Ethanol direct synthesis from dimethyl ether and syngas on the combination of noble metal impregnated zeolite with Cu/ZnO catalyst

Article abstract of DOI:10.1016/j.cattod.2013.10.042

In this report, ethanol (EtOH) was selectively synthesized from dimethyl ether (DME) and syngas (CO + H₂) with a dual-catalyst bed in a single reactor. H-Mordenite (H-MOR) zeolite was used to convert DME into methyl acetate (MA) through carbonylation reaction in the first stage reaction, and then EtOH was produced by MA hydrogenation over the Cu/ZnO catalyst at the second stage. In addition, the metals such as Pt, Pd or Ru were used to impregnate H-MOR catalyst by impregnation method to improve its catalytic activity. The combination of Pt/H-MOR catalyst with Pt loading amount of 0.4 wt.% and Cu/ZnO catalyst showed excellent catalytic performance compared with the conventional combination of pure H-MOR catalyst and Cu/ZnO catalyst.

Full text of DOI:10.1016/j.cattod.2013.10.042

GModel
CATTOD-8668; No. of Pages5
ARTICLE IN PRESS
Catalysis Today xxx (2013) xxx–xxx
Contents lists available at ScienceDirect
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
Ethanol direct synthesis from dimethyl ether and syngas on the
combination of noble metal impregnated zeolite with Cu/ZnO catalyst
Peng Lua, Guohui Yanga, Yuki Tanakaa, Noritatsu Tsubakia,b,∗
a Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan
b JST, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 12 July 2013
Received in revised form 10 October 2013
Accepted 14 October 2013
Available online xxx
In this report, ethanol (EtOH) was selectively synthesized from dimethyl ether (DME) and syngas (CO + H2)
with a dual-catalyst bed in a single reactor. H-Mordenite (H-MOR) zeolite was used to convert DME
into methyl acetate (MA) through carbonylation reaction in the first stage reaction, and then EtOH was
produced by MA hydrogenation over the Cu/ZnO catalyst at the second stage. In addition, the metals such
as Pt, Pd or Ru were used to impregnate H-MOR catalyst by impregnation method to improve its catalytic
activity. The combination of Pt/H-MOR catalyst with Pt loading amount of 0.4 wt.% and Cu/ZnO catalyst
showed excellent catalytic performance compared with the conventional combination of pure H-MOR
catalyst and Cu/ZnO catalyst.
Keywords:
Ethanol synthesis
Carbonylation
Dimethyl ether
Hydrogenation
Zeolite catalyst
Crown Copyright © 2013 Published by Elsevier B.V. All rights reserved.
1. Introduction
CO + CH3OCH3
→
H-MORCH3COOCH3
→
Cu/ZnOCH3OH + CH3CH2OH
Ethanol as one of fuel alternatives is now paid more atten-
tion. It is also one of the important starting feedstock for other
chemicals production [1]. Ethanol is widely blended into the
unleaded gasoline with varied percentages, significantly decreasing
the dependence of our society on crude oil, at the same time reduc-
ing the harmful tailpipe emissions of CO, particulate matter, NOx,
and other pollutants.
Now, ethanol is mainly synthesized by two methods. The first
one is the catalytic hydration of ethylene [2,3], where the ethylene
is from petroleum cracking. The second method is fermentation
method with corn or other foods as the raw material [4]. Unlike
the conventional route, recently, we presented a new ethanol syn-
thesis way [5,6], in which ethanol can be synthesized readily from
dimethyl ether (DME) and syngas (CO + H2) in a dual-catalyst bed
reactor by using the combination of zeolite catalyst and Cu/ZnO
catalysts [7,8] as shown by Scheme 1. The DME is converted into
methyl acetate (MA) by its carbonylation reaction with CO on the
first H-Mordenite (H-MOR) zeolite catalyst [9–13], and then the
formed MA is successively hydrogenated to ethanol and methanol
on the followed Cu/ZnO catalyst. The formed MeOH can be recycled
to produce DME easily by simple dehydration. The total reaction
route is presented below.
