Direct oxidation of dimethyl ether to ethanol over WO3/HZSM-5 catalysts

Article abstract of DOI:10.1016/j.catcom.2012.05.017

The direct oxidation of dimethyl ether (CH₃OCH₃, DME) to ethanol (CH₃CH₂OH) was carried out over WO ₃/HZSM-5 catalysts in a continuous flow type fixed-bed reactor. The effects of different zeolite types, WO₃ loading and reaction temperature on the reaction were investigated. Our results showed that modification of HZSM-5 with 10% WO₃ significantly improved the ethanol selectivity from 0.6% to 19.7%. The surface and structure of the catalysts were characterized by NH₃-TPD, BET, XRD and in situ FT-IR. Ethanol can be mainly synthesized from DME direct oxidation under the cooperation of trifunctional reactive sites offered by WO₃ modified HZSM-5 catalysts.

Full text of DOI:10.1016/j.catcom.2012.05.017

Catalysis Communications 26 (2012) 173–177
Contents lists available at SciVerse ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Direct oxidation of dimethyl ether to ethanol over WO /HZSM-5 catalysts
3
a,b
a
a
a,
Guangbo Liu , Qingde Zhang , Yizhuo Han , Yisheng Tan ⁎
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, P. R. China
Graduate University of Chinese Academy of Sciences, Beijing 100049, P. R. China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
The direct oxidation of dimethyl ether (CH OCH , DME) to ethanol (CH CH OH) was carried out over
3
3
3
2
Received 21 February 2012
Received in revised form 15 May 2012
Accepted 17 May 2012
WO
types, WO
that modification of HZSM-5 with 10% WO
9.7%. The surface and structure of the catalysts were characterized by NH
Ethanol can be mainly synthesized from DME direct oxidation under the cooperation of trifunctional reactive
sites offered by WO modified HZSM-5 catalysts.
3
/HZSM-5 catalysts in a continuous flow type fixed-bed reactor. The effects of different zeolite
loading and reaction temperature on the reaction were investigated. Our results showed
significantly improved the ethanol selectivity from 0.6% to
-TPD, BET, XRD and in situ FT-IR.
3
3
Available online 24 May 2012
1
3
Keywords:
DME
Direct oxidation
Ethanol
3
© 2012 Elsevier B.V. All rights reserved.
WO
3
/HZSM-5
In situ FT-IR
1
. Introduction
In the next decade, the increasing global energy demand would not
a C-C bond [10,11]. Theoretically, DME as the first step product in
MTO and MTG processes may potentially lead to ethanol production
[12–14]. In addition, in the MTO and MTG processes, ethylene is an
be met by traditional fossil energy resources (i.e. coal, oil and natural
gas) [1]. Recently, ethanol has become an important chemical since it
can be used as alternative motor fuel. Ethanol is mainly synthesized
industrially by catalytic hydration of ethylene, which is petroleum
based and quite costly. Traditionally, ethanol is mainly produced by the
fermentation of corn or other food based feedstock. However, industrial
scale ethanol fermentation using traditional food based feedstock is
limited due to the low yield and the worldwide food shortage. Therefore,
finding a new green-route to produce ethanol from other economic raw
material has become a new challenge for many scientists.
3
important product over the HZSM-5 catalysts [15,16]. The WO and
HZSM-5 catalysts were both considered as good performance cata-
lysts in the reaction of gas-phase direct hydration of ethylene[17,18].
However, up to now, there have been no reports on direct oxidation
of DME to ethanol over WO
In this paper, we report a novel route for the synthesis of ethanol
from DME direct oxidation over WO modified HZSM-5 zeolites.
3
modified HZSM-5 catalysts.
3
Moreover, the effects of the type of zeolites and different metal oxides
modifications were investigated. We also characterized the surface
and structure of the catalysts before and after reaction.
