Journal of Natural Gas Chemistry 12(2003)219–227

Direct Dimethyl Ether Synthesis

Takashi Ogawa∗ , Norio Inoue, Tutomu Shikada, Yotaro Ohno

DME Development Co., Ltd, Shoro-koku Shiranuka-ch, Hokkaido, 088-0563 Japan
[Manuscript received September 1, 2003; revised October 20, 2003]

Abstract: Dimethyl ether (DME) is a clean and economical alternative fuel which can be produced from
natural gas through synthesis gas. The properties of DME are very similar to those of LP gas. DME can
be used for various fields as a fuel such as power generation, transportation, home heating and cooking,
etc. It contains no sulfur or nitrogen. It is not corrosive to any metal and not harmful to human body. An
innovative process of direct synthesis of DME from synthesis gas has been developed. Newly developed
catalyst in a slurry phase reactor gave a high conversion and high selectivity of DME production. One
and half year pilot scale plant (5 tons per day) testing, which was supported by METI, had successfully
finished with about 400 tons DME production.
Key words: dimethyl ether, DME, slurry reactor, natural gas, syn-gas, coal, clean fuel, diesel engine

1. Introduction natural gas is converted to DME, it will provide a new

Future energy demand especially in the pacific
and Asian regions is forecasted to be huge. Therefore
limited energy supply as well as environmental issue
caused by consumption of fuel would be substantial
obstacles to realize constant economic growth in these
regions. Dimethyl ether (DME), which is recently rec-
ognized as a new clean fuel and is synthesized from
natural gas, will give a solution of secure energy sup-
ply and environmental conservation.
DME is a colorless gas at an ambient condition
and easily liquefied under light pressure. Since its
physical and chemical characteristics are very similar
to those of LP gas, it is an easy substitute for LP gas.
Almost half of household in Japan use LP Gas for
cooking and home heating. DME is not only an easy
substitute for LP gas, but also a very clean substitute
for diesel fuel because a DME fueled diesel car emits
neither soot nor particle matters (PM) [1].
DME can be distributed and stored by using LP
gas handling technology, which means DME does not
need costly LNG tankers or LNG terminals [2]. Once
∗ Corresponding author. Tel: +81-1547-5-9245; Fax: +81-1547-5-9247
E-mail: ogawa@dme-development.com
competitive route to transport natural gas compared
with the LNG chain.
DME is now manufactured with two processes,
which are methanol synthesis and methanol dehydra-
tion process. In order to use DME as a fuel, it must
be produced at low cost in large quantities. DME
synthesis from synthesis gas (syn-gas: H2 +CO gas)
developed for these years [3–5]. JFE (formally NKK)
Corporation has been making remarkable progress in
a development of direct DME synthesis from syn-gas
with a bubble column slurry reactor since 1989 [6–9].
This JFE Direct DME Synthesis will open a new way
to economical DME mass production.
JFE Co., collaborating with Taiheiyo Coal Mining
Co., Sumitomo Metal Industry, Ltd. and CCUJ (Cen-
ter for Coal Utilization, Japan), finished a project of
5 ton-DME/day (5TPD) pilot plant in 2001 very suc-
cessfully [10]. This project was funded by Ministry of
Economy, Trade and Industry (METI).
Based on this achievement, DME Development
Co., Ltd started 100 ton-DME/day (100TPD) demo-
plant project at Hokkaido Japan in 2002.
220 Takashi Ogawa et al./ Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

2. What’s DME? combustion characteristics of DME and other relat-

DME is the simplest ether having the chemical
formula of CH3 OCH3 . DME is now used almost only
for a spray propellant (paints, agricultural chemicals,
cosmetics, etc.). Approximately 10,000 tons/year
are produced in Japan, and about 150,000 tons/year
worldwide. Table 1 shows physical properties and
ing fuels. DME is a colorless gas at an ambient con-
dition. As its vapor pressure is about 0.6 MPa at
25 , DME is easily liquefied under light pressure.
Its physical properties are similar to those of propane
and butane, which are the principal constituents of
LP gas.