H
2
The DME carbonylation involves the formation of methyl groups
via DME reaction with the OH groups in H-MOR zeolite, the reac-
tion of methyl groups with CO via insertion into the C O bonds in
bound methyls and the followed reaction of the formed acetyls with
DME to produce methyl acetate and regenerate methyl intermedi-
ates. For DME carbonylation reaction on H-MOR zeolite catalyst,
the active sites in eight-member ring channels of zeolite catalyst
are readily saturated with DME-derived intermediates like methyl
groups, the rate of methyl acetate synthesis mainly depends on CO
pressure. In order to improve the DME carbonylation on zeolite
catalyst, in this report, Pt, Pd or Ru as promoter was used to respec-
tively impregnate H-MOR zeolite. The combination of M/H-MOR
(M = Pt, Pd, Ru) and Cu/ZnO catalyst was used for ethanol direct
synthesis from DME and syngas through our developed route. The
combination of Pt/H-MOR with Cu/ZnO showed higher catalytic
activity and ethanol selectivity. The effect of Pt loading amount
to DME carbonylation and ethanol synthesis was investigated in
detail.
2. Experimental
2.1. Catalyst preparation
∗
The H-MOR zeolite (Si/Al2 = 19.9, SBET = 309.05 m2 g−1) was used
for DME carbonylation in this report as a reference. The metal (Pt, Pd
Corresponding author. Tel.: +81 76 445 6846; fax: +81 76 445 6846.
E-mail address: tsubaki@eng.u-toyama.ac.jp (N. Tsubaki).
0920-5861/$ – see front matter. Crown Copyright © 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2013.10.042
Please cite this article in press as: P. Lu, et al., Ethanol direct synthesis from dimethyl ether and syngas on the combination of noble metal
impregnated zeolite with Cu/ZnO catalyst, Catal. Today (2013), http://dx.doi.org/10.1016/j.cattod.2013.10.042

GModel
CATTOD-8668; No. of Pages5
ARTICLE IN PRESS
2
P. Lu et al. / Catalysis Today xxx (2013) xxx–xxx
ZnO
Cu
a
CO+DME
Methyl acetate
Ru/H-MOR
Pd/H-MOR
Pt/H-MOR
Quartz wool
Cu/ZnO
H-MOR or
M/H-MOR
CO+DME+H2
Ethanol
b
H-MOR
Cu/ZnO
Scheme 1. Illustration of catalyst loading in reactor (a) the single zeolite catalyst
for DME carbonylation and (b) the dual-catalyst bed reactor for ethanol synthesis.
or Ru) impregnated H-MOR catalyst was prepared by conventional
impregnation method from the corresponding coordinated com-
pound and named as M/H-MOR (M = Pt, Pd or Ru). Metal loading
amount of M/H-MOR catalyst was 1.0 wt.% by weight. The obtained
catalyst was dried at 393 K for 12 h, calcined in air at 623 K for 1 h,
followed by granulating into the size of 20–40 mesh. Other series
of Pt/H-MOR catalysts with varied Pt loading weight (0.2, 0.4, 0.6,
and 0.8 wt.%) were also prepared by the same way.
The Cu/ZnO catalyst (Cu/Zn = 1:1, molar ratio) was prepared by
conventional co-precipitation method. An aqueous solution con-
taining metal nitrate salts, and an aqueous solution of sodium
carbonate were simultaneously added into 300 ml deionized water
with constant stirring. The precipitation temperature and pH value
were maintained at 333 K and 8.0 respectively. The obtained slurry
was aged for 12 h, then filtrated and washed repeatedly with ade-
quate deionized water in order to remove the excessive sodium
cations. The obtained catalyst was treated by followed drying at
393 K for 12 h and then screened into the size between 20–40 mesh.
Before loading the catalysts into the reactor, the M/H-MOR and
Cu/ZnO catalyst were first reduced by a flow of 5% hydrogen diluted
in nitrogen at 573 K for 10 h, and then passivated by 1% oxygen
diluted in nitrogen at room temperature for 1 h.
0
20
40
60
80
2Theta (degree)
Fig. 1. XRD patterns of H-MOR, M/H-MOR and Cu/ZnO.
the reaction pressure was kept at 1.5 MPa with the syngas flow rate
of 40 mL min−1
.
