in agreement with the recent
results of Hess et al.,41 showing the formation of significant
amout of formaldehyde over mesoporous silica SBA-15, in the
partial oxidation of methanol. This result was explained by the
presence of redox sites on the bare mesoporous silica containing
no vanadium. Our results showing the formation of some
acetaldehyde over the bare MCM-41 also supported this
conclusion that the redox sites of MCM-41 also contributed to
the formation of acetaldehyde. Over the bare MCM-41, we did
not observe the formation of any diethyl ether, and the yield of
ethylene was also quite low (about 0.09). Also, in the work of
Hess et al.,41 formation of dimethyl ether was not observed over
SBA-15 in partial oxidation of methanol and this was explained
by the absence of medium acid sites. However, the results of
Baltes et al.42 on methanol oxidation over MCM-48 indicated
the formation of some dimethyl ether. Our results obtained with
bare MCM-41 agreed with the conclusions of Hess et al.,41
which were obtained over bare SBA-15.
As it was reported in the literature, 22,35,36 basic catalysts
promote alcohol dehydrogenation in nonoxidative processes,
whereas dehydration of ethanol takes place essentially on acidic
catalysts. As a result of the dehydration process over the strongly
acidic sites of the catalysts, formation of diethyl ether and
ethylene are expected to take place. Vanadyl species are reported
to provide weak acid sites.5,23,37 It was also reported in the
literature that bare silica had very low density of acidity and
basicity. Acidity of V2O5 is expected to decrease further as a
result of incorporation of V into the SiO2 structure of MCM-
41. In fact, the recent work of Zhao et al.37 also demonstrated
that the strength of the acid sites decreased with a decrease in
vanadium loading in silica-supported vanadia catalysts. The
acidic properties of vanadium-substituted MCM-41 type materi-
als were also investigated by Lim and Haller.40 In that work, it
was claimed that vanadium-substituted MCM-41 had some
Lewis and Bronsted acid sites and Bronsted acid sites decreased
Ind. Eng. Chem. Res., Vol. 45, No. 10, 2006 3501
with decreasing vanadium content while the density of Lewis
acid sites was constant in all the samples. In that study, the
formation of weak Lewis acid sites was postulated by the
formation of isolated tetrahedrally coordinated vanadium, while
the formation of Bronsted acid sites was reported to take place
by a combination of incorporated vanadium with hydroxyl
groups, on the catalyst surface. With decreasing acidity,
desorption of the C2H4 formed on the surface is also expected
to become faster, reducing further oxidation. Our observation,
showing that the formation of ethylene did not take place in
the absence of oxygen gas, also supported the literature results,37
indicating that the strength of the acidic sites of the V-SiO2
catalysts containing small amounts of vanadium was quite low.
Concluding Remarks
Results of this work showed that ethylene can be produced
from ethanol by a selective oxidative process over V-MCM-
41 type mesoporous catalytic materials prepared by a direct
hydrothermal synthesis procedure. An ethylene yield value of
0.66, which was obtained at 400 °C with an O2/EtOH feed ratio
of 0.5, was highly beneficial. At lower temperatures and for
smaller O2/EtOH feed ratios, acetaldehyde selectivity increased,
while the overall conversion of ethanol and ethylene selectivity
decreased.
To our knowledge, there is no published work for the selective
oxidation of ethanol over V-incorporated MCM-41 type cata-
lysts. Besides, in the published literature on selective oxidation
of ethanol, the main product was observed as acetaldehyde. The
ethylene yield obtained in this work in the selective oxidation
of ethanol over V-MCM-41 type catalysts is very high and
may open new pathways to produce ethylene from a nonpetro-
leum feedstock, namely, bioethanol. Further mechanistic studies
and investigation of catalyst stability will elaborate the design
parameters of these new catalysts for practical applications.
Acknowledgment
Turkish State Planning Organization Research Grant DPT-
03-04-DPT.2003K120920-05, contributions of the Middle East
Technical University Research Fund and of Prof. Dr. Gulsen
Dogu of Gazi University are gratefully acknowledged.
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ReceiVed for reView August 19, 2005
ReVised manuscript receiVed February 21, 2006
Accepted March 17, 2006
IE050952J