Table 1. Physical properties of DME and other fuel

Properties Chemical Boiling Liquid Specific Heat of Vapor Ignition Explosion Cetane Net Net
formula point density gravity vaporization pressure temperature limit number b calorific calorific
(K) (g/cm3 )a (vs. air) (kJ/kg) (atm)a (K) value value
(106 J/Nm3 ) (106 J/kg)
DME CH3 OCH3 247.9 0.67 1.59 467 6.1 623 3.4–17 55–60 59.44 28.90
Propane C 3 H8 231 0.49 1.52 426 9.3 777 2.1–9.4 (5)b 91.25 46.46
Methane CH4 111.5 — 0.55 510 — 905 5–15 0 36.0 50.23
Methanol CH3 OH 337.6 0.79 — 1,097 — 743 5.5–36 5 — 21.10
Diesel — 180–370 0.84 — — — — 0.6–6.5 40–55 — 41.86

a: at 293 K; b: estimated value

Synthesized DME contains neither sulfur nor ni- DME synthesis and their reaction heats. There are
trogen. A toxicity study of DME has confirmed that mainly two overall reaction routes that synthesize
its toxicity is very low, similar to LP gas, far much DME from synthesis gas (syn-gas: H2 +CO gas), re-
lower than Methanol. DME does not corrode any action (a) and (b). The reaction (a) synthesizes DME
metals. Some artificial rubbers swell in liquid DME, in three steps, which are methanol synthesis reaction
but, for example, NBR (Nitric rubber) is durable and (c), dehydration reaction (d) and water-gas shift reac-
can be used in liquid and gas conditions. Since DME tion (e). When the shift reaction does not take place,
is decomposed in a troposphere in dozens of hours, it reaction (c) and (d) are combined to the reaction (b),
does not cause ozone layer depletion [11]. which is the other DME synthesis route. Haldor Top-
DME’s calorific value of 28.90 × 106 J/kg is 1.37 soe A/S and some other direct DME syntheses follow
times higher than that of methanol. Its calorific value reaction (b) [3]. JFE direct DME synthesis follows
of 59.44 × 106 J/Nm3 as a gas is 1.65 times higher reaction (a).
than that of methane. Although DME has about 65%
Table 2. Reaction formulas concerning
of propane’s calorific value, a same size of DME tank DME synthesis
can store or carry 85% energy of propane because
Reaction heat
DME’s liquid density is 1.37 times heavier than that Reaction
(kJ/mol)
of propane.
(a) 3CO+3H2 → CH3 OCH3 +CO2 -246
DME flame is visible blue like that of natural gas. (b) 2CO+4H2 → CH3 OCH3 +H2 O -205
A cooking oven for natural gas can be used for DME (c) 2CO+4H2 → 2CH3 OH -182
with very small modification. Cetane number of DME (d) 2CH3 OH → CH3 OCH3 +H2 O -23
is very high so that it can be used as diesel substitute, (e) CO+H2 O → CO2 +H2 -41
and DME combustion exhaust gas is far much cleaner
than that of diesel [1].
Since both reaction (a) and (b) generate two
3. Direct DME synthesis process molecules of products from six molecules of syn-gas,
the higher reaction pressure gives higher syn-gas con-
3.1. Direct DME synthesis from hydrogen and version. In consideration of process design, JFE Di-
carbon monoxide rect DME Synthesis reaction pressure is around 3 to
7 MPa, and its standard pressure is 5 MPa. Table 3
Table 2 shows reactions concerning with direct shows reaction conditions. A catalyst loading ratio,
 Journal of Natural Gas Chemistry Vol. 12 No. 4 2003 221

W/F, is defined as a ratio of catalyst weight (kg) to reactant gas flow rate ((kg·mol)/h).
Table 3. Reaction conditions of direct DME synthesis
Reaction condition Temperature/
Pressure/MPa Fed syn-gas H 2 /CO ratio W/F/((kg·h)/kg)
Experimental 240–280 3.0–7.0 0.5–2.0 3.0–8.0
Standard 260 5.0 1.0 4.0

Methanol synthesis is an equilibrium-restricted

reaction. However when the dehydration reaction
(d) takes place simultaneously, the syn-gas conver-
sion rises dramatically. Figure 1 shows stoichiometric
equilibrium syn-gas conversion of DME synthesis (a)
and (b) under 5 MPa, and methanol synthesis (c) un-
der 5 and 9 MPa.