All the effluent in gas phase from the reactor outlet was analyzed
by an online gas chromatograph equipped with a thermal conduc-
tivity detector (TCD) and Porapak Q column. The liquid products
were collected by an ice-water trap with 1-butanol acting as sol-
vent, and then analyzed by another chromatograph equipped with
a flame-ionization detector (FID) and a connected dual column
(packed by Gaskuropack 54 and Porapak N packing materials). All
of the selectivity values of products in this report were calculated
in molecular selectivity, instead of carbon molar base.
3. Results and discussion
3.1. Characterization of M/H-MOR zeolite catalyst
2.2. Catalyst characterization
Fig. 1 shows the XRD patterns of H-MOR zeolite and metal
impregnated H-MOR zeolite. Comparing the XRD patterns of metal
impregnated H-MOR with pure H-MOR, it is difficult to find some
obvious changes because the metal loading amount is relatively low
(1 wt.%). However, it should be noted that the relative crystallinity
of M/H-MOR zeolite decreased slightly after metals impregnating.
The average crystallite sizes of the Cu and ZnO calculated by Scher-
rer equation are 9.0 nm and 7.9 nm respectively.
Powder X-ray diffraction (XRD) patterns of catalysts were
recorded on a Rigaku RINT 2400 X-ray Diffractometer equipped
˚
with a Cu-K␣ radiation (ꢀ = 1.5406 A). Scans were recorded in the
2ꢁ range of 5–80◦ with a step size of 0.02◦ s−1. The crystallite sizes
were calculated based on the Scherrer equation. The surface area
of catalyst was measured in an automatic gas adsorption system
(Quantachrome, Autosorb-1, Yuasa Co.) by N2 adsorption.
2.3. Catalytic reactions
All of the catalytic reactions were conducted with a stain-
less steel reactor (9.5 mm OD). In order to compare the influence
of different reactant gas for DME carbonylation, single H-MOR
(0.5 g) zeolite catalyst was also loaded into the reactor and
then heated from room temperature to 573 K (8 K min−1) under
flowing nitrogen (40 mL min−1), and maintained at that tem-
perature for 2 h to remove the adsorbed water and organic
impurities. To investigate the influence of varied syngas to
DME carbonylation, different syngas, such as Ar/DME/CO/H2
(1.54:1.02:47.44:50.00), Ar/DME/CO/H2 (1.47:1.99:46.54:50.00),
and Ar/DME/CO/H2 (1.55:2.35:46.10:50.00) were tested respec-
tively after the reactor being cooled to the reaction temperature
of 493 K.
100
60
80
40
60
40
20
0
20
0
420 440 460 480 500 520 540
Reaction temperature (K)
For EtOH synthesis, the dual-catalyst bed model in one reactor
was used. H-MOR zeolite or M/H-MOR zeolite catalyst for DME car-
bonylation was put into the reactor at the upper layer and Cu/ZnO
catalyst for MA hydrogenation was loaded at the lower layer. The
reactant gas Ar/DME/CO/H2 (1.55:2.35:46.10:50.00) was used and
Fig. 2. Effect of the reaction temperature for DME carbonylation on H-MOR cat-
alyst. The conversion of DME (ꢀ) and selectivity of products CO2 (ꢁ), MA (ꢂ),
EA (ꢂ), and CH4 (ꢃ). Reaction conditions: P = 1.5 MPa; weightH-MOR = 0.5 g. Syngas:
Ar/DME/CO/H2 = 1.54/1.02/47.44/50.00.
Please cite this article in press as: P. Lu, et al., Ethanol direct synthesis from dimethyl ether and syngas on the combination of noble metal
impregnated zeolite with Cu/ZnO catalyst, Catal. Today (2013), http://dx.doi.org/10.1016/j.cattod.2013.10.042

GModel
CATTOD-8668; No. of Pages5
ARTICLE IN PRESS
P. Lu et al. / Catalysis Today xxx (2013) xxx–xxx
3
Table 1
Table 2
Effect of the reaction temperature for DME carbonylation on H-MOR catalyst.
