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

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


RECENT ADVANCES in ENERGY & ENVIRONMENT

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

ISSN: 1790-5095 410 ISBN: 978-960-474-159-5


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