Figure 2. Equilibrium conversion of synthesis gas

vs. H2 /CO ratio

Reaction (a) has some other process advantages

compared with reaction (b). In overall reaction (a),
reaction (e) simultaneously converts by-product wa-
ter, therefore the water does not accumulate near the
synthesis catalyst. Water leads the catalyst to degra-
dation. To bring longer catalyst life, it’s important to
avoid water accumulation over time.
By-product of reaction (a) is CO2 . Separation
or distillation of DME from CO2 is much efficient and
Figure 1. Stoichiometric equilibrium conversion of not energy consuming compared with separation from
DME and methanol synthesis
water (in the case of reaction (b)). Because of these
Compared DME synthesis reaction (a) with reac- reasons, JFE direct DME synthesis focused the devel-
tion (b), reaction (a) gives much higher syn-gas con- opment of the catalyst system and its reaction process
version in all temperature conditions. on the reaction (a).
Figure 2 also shows syn-gas conversions of the two In the process of direct DME synthesis from nat-
overall DME syntheses, (a) and (b), and the methanol ural gas, the natural gas will be converted to syn-gas
synthesis (c), as a function of H2 /CO ratio of syn-gas. of H2 /CO=1 at first with O2 and by-product CO2 of
In each reaction, the equilibrium conversion reaches the reaction (a) in an auto-thermal reformer (ATR)
its maximum point when the H2 /CO ratio is equal to by the following overall reaction (f). Then the total
its stoichiometric number, which are 1.0 for (a) and reaction follows overall reaction (g), and eventually
2.0 for both (b) and (c). The maximum equilibrium natural gas (methane) is converted DME and water
conversion of (a) is higher than (b) by more than 10 via reaction (g), just like via natural gas steam re-
points. forming plus DME synthesis reaction (b).
Table 4. DME synthesis from natural gas in the direct DME synthesis plant
Unit Reaction
(ATR) 2CH4 +O2 +CO2 → 3CO+3H2 +H2 O↓ (f)
(DME synthesis reactor) 3CO+3H2 → CH3 OCH3 (DME)+CO2 (a)
(DME plant total) 2CH4 +O2 → CH3 OCH3 (DME)+H2 O↓ (g)
222 Takashi Ogawa et al./ Journal of Natural Gas Chemistry Vol. 12 No. 4 2003
3.2. A liquid phase slurry reactor
The reaction of DME synthesis is highly exother-
mic, and catalyst is gradually deactivated at high tem-
perature (over 300 ). Then it is very crucial to re-
move the reaction heat and to control the reactor tem-
perature even. The direct DME synthesis reactor is
specialized with a liquid phase reactor (DME slurry
reactor) and newly developed catalyst system that re-
alizes the reaction (a) efficiently. Figure 3 shows an
image of the DME slurry reactor.
Figure 3. Concept of slurry reactor for direct DME
synthesis
Catalyst is present as a fine powder slurried in in-
ert high-boiling-point oil. Syn-gas is fed from the bot-
tom of the reactor and forms small and homogeneous
bubbles that react while rising in the catalyst slurry.
Thanks to its homogeneous liquid phase mixing, tem-
Figure 4. Schematic process flow diagram of JFE direct DME synthesis process
4. Process development
4.1. 5TPD project
JFE started the DME synthesis process devel-
opment with a 50 kg/d bench plant in 1994 [8].
5TPD pilot plant project started in 1997 at Kushiro-
city in Hokkaido Japan, collaborating with Taiheiyo
Coal Mining Co., Sumitomo Metal Industry LTD and
CCUJ (Center for Coal Utilization, Japan). This
perature in the reactor is homogenized so that it is
easily controlled at a high syn-gas conversion (very
exothermic condition). The catalyst was modified to
promote the three reactions (c), (d) and (e) simulta-
neously in the slurry reactor. There are much fewer
restrictions to the catalyst shape and strength in the
slurry reactor than in a fixed bed reactor.
3.3. JFE direct DME synthesis process
Figure 4 shows a schematic process flow diagram
of the direct DME synthesis process from natural gas.
The process consists of mainly three sections, syn-gas
preparation (auto-thermal reformer), DME synthe-
sis (slurry reactor), and separation/purification (CO2 ,
DME, methanol distillation columns).
Natural gas is converted to syn-gas with O2
(steam) and by-product CO2 in an auto-thermal re-
former (ATR). The syn-gas is compressed and fed to
the DME slurry reactor. The effluent from the reactor
is DME, by-product CO2 , small amount of methanol
and unreacted syn-gas. DME and other by-products
are chilled and separated as a liquid from unreacted
gas. In this separation DME works as a solvent to re-
move CO2 from unreacted syn-gas, which is recycled
to the reactor. DME and other by-products are fed
to the distillation columns. DME and methanol are
purified. CO2 is recycled to the ATR and converted
to syn-gas. Methanol is also recycled to the DME
reactor and finally converted to DME.
project was funded by METI.
After finishing the construction of the plant, its
operation started in September 1999 and very suc-
cessfully finished in December 2000. During the one
and half years, six plant operation runs were con-
ducted. Total plant operation time reached 4,300
hours (syn-gas production: about 4,100 h, DME pro-
duction: about 3,000 h). Total amount of produced
DME was about 400 tons.
 Journal of Natural Gas Chemistry Vol. 12 No. 4 2003
4.2. Process flow of 5TPD pilot plant
Figure 5 shows the process flow of 5TPD pilot
plant. Picture 1 shows the plant. Since natural
gas was not available at Kushiro-city (the plant site)
Figure 5. Process flow of the 5TPD DME pilot plant
Picture 1. The 5TPD DME pilot plant
4.3. Experimental results
(1) Effect of reaction temperature and pressure
The dependence of once-through conversion on
the reaction pressure and temperature is shown in
Figures 6 and 7.
In the Figure 7, by-product CO2 was eliminated
223
during the operation period, LP gas and Coal Bed
Methane were used as feedstock. Basic process flow
of the plant was almost same as those of Figure 4.
The dimensions of the slurry phase reactor were of
0.55 meter-diameter and 15 meter-height.
from the selectivity calculation. Figure 6 shows that
the CO conversion increased with pressure, corre-
sponding to the higher equilibrium conversion at the
higher pressure.
The once-through CO conversion reached higher
than 50% at 260 and 5 MPa. The conver-
sion increased kinematically with temperature but has
224 Takashi Ogawa et al./ Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