DME carbonylation on H-MOR zeolite with different syngas.
Temp.(K)
DME conv. (%)
Selectivity (mol%)
Type
DME conv. (%)
Selectivity (mol%)
MA
MA
100
CH4
CO2
EA
CO2
423
453
473
493
513
533
0.7
27.2
47.6
63.7
66.9
67.5
–
–
0
0.1
2.5
3.1
22.5
23.7
0
Syngas a
Syngas b
Syngas c
63.7
46.3
20.7
96.8
97.2
97.9
3.1
2.8
2.1
98.5
1.4
1.6
2.1
4.8
6.3
95.9
94.8
72.7
38.8
–
–
–
31.2
Reaction conditions: T = 493 K, P = 1.5 MPa; weightH-MOR = 0.5 g. Syngas a: Ar/
DME/CO/H2 = 1.54/1.02/47.44/50.00. Syngas b: Ar/DME/CO/H2 = 1.47/1.99/
46.54/50.00. Syngas c: Ar/DME/CO/H2 = 1.55/2.35/46.10/50.00.
Reaction conditions: P = 1.5 MPa; weightH-MOR = 0.5 g. Syngas: Ar/DME/CO/
2 = 1.54/1.02/47.44/50.00.
H
In addition, a small amount of CO2 as by-product is detected in
the final products, which is attributed to the WGS reaction. Ethanol
and methanol are not detected on the single H-MOR zeolite catalyst
since there is no Cu/ZnO catalyst in reactor for MA hydrogenation
[18,19].
3.2. DME carbonylation on pure H-MOR catalyst at different
temperature
Fig. 2 shows the effect of reaction temperature for DME carbony-
lation on pure H-MOR zeolite catalyst and the related data are also
showed in Table 1. The conversion of DME rises from 0.7 to 63.7%
with increasing reaction temperature from 423 to 493 K. The prod-
ucts of DME carbonylation include MA, ethyl acetate (EA) and CO2,
and the selectivity of MA is higher than 94.8%. With further increas-
ing the temperature higher than 493 K, the conversion of DME rises
slightly, but the selectivity of MA decreases rapidly and the selectiv-
ity of CO2 rises obviously. When the temperature reaches to 533 K,
CH4 is detected as showed in Fig. 2 and Table 1.
3.4. Metal impregnated H-MOR zeolite combined with Cu/ZnO
catalyst for ethanol synthesis
In this report, a dual-catalyst bed reactor with H-MOR or M/H-
MOR zeolite catalyst as the first catalyst and Cu/ZnO as the second
catalyst is used for ethanol synthesis. By this method, DME is ini-
tially converted to MA through DME carbonylation on the H-MOR
zeolite catalyst, and then the produced MA is hydrogenated to
ethanol on the Cu/ZnO catalyst.
It is deduced that Water-Gas-Shift (WGS) reaction happens on
H-MOR zeolite catalyst at 513 K and higher reaction temperature
of 533 K, which will result in the formation of CO2. In addition, at
higher reaction temperature, the formed MA can be decarbonized
to hydrocarbons such as CH4 [14], yielding CO2 at the same time.
Besides that, DME can also be decomposed into CO, H2 and CH4 on
the acidic sites at high reaction temperature [5,15,16].
