RECENT ADVANCES in ENERGY & ENVIRONMENT

Direct Synthesis of Dimethyl Ether (DME) from Syngas

Kaoru TAKEISHI, and Yoshimi AKAIKE
Department of Materials Science and Chemical Engineering
Shizuoka University
3-5-1, Jouhoku, Naka-ku, Hamamatsu-shi, Shzuoka-ken, 432-8561
JAPAN
tcktake@ipc.shizuoka.ac.jp

Abstract: We have developed appropriate and excellent catalysts for direct DME synthesis. The catalysts,
Cu-Zn/Al2O3 catalysts prepared by the sol-gel method, produce DME with high DME activity and high DME
selectivity under milder reaction temperature and pressure compared with the usual direct DME synthesis catalysts
(mixed catalysts of methanol synthesis catalysts and methanol dehydration catalysts). It will be the reason why the
methanol synthesis active sites (copper) and the methanol dehydration active sites (alumina) on the sol-gel
Cu/Al2O3 catalysts exist closer than those of the mixed catalysts.

Key-Words: Dimethyl ether, DME, hydrogen, clean fuel, catalyst, sol-gel method, alumina, copper, direct
synthesis, syngas.

1 Introduction used. This mixed catalyst is similar catalysts for patent

Dimethyl ether (DME) is slightly expensive chemical
now, because DME is manufactured by dehydration
process of methanol. However, DME is expected as a
clean fuel for the 21st century, from the reasons that
DME does not contain poisonous substances, and
DME burns without particulate matters (PM) [1].
DME will be used as substitutes of liquefied
petroleum gas (LPG) and diesel oil, and will be used
for hydrogen carrier. Therefore, demand of DME will
increase rapidly, and it is necessary to mass-produce
DME economically. There is a method, direct
synthesis of DME, that DME is synthesized directly
from syngas (hydrogen and carbon monoxide), not
synthesized by dehydration of methanol. Excellent
catalysts for the direct synthesis are necessary. In this
study, copper alumina catalysts prepared by the
sol-gel method that is appropriate for DME steam
reforming [2, 3] are applied for direct DME synthesis
(3H2 + 3CO CH3OCH3 + 2CO2) that is similar
reaction of DME steam reforming (CH3OCH3 + 3H2O
3H2 + 2CO2).
2 Experimenals
For hydrogenation of carbon monoxide, Cu-Zn
(36-4wt.%)/Al2O3 catalyst prepared by the sol-gel
method was used in single, not mixed with other
catalysts such as alumina. As the comparison, a mixed
catalyst with a commercial catalyst CuO-ZnO
(50-50wt.%) (N211, Nikki Chemical Co., Ltd.) and
alumina (BK-105, Sumitomo Chemical Co., Ltd.) was
catalysts for direct DME synthesis [4]. The all
catalysts were calcined at 500 oC for 5 h and were
reduced by flowing H2 at 450 oC for 10 h. This severe
pretreatment was particularly performed for reactive
comparison to avoid the catalytic deterioration with
sintering of the catalysts by the reaction heat on
continuous experiments with the same catalysts. A
flow reactor was used for CO hydrogenation. The used
weight of catalysts was 0.5 g, and the supply of the
reaction gas flow was mainly H2/CO/Ar = 7.5/7.5/1.5
ml min-1. Argon gas was an internal standard for gas
chromatography. The reaction gas and products were
analyzed by gas chromatographs (TCD and FID).
Scanning electron microscopy - energy dispersion
X-ray spectrometry (SEM-EDS) analysis was
performed for the surface characterization.
3 Results and discussion
3.1 CO hydrogenation
The single type catalyst and the mixed catalyst were
carried out for CO hydrogenation. The part of the
results is shown in Fig. 1. Much amount of DME was
produced over Cu-Zn(36-4wt.%)/Al2O3 catalyst
prepared by the sol-gel method at 250 oC of the lower
reaction temperature. The less amount of DME was
produced over the mixed catalyst of the methanol
synthesis catalyst (N211) and the methanol
dehydration catalyst (BK-105) at 310 oC of the higher
reaction temperature. In other experiments, even if the
reaction gases contain some oxygen, the sol-gel