its maximum because the equilibrium conversion re-
stricts it. Figure 7 shows the DME catalyst did not
synthesize undesirable heavier by-products such as
wax or higher alcohols.
(2) The catalyst life
Continuous experiment for 1,000 h was conducted
to clarify the change of catalyst activity. Sulfur con-
tent in the syn-gas was controlled under 1.0×10−6
to avoid poisoning the catalyst. The degradation of
the CO conversion was confirmed to be lower than
10 points of the initial value after 1,000 h operation.
The selectivity was almost constant. This pattern of
degradation of the activity was almost same as that
of conventional methanol synthesis catalyst or fixed
bed DME synthesis catalyst [3]. As a result of the life
test, this catalyst system has commercial durability.

Figure 6. CO conversion vs. reaction conditions

Figure 8. The catalyst life test

Reaction conditions: 260 , 5 MPa, W/F=4 (g·h)/mol, molar

ratio of H2 to CO is 1.0

(3) Process material balance

Figure 7. Product selectivity vs.
tions
Figure 9 shows a typical example of the mate-
rial balance of 5TPD pilot plant. Steam and recycled
CO2 were both fed to the ATR to control the reform-
ing reaction and the composition of syn-gas. H2 /CO
ratio of this syn-gas was controlled to 1.04, which was
the best ratio to maximize DME productivity in this
case. DME yield achieved 5.7 tons per day and total
CO conversion reached almost 95% in this material
reaction condi-
balance.

Figure 9. Typical material balance of 5TPD pilot plant

 Journal of Natural Gas Chemistry Vol. 12 No. 4 2003
(4) The catalyst activity in terms of W/F
Figure 10 shows once-through CO conversion of
the 50 kg/d bench plant and the 5TPD pilot plant,
as a function of W/F. Once-through CO conversion
deeply depends on W/F. Since the catalyst slurry is
solely stirred by gas flow in the reactor, the range of
W/F is depends on the reactor dimensions and cata-
lyst concentration.
Figure 10. Effect of W/F on once-through CO con-
version
Figure 11 shows CO conversion as a function of
recycle ratio. Recycle ratio was a ratio of recycled
unreacted gas flow rate to make-up syn-gas flow rate.
While recycle ratio was changed, W/F was kept at
3.8, then once-through CO conversion was almost con-
stant.
Figure 11. Total CO conversion as a function of re-
cycle ratio
(W/F=3.8 (g·h)/mol, 260 , 5 MPa)