Fig. 4 shows the reaction results of different metal impregnated
H-MOR zeolite catalyst for ethanol synthesis, and the correspond-
ing data are also listed in Table 3. The reaction temperature and
pressure are 493 K and 1.5 MPa respectively. All of the catalysts
have the metal loading amount of 1.0 wt.%. For the combination of
pure H-MOR zeolite and Cu/ZnO catalyst, the conversion of DME
is only 21.0%. To the metal impregnated H-MOR zeolite catalyst,
the conversion of DME is improved obviously. It is considered that,
with the loading of Pt, Pd or Ru, the gaseous CO can be readily
adsorbed on these metallic sites and enrich the surface CO con-
centration. The key step of the total reaction is the attack of CO at
the adsorbed methyl species that are formed on the Brønsted acid
sites of zeolite catalyst, and CO can be activated at the metal sites
located in the neighboring aluminum frameworks. Consequently,
DME conversions are enhanced due to the accelerated CO insertion
reaction pushed by the high surface CO concentration. But the Ru
and Pd impregnated H-MOR zeolite catalyst decrease the selectiv-
ity of EtOH to 24.4 and 24.8% respectively, which is much lower
than the catalyst combination of pure H-MOR zeolite and Cu/ZnO
catalyst. Possibly, the used promoter of Pd or Ru in the first
3.3. Varied syngas for DME carbonylation on pure H-MOR zeolite
Fig. 3 summarizes the reaction results obtained with varied syn-
gas composition. DME conversion decreases from 63.7 to 20.7%
along with the syngas from a to c and the corresponding data are
also showed in Table 2. The formation rate of methyl acetate is pro-
portional to CO pressure [17]. The active sites in the eight-member
ring channels of zeolite catalyst are saturated with DME-derived
intermediates like methyl groups. Kinetically relevant steps involve
the interaction of gas-phase or adsorbed CO with DME-derived
intermediates to form acetyls, and then these acetyls further react
with DME to produce MA.
60
50
100
60
40
80
30
30
20
10
60
40
25
20
3
2
1
0
40
20
20
0
Syngas a
Syngas b
Syngas c
Fig. 3. DME carbonylation on H-MOR zeolite with different syngas. The con-
version of DME (ꢀ) and the selectivity of products CO2 (ꢁ) and MA (ꢂ).
Reaction conditions: T = 493 K, P = 1.5 MPa; weightH-MOR = 0.5 g. Syngas a:
Ar/DME/CO/H2 = 1.54/1.02/47.44/50.00. Syngas b: Ar/DME/CO/H2 = 1.47/1.99/
46.54/50.00. Syngas c: Ar/DME/CO/H2 = 1.55/2.35/46.10/50.00.
Fig. 4. Ethanol synthesis on H-MOR catalyst and M/H-MOR catalysts. The con-
version of DME (ꢀ) and selectivity of products MeOH (᭹), EtOH (ꢄ), CO2 (ꢁ),
MA (ꢂ), and EA (ꢂ). Reaction conditions: T = 493 K, P = 1.5 MPa; weightH-MOR = 0.5 g,
weightCu/ZnO = 0.5 g. Syngas: Ar/DME/CO/H2 = 1.55/2.35/46.10/50.00.
Please cite this article in press as: P. Lu, et al., Ethanol direct synthesis from dimethyl ether and syngas on the combination of noble metal
impregnated zeolite with Cu/ZnO catalyst, Catal. Today (2013), http://dx.doi.org/10.1016/j.cattod.2013.10.042

GModel
CATTOD-8668; No. of Pages5
ARTICLE IN PRESS
4
P. Lu et al. / Catalysis Today xxx (2013) xxx–xxx
Table 3
Ethanol synthesis on H-MOR catalyst and M/H-MOR catalysts.
Type
DME conv. (%)
BET surface
area (m2 g−1
Selectivity (mol%)
)
MeOH
EtOH
CO2
MA
EA
H-MOR and C-Z
21.0
23.7
23.6
32.7
309.05
317.56
316.67
319.29
48.7
57.0
55.4
51.0
31.6
24.4
24.8
28.7
15.9
15.6
16.1
17.3
2.2
1.9
2.0
1.8
1.7
1.2
1.7
1.3
Ru/H-MOR and C-Z
Pd/H-MOR and C-Z
Pt/H-MOR and C-Z
Reaction conditions: T = 493 K, P = 1.5 MPa; weightH-MOR = 0.5 g, weightCu/ZnO = 0.5 g; Syngas: Ar/DME/CO/H2 = 1.55/2.35/46.10/50.00. The metal loading weight on each one
zeolite catalyst is 1.0 wt.%.
40
30
20
DME rises rapidly with Pt loading amount rises from 0 to 0.4 wt.%.
