Slurry Phase Synthesis and Utilization of Dimethyl Ether

Yotaro Ohno*, Norio Inoue**, Takashi Ogawa***,

Masami Ono***, Tsutomu Shikada**** and Hiromasa Hayashi*****
*
**
***
****
*****

Chief Engineer, Dr, Environmental Solution Center

Manager, Environmental Solution Center
Senior Research Engineer, Engineering Research Center
Chief Researcher, Dr, Applied Technology Research Center
Senior Research Engineer, Applied Technology Research Center

DME (dimethyl ether) has been attracting the attention of industry as a clean fuel for the 21st century. NKK has
been conducting original DME synthesis research since 1989. Operational research was performed in a 5 tons-DME
production/day pilot plant, which operated continuously under very stable conditions for periods up to two months.
These studies led to the successful synthesis of DME from methane directly from coal layers. Combustion tests of
DME in a commercial type household cooking gas stove and diesel truck driving tests confirmed that DME has high
potential as an alternative fuel.

1.

Economics and Industry). The technology was implemented jointly by the CCUJ (Center for Coal Utilization,
Japan), Taiheiyo Coal Mining Co., Ltd., and Sumitomo
Metal Industries, Ltd. at a plant constructed at the Taiheiyo Coal Mining site in Kushiro City. Construction began in the summer of 1999, and operation and research
commenced approximately 18 months later. A total of six
continuous trials have been conducted, and operation of
the plant has proven to be extremely stable, with the longest continuous period of operation being two months. A
total of approximately 400 tons of high-purity DME has
been produced during these trials.

Introduction

DME (Dimethyl ether) is a new, easily handled fuel that

is currently the subject of considerable interest. NKK began basic research and development on a new synthesizing
catalyst in 1989. Following completion of this work in
1995, NKK established a small-scale bench plant capable
of producing DME at a rate of 50 kg per day. In 1997 a
large-scale bench plant capable of producing approximately five tons per day was constructed to develop a new,
high-efficiency, DME synthesis process1).
DME is currently manufactured at a rate of approximately 10000 tons annually for such applications as cosmetics and aerosol paint propellants. This DME is produced using methanol as the raw material and involves a
dehydration reaction to remove a single water molecule
from two methanol molecules.
NKK developed new production technology that uses
carbon monoxide (CO) and hydrogen (H2) gases as the raw
material for synthesizing DME in a highly-efficient, single-step reaction process. The conversion efficiency for
the raw material gases for the synthesis reaction and the
selectivity level to the DME product are extremely high.
Thus, the synthesis process is more compact and simple
than that for the production of methanol from CO and H2.
The large-scale bench plant introduced in 1997 was a
technology development program supported by the Resources and Energy Agency within the Ministry of International Trade and Industry (now the Ministry of Trade,

2.

Characteristics of DME as a fuel

DME has similar properties to LPG in that it is a gas at

ambient temperature and atmospheric pressure. It becomes
a colorless clear liquid under six atmospheres at ambient
temperature or at atmospheric pressure and a temperature
of 251). Thus, DME can be transported and stored as a
liquid at low temperature in a similar manner to LPG.
DME is a clean fuel that contains no sulfur or nitrogen
compounds, has extremely low toxicity for humans, and
has no corrosive effect on metals. Its calorific value is approximately 65% that of methane (natural gas) and approximately 40% that of methanol. Although DME has a
lower calorific value than LPG because of differences in
the chemical structure, the density of liquid DME is
greater, so the total calorific value of a tank of DME is approximately 90% of that of a similar tank of LPG.