ISSN: 1790-5095 408 ISBN: 978-960-474-159-5

 RECENT ADVANCES in ENERGY & ENVIRONMENT
Cu-Zn/Al2O3 catalysts produce DME effectively with
long durability. The single type catalysts that have
copper sites for methanol synthesis and alumina sites
for methanol dehydration on the surface are more
appropriate and more excellent for direct DME
synthesis than the mixed catalysts that are one of the
patent catalysts for direct DME synthesis.
3.2 Hydrogen ratio for direct DME synthesis
Dependency of H2/(H2+CO) ratio was investigated on
Cu-Zn(36-4wt.%)/Al2O3 catalyst prepared by the
sol-gel method. Fig. 2 shows the part of the results.
DME is produced with the fastest production rate at
the ratio of H2/(H2+CO) = 0.5. It is suggested that
DME is produced over Cu-Zn/Al2O3 catalyst prepared
by the sol-gel method, with the reaction of the
chemical equation, 3H2 + 3CO CH3OCH3 + CO2.
3.3 Surface analysis of the catalysts
SEM-EDS analysis confirmed that copper sites for
methanol synthesis (and water gas shift reaction) and
alumina sites for methanol dehydration are co-existing
and the both sites are dispersed well on the surface of
Cu-Zn/Al2O3 catalyst prepared by the sol-gel method.
The distances of the sites for each reaction (methanol
synthesis, methanol dehydration, and water gas shift
reaction) are shorter than those of the mixed catalyst,
so the reactions are more sequentially and
systematically occurred, and the DME production rate
will be faster.
3.4 Pressure effect for direct DME synthesis
Dependency of pressure for CO hydrogenation was
investigated on Cu-Zn(36-4wt.%)/Al2O3 catalyst
prepared by the sol-gel method. Fig. 3 and Fig. 4 show
the part of the results. Rate of DME production is
linearly increased with increasing of the reaction
absolute pressure. Production rate of methanol also
increases with increasing the pressure. Methane
production rate is almost stable. (Cf. Fig. 3) From
these phenomena, selectivity for DME is increased to
100% depending on the increase of the reaction
pressure. The DME selectivity is 98% under the
pressure of 1.6 MPa. (Cf. Fig. 4) This value is very
high compared with some companies data and the
reaction condition is milder than those of the
companies (Cf. Table 1 [5]).
3.5 Durability test of the catalyst for direct
DME synthesis
ISSN: 1790-5095
Durability test for direct DME synthesis, catalyst
life-time test was carried out. Fig.5 and Fig. 6 show the
part of the results. In case of DME production rate,
there was a decrease of about 100 mol g-cat-1 h-1 from
the first biggest rate. However, the DME rate
production is almost constant after this decrease. Rate
production of methane and methanol also slightly
decreased. However, there is no obvious big
deactivation such as less production. The further
development is still need, but the catalysts are stable
and they have enough capability for practical use.
4 Conclusion
We have developed the appropriate and excellent
catalyst for direct DME synthesis. The catalysts,
Cu-Zn/Al2O3 catalysts prepared by the sol-gel method,
produce DME with high activity and high selectivity
under the mild reaction temperature and pressure.
References:
[1] T. H. Fleisch, A. Basu, M. J. Gradassi, J. G. Masin,
Dimethyl ether: A fuel for the 21st century, Studies
in Surface Science and Catalysis, Vol. 107, 1997,
pp. 117-125.
[2] K. Takeishi, H. Suzuki, Steam reforming of
dimethyl ether, Applied Catalysis A: General, Vol.
260, 2004, pp. 111-117.
[3] K. Takeishi, K. Yamamoto, Catalysts for hydrogen
production from dimethyl ether, Japan Patent No.
3951127; US Patent No. 7,241,718; etc.
[4] WO93/10069; JP1991-8446; JP1991-181435;
JP1992-264046; etc.
[5] K. Takeishi, Dimethyl ether and catalyst
development for production from syngas, Biofuels,
Vol. 1, No. 1, 2010, pp. 217-226.
409 ISBN: 978-960-474-159-5
 RECENT ADVANCES in ENERGY & ENVIRONMENT

-1
30 500 10

Rate of DME production / C . mol g -cat h

-1
Me2O(Sol) Me2O
-1
Production rate / C .mol g-cat h

25 C1
CH4

-1 -1
-1

Me2O(N211)