More Pt loading on H-MOR zeolite higher than 0.8 wt.% cannot fur-
ther promote its catalytic activity. It is deduced that the formation
of DME-derived intermediates methyl groups on the active sites
of zeolite catalyst may be restricted by the excess metal loading
amount. Much more metal loading on zeolite or the replacement
of H+ on zeolite by other cations significantly decrease the total
amount of Brønsted acid sites, restricting the formation of DME-
derived intermediates of methyl groups and acetyl species, finally
depressing the activity of zeolite catalyst on DME carbonylation.
The products selectivity are showed in Fig. 5 and Table 4, where
we can find that the ethanol synthesis can be realized through this
developed route. Better DME conversion of 35.2% and the high-
est ethanol selectivity of 32.6% are realized on the combination of
0.4 wt.% Pt/H-MOR zeolite with Cu/ZnO catalyst.
50
40
30
20
10
0
0.0
0.2
0.4
Pt (wt%)
0.6
0.8
1.0
Fig. 5. Influence of different Pt loading amount on ethanol synthesis. The con-
version of DME (ꢀ) and selectivity of products MeOH (᭹), EtOH (ꢄ), CO2 (ꢁ), MA
(ꢂ), and EA (ꢂ). Reaction conditions: T = 493 K, P = 1.5 MPa; weightPt/H-MOR = 0.5 g,
weightCu/ZnO = 0.5 g. Syngas: Ar/DME/CO/H2 = 1.55/2.35/46.10/50.00.
4. Conclusions
catalyst layer contribute part of methanol to the final reaction prod-
ucts, therefore leading to higher methanol selectivity and lower
ethanol selectivity. On the other hand, Pt impregnated H-MOR cat-
alyst shows the highest DME carbonylation conversion of 32.7%
among the tested catalysts. At the same time, it also gives a higher
EtOH selectivity of 28.7%.
Therefore, in the following section, the combination of
Pt/H-MOR zeolite with Cu/ZnO catalyst is adopted for further inves-
tigation due to its excellent catalytic activity on ethanol synthesis.
Different from the conventional ethanol synthesis way, in this
report, we presented an ethanol synthesis method with syngas
as feedstock in a dual-catalyst bed reactor. The catalyst combina-
tion in reactor comprised of an H-MOR zeolite catalyst layer and a
followed Cu/ZnO catalyst layer. The dimethyl ether (DME) carbony-
lation on zeolite catalyst was the key step in the total reaction. The
reaction result on the single H-MOR zeolite catalyst showed better
catalytic activity at reaction temperature of 493 K. To promote the
zeolite catalyst activity on DME carbonylation, we employed dif-
ferent metals (Pt, Pd or Ru) to impregnate H-MOR zeolite catalyst.
The reaction results showed that Pt impregnated zeolite catalyst
obviously promoted the DME carbonylation reaction. The Pt load-
ing amount of 0.4 wt.% on H-MOR zeolite could make dimethyl
ether conversion reach 35.2% with ethanol selectivity of 32.6%.
The presented ethanol synthesis method by using the combina-
tion of Pt impregnated H-MOR zeolite catalyst and Cu/ZnO catalyst
was more effective and environmental friendly, offering a promis-
ing alternative ethanol synthesis route for chemical or energy
industry.
3.5. Pt impregnated H-MOR zeolite with varied amount for
ethanol synthesis
Fig. 5 shows the reaction results of different Pt impregnated H-
MOR zeolite catalyst for ethanol synthesis, the corresponding data
are also listed in Table 4. If the pure H-MOR zeolite is used as the first
catalyst, DME conversion is only 21.0%, the lowest value among the
tested catalysts. Increasing the Pt loading amount from 0 to 0.8 wt.%
on the H-MOR can obviously improve the conversion of DME from
21.0 to 36.4%, as showed by Fig. 5 and Table 4. The conversion of
References
Table 4
Influence of different Pt loading amount on ethanol synthesis.
[1] H.V. Fajardo, L.F.D. Probst, Appl. Catal. A: Gen. 306 (2006) 134–141.
[2] C.M. Fougret, W.F. Hölderich, Appl. Catal. A: Gen. 207 (2001) 295–301.
[3] J.W. van Hal, J.S. Ledford, X.K. Zhang, Catal. Today 123 (2007) 310–315.