Presently, dimethyl ether is used to synthesize formaldehyde and
dimethoxymethane since it can be directly synthesized from syngas
at low cost [2–5]. In addition, DME has been used as a potential and
nontoxic chemical feedstock for the synthesis of ethanol. Tsubaki et al.
have reported a two-step synthesis of ethanol from DME and CO over
combined H-Mordenite and Cu/ZnO catalysts via DME carbonylation
followed by intermediate hydrogenation [6–8]. Yu et al. obtained trace
ethanol from DME oxidation over metal oxides modified HZSM-5 cata-
lysts and they regarded ethanol as the product of the free radical
reaction [9].
2. Experimental
2.1. Catalyst preparation
The zeolite catalyst was prepared by mixing HZSM-5 powder
(SiO /Al O =25, Nankai Catalysts Plant) with a pre-determined
2 2 3
amount of pseudo-boehmite, and then the mixture was extruded.
The extrudates were dried at 383 K overnight and calcined at 773 K
for 6 h. HY (SiO
were also obtained under the same conditions.
WO /HZSM-5 catalysts were prepared by an incipient wetness im-
pregnation method. HZSM-5 support was impregnated with an aqueous
solution of ammonium tungsten oxide hydrate ((NH 39·xH O,
2 2 3 2 2 3
/Al O =4.8) and HMOR (SiO /Al O =20) zeolites
Theoretical studies of C-C bond formation in the methanol-
to-gasoline (MTG) and methanol-to-olefin (MTO) processes have
shown that ethanol as an intermediate is the first formed species with
3
4
)
6
W
12
O
2
Alfa Aesar) at room temperature for 4 h, then dried in air at 383 K for
overnight, and calcined at 773 K for 5 h. Thus, 2%, 5%, 8%, 10%, 20%, 25%,
⁎
Corresponding author. Tel./fax: +86 351 4044287.
E-mail address: tan@sxicc.ac.cn (Y. Tan).
3
30%WO /HZSM-5 (wt %) catalysts were prepared.
1566-7367/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2012.05.017

174
G. Liu et al. / Catalysis Communications 26 (2012) 173–177
2
.2. Catalytic oxidation of dimethyl ether
mainly limited by C-H bond activation in chemisorbed DME, a step
that forms methoxy methyl intermediates, on site pairs consisting of
chemisorbed oxygen atoms with vicinal vacancy sites present on
surfaces nearly saturated with chemisorbed oxygen atoms [19,20].
In this reaction, COx may be generated by the C-O bond breaking
The catalytic oxidation reactions were carried out in a continuous
flow type fixed-bed reactor containing the catalyst (3 ml, 20–40
mesh). The catalyst was treated with a flow of O (25 ml/min) for 1 h
before reaction at 673 K. The reactant mixture consisted of DME and
(nDME/nO2 =1:1). The outlet stream line from the reactor to the
2
3 3
and the over-oxidation of the CH and CH O groups over metal oxides
O
2
modified ZSM-5 catalysts [21].
gas chromatograph was heated at 423 K. The hydrocarbon reaction
products were analyzed on gas chromatograph (GC-9A, Shimadzu)
equipped with a FID and a PEG-40 M column (30 m×0.32 mm) and a
GC-4000A with TCD (Porapak T column), and on a GC-4000A equipped
Therefore, the different oxidizability of metal oxides and the
interaction with HZSM-5 may lead to different main products during
the catalytic reaction. The strong oxidation capacity and interaction
between metal oxide and zeolite easily result in more COx generated as
with a TCD (TDX-01 column) for analyzing H
.3. Catalyst characterization
XRD patterns were measured on a Bruker Advanced X-Ray Solutions/
2
, CO, CO
2
and CH
4
.
the main products. However, WO
achieves much higher selectivity of ethanol maybe due to the appropriate
redox properties and the interaction between WO and zeolite.
3
modification to HZSM-5 significantly
3
2
3.2. Effect of supports on the catalyst performances
D8-Advance using Cu Kα radiation. The anode was operated at 40 kV
and 40 mA. The 2θ angles were scanned from 5° to 70°.
It can be seen from Table 2 that the conversion of DME is relatively
high over the strong acidic zeolite catalysts. For the HZSM-5 and
Surface area and micropore area of the samples were measured
by BET nitrogen adsorption isotherms at 77 K using a Tristar 3000
machine. Micropore volume was obtained by the t-plot method.