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NKK TECHNICAL REVIEW No.85 (2001)

Slurry Phase Synthesis and Utilization of Dimethyl Ether

kcal per kilogram of DME). This reaction heat must be

removed efficiently from the reactor to maintain a stable
temperature and to allow stable control of the DME direct
synthesis reaction. NKK therefore developed a
high-pressure DME slurry bed reactor that has excellent
mixing characteristics and easy control of the reaction
temperature. This slurry bed reactor contains a high boiling point solvent (reaction medium) in which fine catalyst
particles are mixed. The gases that form the raw materials
of the reaction provide strong mixing of the catalyst. This
ensures good flow of the gases within the reactor, a very
even temperature distribution, and ready control of the
DME direct synthesis in the presence of the highly exothermic reaction.
The DME direct synthesis reaction is characterized by
NKKs proprietary highly active catalyst and the DME
slurry bed reactor technology, which controls the reaction
to extract the maximum performance from this catalyst.

When used as a replacement for diesel fuel, DME has a

high cetane value, contains oxygen, and has a chemical
structure that forms carbon-carbon bonds, so that its combustion is not accompanied by black smoke or soot. This
property has attracted considerable interest in DME as a
clean fuel.
DME may be used in the same domestic applications as
LPG, as well in an extremely wide range of industrial applications, such as a replacement for diesel fuel and for
high-efficiency power generation fuels (e.g. for gas turbine
powered generators). DME is also easily stored and transported.

3.

Features of DME direct synthesis technology

The technology for direct synthesis of DME developed

by NKK employs a single-step reaction to synthesize
DME from CO and H2 as shown in (1) below.
3CO + 3H2 CH3OCH3(DME) + CO2

(1)

4. Five tons per day large-scale bench plant

4.1 Process flow

This formula summarizes the DME direct synthesis reaction. In practice, the reactions shown in the formulae (2),
(3), and (4) below occur simultaneously.
2CO + 4H2 2CH3OH (methanol)

(2)

2CH3OH CH3OCH3 (DME) + H2O

(3)

H2O + CO H2 + CO2

(4)

The large-scale bench plant is shown in Photo 1. Process flow is shown in Fig.1.

The two molecules of methanol synthesized from CO

and H2 in formula (2) are dehydrated in formula (3) to
produce DME. The water produced in formula (3) is recycled as hydrogen in formula (4).
It is important to note that the hydrogen produced at the
completion of the direct synthesis reaction becomes raw
material for the reaction in step (2). In this way, a reaction
cycle is formed in which the three reactions consume the
by-products in each step. The by-products of the reactions
therefore accumulate only to a minimal extent, allowing an
extremely high conversion efficiency for the total reaction
formula (1).
Formula (1) becomes increasingly favorable with increasing pressure, so the reaction is conducted at a pressure of 3 to 7MPa and temperature of 250 to 280 (basic
reaction conditions are 5MPa and 260).
Formula (1) is a highly exothermic reaction that produces 58.8 kcal per mole of DME (approximately 1280
NKK TECHNICAL REVIEW No.85 (2001)

Photo 1

Five ton per day DME test plant

Off-gas
CBM
DME

O2
LP gas

CO, H2, CO2

Methanol
Syn-gas reformerCO2 absorberReactor

Fig.1

24

Distiller

Process flow for five ton per day DME test plant

Slurry Phase Synthesis and Utilization of Dimethyl Ether

This plant employs refined methane from coal layers or

simulated coal gas (produced from LPG in this plant) as a
raw material to efficiently produce DME in a single-step
reaction using a slurry bed reactor.
The process components are described below.
(1) Synthesis gas production system incorporating a reformer to produce CO and hydrogen from the coal bed
methane (or LPG)
(2) Reaction system for direct synthesis of DME
(3) Distillation system for refining the DME produced, and
separating and recovering the by-product CO2
(4) Product storage and utility equipment system.
Each unit is controlled from a central computer in the
control room.
The coal bed methane or LPG is burned in the
auto-thermal reformer in an atmosphere of pure oxygen to
produce CO and H2 in a ratio of 1:1 (H2/CO=1). The CO2
produced in the reformer and the CO2 produced as a
by-product of direct synthesis of DME are separated and
partially recycled back to the reformer for use as a raw
material for gas synthesis.
If an efficiency of 100% was possible for the reforming
and DME direct synthesis reactions, natural gas (methane)
could be used in the ideal synthesis process described in
formula (7).