[4] J.J. Spivey, A. Egbebi, Chem. Soc. Rev. 36 (2007) 1514–1528.
[5] X. Li, X. San, Y. Zhang, T. Ichii, M. Meng, Y. Tan, N. Tsubaki, ChemSusChem 3
(2010) 1192–1199.
[6] G. Yang, X. San, N. Jing, Y. Tanaka, X. Li, Q. Jin, K. Tao, F. Meng, N. Tsubaki, Catal.
Today 164 (2011) 425–428.
[7] X. San, Y. Zhang, W. Shen, N. Tsubaki, Energy Fuels 23 (2009) 2843–2844.
[8] Y. Zhang, X. San, N. Tsubaki, Y. Tan, J. Chen, Ind. Eng. Chem. Res. 49 (2010)
5485–5488.
Pt loading
DME conv. (%)
Selectivity (mol%)
amount (wt.%)
MeOH
EtOH
CO2
MA
EA
0
21.0
30.0
35.2
35.5
36.4
32.7
47.7
48.7
50.8
52.3
52.8
51.0
31.6
32.1
32.6
27.8
27.1
28.7
13.2
12.8
11.8
14.9
15.9
17.3
3.2
3.2
3.1
3.2
2.7
1.8
4.4
3.3
1.6
1.7
1.5
1.3
0.2
0.4
0.6
0.8
1.0
[9] P. Cheung, A. Bhan, G.J. Sunley, D.J. Law, E. Iglesia, J. Catal. 245 (2007) 110–123.
[10] F.E. Celik, T.J. Kim, A.T. Bell, J. Catal. 270 (2010) 185–195.
[11] Y.Y. Liu, K. Murata, M. Inaba, I. Takahara, Fuel Process. Technol. 110 (2013)
206–213.
Reaction
conditions:
T = 493 K,
P = 1.5 MPa;
weightPt/H-MOR = 0.5 g,
weightCu/ZnO = 0.5 g. Syngas: Ar/DME/CO/H2 = 1.55/2.35/46.10/50.00.
Please cite this article in press as: P. Lu, et al., Ethanol direct synthesis from dimethyl ether and syngas on the combination of noble metal
impregnated zeolite with Cu/ZnO catalyst, Catal. Today (2013), http://dx.doi.org/10.1016/j.cattod.2013.10.042

GModel
CATTOD-8668; No. of Pages5
ARTICLE IN PRESS
P. Lu et al. / Catalysis Today xxx (2013) xxx–xxx
5
[12] M.S. Kazantsev, M.V. Luzgin, G.G. Volkova, A.G. Stepanov, J. Catal. 291 (2012)
9–16.
[16] T.A. Semelsberger, K.C. Ott, R.L. Borup, H.L. Greene, Appl. Catal. B: Environ. 61
(2005) 281–287.
[13] J.L. Liu, H.F. Xue, X.M. Huang, P.H. Wu, S.J. Huang, S.B. Liu, W.J. Shen, Chin. J.
Catal. 31 (2010) 729–738.
[17] P. Cheung, A. Bhan, G.J. Sunley, E. Iglesia, Angew. Chem. Int. Ed. 45 (2006)
1617–1620.
[14] P. Mäki-Arvela, I. Kubickova, M. Snare, K. Eranen, D.Y. Murzin, Energ. Fuels 21
(2007) 30–41.
[15] K. Faungnawakij, Y. Tanaka, N. Shimoda, T. Fukunaga, S. Kawashima, R. Kikuchi,
K. Eguchi, Appl. Catal. A: Gen. 304 (2006) 40–48.
[18] J. Liu, H. Xue, X. Huang, Y. Li, W. Shen, Catal. Lett. 139 (2010) 33–37.
[19] T. Shikada, K. Fujimoto, M. Miyauchi, H. Tominaga, Appl. Catal. 7 (1983)
361–368.
Please cite this article in press as: P. Lu, et al., Ethanol direct synthesis from dimethyl ether and syngas on the combination of noble metal
impregnated zeolite with Cu/ZnO catalyst, Catal. Today (2013), http://dx.doi.org/10.1016/j.cattod.2013.10.042