Diffuse reflectance infrared spectra were measured by a Bruker
Tensor 27 with a MCT detector (64 scans, 4 cm− ). The catalyst was
placed in an in situ IR cell equipped with KBr windows (Harrick).
HMOR zeolites, trace amount of ethanol was found, while CO, CO
and CH were the main products during the DME catalytic oxidation
2
4
reaction. In contrast, there is no ethanol found in the products over
the HY zeolite, which may be due to the much greater average pore
size of HY zeolite [22], and methanol was the main product instead.
We assumed that the acidity of the HY zeolite may be apt to obtain
methanol due to the hydrolysis reaction of DME and H O produced
2
in the DME oxidation, and the pore structure and the larger pore
1
−
4
After heating at 673 K for 2 h and evacuating at 10
was cooled down to reaction temperature and the spectrum was
recorded. Next, the mixture gas of DME and O (nDME/nO =1:1)
bar, the cell
2
2
was introduced into the cell, and the spectra of catalyst adsorption
were recorded. Finally, the catalyst desorption spectra were recorded
after 30 min of reaction and the pressure of the cell was evacuated to
size in HY zeolite may not be benefit for the C-C bond generation.
However, when the zeolites were modified by WO
conversion decreased except for HZSM-5. Over the WO
3
, the DME
/HMOR
3
−
3
1
0
bar.
The NH
catalyst, no ethanol was detected, but the selectivity of methanol
was obviously increased. The ethanol selectivity was significantly
3
-TPD spectra were recorded in a fixed-bed reactor system
equipped with a thermal conductivity detector. The catalyst (100 mg)
3
improved from 0.6% to 19.7% when WO was used to modify HZSM-5.
was pretreated at 773 K under Ar flow (40 ml/min) for 2 h and then
cooled down to 373 K under Ar flow. Then NH was introduced into
3
the flow system. The TPD spectra were recorded at a temperature
It is suggested that there maybe exists the cooperation between the
acid-redox sites and the special pore channel function of the catalyst,
which could further promote the synthesis of ethanol in the reaction.
rising rate of 5 K/min from 373 to 800 K.
3
3.3. Effect of WO loading on the performances of catalysts
3
. Results and discussion
Fig. 1 shows the performance of the catalysts with different WO
loading on the catalytic oxidation of DME. For the HZSM-5 catalyst,
the main products observed were CO, CH and CO , while the selectivity
of ethanol was only 0.6%. When the 10% WO /HZSM-5 catalyst was
3
3
.1. Effect of different metal oxide modification on the catalyst performance
4
2
Table 1 lists the results of catalytic oxidation of DME over catalysts
3
with different metal oxide loading on HZSM-5. CO and CO
main products when the Nb /HZSM-5 catalyst was used. The highest
selectivity of CO was obtained with V
catalysts. In the presence of MnO /HZSM-5 catalyst, CO
major product. Interestingly, when WO
2
are the
used, the ethanol selectivity reached 19.7% and a 99.7% conversion of
DME was observed. The selectivity of ethanol increases with increasing
2 5
O
2
O
5
/HZSM-5 and MoO
3
/HZSM-5
was the
was used to modify HZSM-5
WO
CO and CO
3
loading initially and then decreases, while the selectivities of the
side-products exhibit an opposite trend. WO , as a kind of
2
2
2
3
3
oxidation component, was introduced into the HZSM-5 zeolite, which
moderated the acidity and enhanced the oxidizability of the catalyst.
The decrease of the catalysts acidity was also proved by comparing
catalyst, the products have a greater ratio of organic compounds con-
taining oxygen and the ethanol selectivity reached 19.7%.
However, there is massive COx formation in the products, but
DME flammability may not exist in the reaction. DME combustion is
weak acid support (Al
2
O
3
) and the WO
3
supported on weak acid support
(10%WO /Al O ). When HZSM-5 was modified with an appropriate
3 2 3
Table 1
a
Catalytic oxidation of DME over different metal oxides loading on HZSM-5 .