tions. Figure 12 shows stability and homogeneousness
225
Total CO conversion reached more than 95%
with the recycle ratio of 1.8. Since by-products of
this DME reaction were CO2 and small amount of
methanol, these by-products were easily removed from
unreacted syn-gas, so that high total CO conversion
was achieved.
(5) Product selectivity and DME quality
Table 5 shows typical product selectivity of 5TPD
pilot plant (CO2 was eliminated from the product se-
lectivity calculation).
Table 5. Selectivity of 5TPD pilot plant
(Product C-mol ratio) DME/(DME+Methanol)=0.91
(Product H-mol ratio) H2 O/(DME+Methanol+H2 O)=0.013
DME yield was as much as 90%. Very small
amount of H2 O was produced, which means that over-
all reaction well followed the DME synthesis reaction
(a). Table 6 shows typical product DME quality of
the plant. This quality was sufficient for IEA’s rec-
ommended standards for DME as vehicle fuel, which
states that acceptable concentration of methanol is
lower than 0.01% and water is lower than 0.05%.
Table 6. Product DME quality of 5 ton/day Plant
Product content
DME 99.9%
Methanol + H2 O < 0.01%
5. Engineering of the DME slurry reactor
When the DME slurry reactor is scaled-up, both
catalyst activities and hydrodynamics of the cata-
lyst slurry must be well considered. JFE started the
study of high pressure DME slurry reactor with a (9
cm-diameter×2 meter-height) reactor and a (4 cm-
diameter×4 meter-height) reactor. Effects of reac-
tion conditions and products’ yields were studied with
these reactors.
The size of the reactor of the 5TPD pilot plant was
0.55 meter-diameter×15 meter-height. Axial slurry
mixing, gas-hold-up as well as the temperature con-
trollability were tested with this reactor. The reactor
has 30% to 50% of gas-hold-up, which is very typi-
cal feature of a high-pressure slurry reactor. Liquid
(catalyst+oil) height itself was about 7 m, but slurry
height was about 10 to 14 m under operation condi-
226 Takashi Ogawa et al./ Journal of Natural Gas Chemistry Vol. 12 No. 4 2003

of the reactor inner temperature. In Figure 12, each

circle indicates temperatures of every 15 minutes at
each TI (Thermocouple) position for 8 h.
Since the temperature of the fed syn-gas to the
reactor was around 200–220 , temperature of the
lower part of the reactor was slightly lower than 260
. As shown in Figure 12, most of reactor tempera-
ture in the slurry phase was even. The temperature
difference of the reactor higher than 1.8 m was almost
within 2 , which means that the slurry mixing was
very homogeneous. Also the sharp temperature drop
at the 10.1 meter TI position meant the slurry phase
did not form and had clear upper level.

Figure 13. Effect of gas residence time RTg on CO

conversion

6. Conclusions

JFE direct DME synthesis technology successfully

Figure 12. Temperature stability of 5TPD DME re-
actor
DME yield deeply depends on W/F (Figure 9),
but gas residence time (RTg) in the slurry phase must
be considered because necessary time for reactants’
phase transfer in the slurry phase is crucial in a large
reactor.
Figure 13 shows an effect of RTg on once-through
CO conversion. RTg was defined as the ratio of actual
fed gas flow rate to the slurry volume.
RTg=[slurry volume]/[actual gas flow rate] (sec)
As shown in Figure 13, when RTg was more than
around 100 s, CO conversion reached almost constant.
This result means that the time for reactants transfer
in the slurry phase should be sufficient. The result
of Figure 13 also means that, as far as the reactor
diameter can be scaled-up, scale-up of the reactor is
scale-up of the reactor diameter because the reactor
does not need extra slurry height for excess RTg.
finished 5TPD pilot plant project with achieving suf-
ficient DME synthesis results and very stable DME
slurry reactor operation. Based on these results, DME
Development Co., Ltd is now conducting a 100TPD
DME demo-plant project in Hokkaido Japan in order
to establish commercial DME production technology.
This project is also supported by METI. The produc-
tion of 100 tons of DME per day will start in 2004.
Acknowledgements
The authors would like to express sincere appre-
ciation for Agency of Natural Resources and Energy,
Coal Division (METI) for their long term financial
support to the DME research Project.
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