Rate of methane or methanol

400 8

production / C . mol g -cat h

MeOH
MeOH(N211)
20
300 6
15

10 200 4

5
100 2
0
140 180 220 260 300 340 380 0 0
Temperature / 0.0 0.3 0.6 0.9 1.2 1.5 1.8
Fig. 1. Activity of CO hydrogenation over Absolute pressure / MPa
Cu-Zn(36-4wt.%)/Al2O3 (Sol), and a catalyst (N211) Fig. 3. Effect of pressure on activity of CO
physically mixed CuO-ZnO(50-50wt.%) and Al2O3. hydrogenation over Cu-Zn(36-4wt.%)Al2O3 catalyst
Catalyst: 0.5 g, H2/CO/Ar = 7.5/7.5/1.5 ml min-1. at 220 oC. Catalyst: 0.5g, H2/CO/Ar = 7.5/7.5/1.5 ml
min-1.

45 100 20
-1

40 90 18
Production rate / C . mol g-cat h

Selectivity for DME / C . %

Selectivity for methane or

-1

35 80 16
70 14

methanol / C . %
Me2O
30
Me2O 60 CH4
C1 12
25 50 MeOH 10
CH4
20 40 8
15 30 6
20 4
10
10 2
5 0 0
0 0.0 0.3 0.6 0.9 1.2 1.5 1.8
0.2 0.3 0.4 0.5 0.6 0.7 0.8 Absolute pressure / MPa
H2/(H2+CO)
Fig. 4. Effect of pressure on selectivity of CO
Fig. 2. H2/(H2+CO) and activity of CO hydrogenation hydrogenation over Cu-Zn(36-4wt.%)Al2O3
over Cu-Zn(36-4wt%)/Al2O3 at 220 oC. Catalyst: catalyst at 220 oC. Catalyst: 0.5g, H2/CO/Ar =
0.5 g, (H2+CO)/Ar = (Total 15 ml min-1)/1.5 ml 7.5/7.5/1.5 ml min-1.
min-1.

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 RECENT ADVANCES in ENERGY & ENVIRONMENT

100 10
-1

600 50
Rate of DME production/ C . mol g -cat- h

-1 -1
-1

Rate of methane or methanol

Me2O CH4 45

Selectivity for DME / C . %

Selectivity for methane or

produtcion / C . mol g -cat h
500 MeOH
40 80 8
Me2O CH4 MeOH

methanol / C . %
400 35
60 6
30
300 25 40 4
20
200 15 20 2

100 10
0 0
5
0 40 80 120 160 200
0 0
Reaction time / h
0 40 80 120 160 200
Reaction time / h Fig. 6. Time course of selectivity on CO
hydrogenation over Cu-Zn(36-4wt.%)Al2O3 catalyst
Fig. 5. Time course of activity on CO hydrogenation at 220 oC under 1.1 MPa. Catalyst: 0.5g, H2/CO/Ar =
over Cu-Zn(36-4wt.%)Al2O3 catalyst at 220 oC under 7.5/7.5/1.5 ml min-1.
1.1 MPa. Catalyst: 0.5g, H2/CO/Ar = 7.5/7.5/1.5 ml
min-1.

Table 1 Comparison of reaction results on direct DME synthesis between our single-type catalyst and
some mixed catalysts developed by some companies [5]

Catalystr Single type Mixed type

(Cu-Zn/Al2O3
(Methanol-synthesis, dehydration condensation, and
prepared using
water-gas shift reaction catalysts)
sol-gel method)
Haldor
Developer Shizuoka Univ. JFE (NKK) Air Products KOGAS
Topsoe
H2/CO Ratio 1.0 1.0 0.7 2 1.0
Fixed bed Slurry Slurry Fixed bed Fixed bed
Reactor type
reactor reactor reactor reactor reactor
Reaction temperature (oC) 220 250-280 250-280 210-290 240-260
Reaction pressure (MPa) 1.6 5-6 5-10 7-8 5-6
One-pass conversion (%) 5-15 55-60 33 18 ?
DME/(DME+Methanol)(%) 98 90 30-80 60-70 85-95

ISSN: 1790-5095 411 ISBN: 978-960-474-159-5