Catalysts
DME
Selectivity (C-mol%)
Conversion (%)
CO
CH
4
CO
2
HCHO
CH
3
OH
MF
DMM
ETOH
Toluene
Nb
2
O
5
/HZSM-5
98.9
99.9
99.8
99.9
99.7
35.7
70.3
16.2
75.7
15.9
7.8
18.8
1.6
10.9
8.1
47.5
10.9
81.9
13.3
22.2
5.8
0
0.09
0
0.5
0
0.08
0
0.06
0
0
0
0.05
0.04
0
0.02
0
0.9
0
0
0
19.7
1.6
0
0.01
0
V
2
O
5
/HZSM-5
MnO
MoO
WO
2
/HZSM-5
/HZSM-5
3
3
/HZSM-5
17.7
12.8
1.1
3.1
M
x
O
y
-10%M
x
O
y
(M=Nb, V, Mn, Mo, W).
a
=1:1, GHSV=800 h−1
.
Reaction conditions: 563 K, atmospheric pressure, DME:O
2

G. Liu et al. / Catalysis Communications 26 (2012) 173–177
modified zeolitesa.
3
175
Table 2
Catalytic oxidation of DME over different zeolites and WO
Catalysts
DME
Selectivity (C-mol%)
Conversion (%)
CO
CH
4
CO
2
HCHO
CH
3
OH
MF
DMM
ETOH
Toluene
HZSM-5
HMOR
HY
80.2
75.4
40.1
99.7
41.1
28.6
48.6
42.7
0
15.9
0
13.2
30.6
3.8
8.1
29.2
0.02
24.9
19.3
0
22.2
1.8
2
6.3
4.7
5.9
17.7
7.9
1.1
3.6
1.8
88.5
12.8
61
0.03
0
0.01
0.05
0
0.4
0.4
0.4
1.1
0
0.6
0.05
0
19.7
0
2.2
0.3
0
3.1
0
1
1
1
0%WO
0%WO
0%WO
3
3
3
/HZSM-5
/HMOR
/HY
86.1
10.5
0.01
0.2
0
0
a
=1:1, GHSV=800 h−1
.
Reaction conditions: 563 K, atmospheric pressure, DME: O
2
amount of WO
3
, the strong acid sites on the HZSM-5 catalyst was
The DME conversions at different Gas Hourly Space Velocity were
also investigated. The results show that the DME conversion did not
change significantly at 563 K when the GHSV increased in a certain
weakened as new redox sites were generated. The strong acid sites result
in a high selectivity of CO and the over-oxidation sites may lead to more
−
1
2
CO .
range (600–1000 h ).
3
3
.5. Catalysts characterization
3
1
.4. Effects of reaction temperature on the catalytic performance of
0%WO /HZSM-5
3
.5.1. XRD
3
Fig. 3 shows the XRD patterns of the 10%WO /HZSM-5 catalyst
before and after reaction. The peaks at 8.1° and 9.1° were assigned to
HZSM-5, the peaks at 23.1° and 45.2° were assigned to both HZSM-5
Fig. 2 shows the DME conversion, selectivity of ethanol and other
side-products obtained over WO /HZSM-5 catalysts at different
temperatures. When the reaction temperature was at 543 K, the
selectivity of ethanol reached 3.9% and DME conversion was 73.8%,
while the selectivity of CO and CO were at 31.6% and 21.7%, respectively.
2
When the reaction temperature was increased to 563 K, the selectivity of
ethanol was increased to 19.7% and the DME conversion was almost
3
3 3
and WO , and the peak at 63.9° was assigned to WO . After the reaction,
the diffraction peaks intensity at 23.1° and 45.2° apparently increased,
the peaks at 8.1°and 9.1° decreased and a new peak at 63.9° appeared.
This result may be generated by the change of HZSM-5 structure and
the aggregation of WO
WO /HZSM-5 catalysts before and after the reaction, the results show
that the dispersion of WO and the structure of HZSM-5 may affect
the activation of the catalyst.
3
after the reaction. Through comparing the
1
00%, while the selectivity of CO and CO
in the reaction temperature resulted in a significant decrease in the
selectivity of ethanol, but a sharp increase in CO and CO selectivity.
2
decreased. However, further
3
3
2
As can be seen in Fig. 2, the optimum reaction temperature is 563 K
with relatively high ethanol selectivity and low COx selectivity.
Therefore, we suggest that the effect of the zeolite acidity is related to
the temperature. The temperature also affects the cooperation of the
acid sites, redox sites and pore channel function. When the temperature
is higher than 563 K, COx becomes the main products. It may be because
the DME molecules reacted acutely and were oxidized deeply over the
catalyst at high temperature. At the lower temperature, the DME mole-
cule was mainly oxidized to COx. This may be because the cooperation
of acid sites, redox sites and pore channel function can not promote
the oxidation of DME molecule to ethanol, but to COx. When the reaction
occurred at 563 K, the optimum cooperation of acid sites, redox sites and
pore channel function can effectively promote the oxidation of DME to
ethanol and DME is not over oxidized.
3
.5.2. Surface textural properties
The surface textural properties obtained for the different catalysts
are shown in Table 3. The surface area, micropore area and micropore
volume exhibited by zeolites with metal oxide loading were smaller
than that of pure zeolites. This may be due to the pore blocked partly
by the WO
obviously over the catalysts except the WO
these catalysts, there exists a positive correlation between the DME
conversion and the surface area. Comparing the WO /HZSM-5 catalysts
before and after the reaction, the surface area, micropore area and the
micropore volume of the catalysts decrease sharply after the reaction.
It is shown that there exists carbon deposited on the WO
3
. After the 10% WO
3
loading, the DME conversion decreases
3
/HZSM-5 catalyst. Over
3
3
/HZSM-5
1
00
100
80
60
40
20
0
100
100
80
60
40
20
8
0
0
0
0
8
6
4
2
0
0
0
0
0
DME
CO
HCHO
CH OH
DME
CO
HCHO
CH
CH
3
OH
3
CH
4
Ethanol
Toluene
6
4
2
CH
4
3
CH
2
OH
CO2
CO
2
Toluene
0
0
0
5
10
15
20
25
30
540
550
560
570
580
590
600
610
WO3 loading (wt%)
Temperature (K)
Fig. 1. Catalytic oxidation of DME over different WO
Reaction conditions: 563 K, atmospheric pressure, DME:O
3
contents modified HZSM-5 zeolites.
Fig. 2. Catalytic oxidation of DME over 10%WO
Reaction conditions: atmospheric pressure, DME:O
3
/HZSM-5 at different temperatures.
=1:1, GHSV=800 h−
1
.
=1:1, GHSV=800 h
−1
.
2
2

176
G. Liu et al. / Catalysis Communications 26 (2012) 173–177
3
6
0
6
3
6
6
2
3
7
2
0
3
7
8
0
HZSM-5/WO
3
before reaction
after reaction
3000 3200 3400 3600 3800 4000
λ cm-1
HZSM-5
DME and O desorption
2
DME andO adsorption
2
HZSM-5/WO
3
WO
3
Catalyst before adsorption
HZSM-5
500
1000
1500
2000
2500
3000
3500
4000
10
20
30
40
50
60
70
λ /cm-1
2
θ / degree
Fig. 4. The IR spectra of DME and O
catalyst.
2
adsorption and desorption on the 10%WO
3
/HZSM-5
Fig. 3. The XRD patterns of the catalyst before and after the reaction.
catalyst after the reaction from the results of the element analysis. The
deposed carbon probably blocked the pores and the aggregation of
when the WO
the interaction between WO
the acid site number of the 10%WO
3
3
loading increased from 0% to 10%. This may be due to
and HZSM-5(see Fig. 4). After the reaction,
/HZSM-5 catalyst decreased and the
3
WO
3
after the reaction, resulting in the sharp decrease of surface area,
micropore area and micropore volume, and further resulting in the de-
crease of DME conversion and the catalyst deactivation. Thus, the re-
sults suggest that the effect of the HZSM-5 pore channel is related to
the activation of the catalyst.
strong acid site disappeared probably owing to the carbon deposition of
the catalyst after the reaction. According to the results of the catalytic
oxidation and the characterization of catalysts, we suggest that the
acid sites may be one kind of active sites for the titled reaction and the
catalyst acidity could affect the product distribution. Then, the 10%
WO
According to the results of the catalytic oxidation of DME and the
characterization of the 10%WO /HZSM-5 catalysts before and after
the reaction, we propose that the acid sites, redox sites and pore
channel function of WO /HZSM-5 were all necessary for the reaction.
For the titled reaction, the acid sites maybe activate the DME molecules,
the pore channel function may lead to the C-C bond formation and the
redox sites may be the reason for the C2 to ethanol. To a great extent,
ethanol can be synthesized under the cooperation of the acid-redox
sites and the special pore channel function of catalyst.
3
/HZSM-5 catalyst with optimum acidity is efficient to form ethanol.
3
.5.3. In situ FT-IR spectra of catalysts
Fig. 4 shows the in situ FT-IR spectra of HZSM-5 and the 10%WO /
3
3
HZSM-5 zeolites. After purification under vacuum condition, infrared
spectra of the catalysts show some bonds in the ν(OH) region at
−
1
−1
3
3
600–3800 cm . The 3606, 3662 and 3720 cm
assigned to hydroxyl and silanol groups [21]. By comparing the spectra
of HZSM-5 and the WO modified catalyst, it can be seen that the
peak appeared after the WO was loaded on HZSM-5. The
region; however, when WO-H
interacts with HZSM-5, the WO-H bond shifts to the higher frequency
peaks have been
3
−
1
3
780 cm
3
−
1
O-H of H
2
4
WO is at 3200–3550 cm
−
1
[
23,24]. The 3780 cm
tion. When the mixture gas (DME:O
cell, we can see that all the ν(OH) bonds disappeared. After the cell
bond may be the v(WO-H) stretching vibra-
4
. Conclusions
2
=1:1) was introduced into the
In conclusion, the direct oxidation of DME to ethanol has been
−
1
was pumped under vacuum, all the peaks except the 3780 cm
successfully conducted over WO
selectivity of 19.7% was achieved with 10% WO
63 K. Ethanol can be synthesized by DME direct oxidation under the
3
modified HZSM-5 catalysts. Ethanol
were recovered. We suggest that the WO-H bond may be the active
site for DME adsorption. This new active site could play very important
role in the selective synthesis of ethanol from DME oxidation.
3
/HZSM-5 catalyst at
5
3
10% WO /HZSM-5
3
.5.4. Temperature programmed desorption
The NH -TPD results for the different catalysts are shown in Fig. 5.
With the increase of WO loading, both of the total acid site number and
2
0% WO HZSM-5
3
3
HZSM-5
0% WO
3
1
3
/HZSM-5 after reaction
the strong acid site number of catalyst decreased obviously, especially
Table 3
The textural properties of zeolites, 10% WO
reaction.
3
modified zeolites and the catalysts after
Catalysts
BET surface Micropore area Micropore volume
2
2
3
(m /g)
(m /g)
(cm /g)
HZSM-5
355
220
212
142.2
6.77
302
219
4.2
253.6
242
8.9
0.1
1
1
0%WO
0%WO
3
/HZSM-5
0.065
0.003
0.14
0.1
0.002
0.12
0.11
0.004
3
/HZSM-5 after reaction 19.7
329
HMOR
1
1
0%WO
0%WO
3
/HMOR
248
3
/HMOR after reaction 13.4
298
400
500
600
700
800
800
HY
Temperature (K)
1
1
0%WO
0%WO
3
/HY
279
21
3
/HY after reaction
3 3 3
Fig. 5. NH -TPD spectra of WO /HZSM-5 catalysts with different WO loading.

G. Liu et al. / Catalysis Communications 26 (2012) 173–177
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This work was supported by the National Natural Science Foundation
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