Table 1

(6)

Overall process
2CH4 + O2 DME + H2O

(7)

Plant
operation [h]

Syn-gas
production [h]

DME
production [h]

Run.

Test period

100

1999/Sep.9Sep.23

270

207

200

Oct.9Nov.2

466

460

408
457

300

Nov.11Dec.2

492

488

400

2000/Jun.12Jul.9

700

652

464

500

Jul.18Aug.6

495

484

458

600

Sep.18Dec.6

1870

1780

1650

4293

4071

3437

Sum.

Run 200 was the first in which DME was produced. The
entire plant was started, and various tests were conducted
on all systems.
Run 600 involved continuous and stable operation of the
plant for a period of two months. Approximately 400 tons
of DME was produced during Run 200 through Run 600.

4.3 Results of operation and research

4.3.1 Outline of results
All systems in the plant operated in a stable manner
during Run 200 through Run 600, and a detailed process
mass-balance data was recorded for further analysis. The
primary operation and research results are as follows.
(1) A per-pass synthesis gas conversion of higher than
50% and a product DME selectivity of higher than 90%
were achieved in the direct synthesis of DME.
(2) A total synthesis gas conversion of at least 95% was
achieved.
(3) The purity of the DME produced was at least 99.5%.
(4) The successful direct synthesis of DME from 100%
coal bed methane was a world first.
(5) The daily production was attained up to 5.7 tons while
the plant was designed for a daily production of 5 tons.
(6) A stable operation of the reaction system was maintained for 1650 hours (the plant operated for 1870 hours in
total).
(7) Data was recorded for use in scaling-up the DME
slurry bed reactor.
4.3.2 Plant material balance and product selectivity
The mass-balance data (materials used, product) for a
representative plant producing 5.7 tons of DME per day is
shown in Table 2. The process consists of partial oxidation with pure oxygen to synthesize gas at a ratio of
H2/CO=1 using LPG as the primary raw material and CO2
and steam as the secondary raw materials. Production was
approximately 5.7 tons of DME per day and 0.6 tons of
methanol per day from the synthesis gas. The CO and H2
in Table 2 are un-reacted gases included in the gas purged

Reformer
2CH4 + CO2 + O2 3CO + 3H2 + H2O (5)
DME synthesis
3CO + 3H2 CH3OCH3(DME) + CO2

Continuous plant operation details

4.2 Operation and research

Operation and research of the large-scale bench plant
commenced in September 1999 and continued until December 2000. The objective of the work was to establish
technology for a high-performance DME synthesis process
under the long-term and stable operation of a large-scale
plant, to obtain detailed data for use in scaling-up the
process, and to produce large volumes of DME. The plant
was run continuously six times (Run Nos. 100 to 600).
Details are shown in Table 1.
Run 100 was conducted solely to test the gas synthesis
system. The reaction and distillation systems were tested
without producing DME.
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NKK TECHNICAL REVIEW No.85 (2001)

Slurry Phase Synthesis and Utilization of Dimethyl Ether

4.3.3 Total conversion of synthesis gas

Between 40 and 50% of the raw material gas is converted to DME after passing through the reactor (the
once-through conversion varies with the operating conditions). As shown in the process flow diagram, the
un-reacted raw material gas discharged from the reactor
passes through the recycling compressor before being recirculated to the reactor. The amount of this un-reacted
gas that is recycled depends upon the conversion efficiency of the reaction process and affects such factors as
the scale of the equipment (e.g., the compressor size), the
operating costs of the equipment, and the final cost of
production.
As DME direct synthesis has a very high once-through
conversion level in comparison to methanol synthesis, the
volume of un-reacted, recycled gas is small, permitting a
plant of compact design. Fig.2 shows the effect of the recycling ratio, i.e., the ratio of the un-reacted, recycled gas
volume to the volume of synthesized gas introduced into
the reactor system (make-up gas). The total conversion of
CO in the make-up synthesized gas as calculated from
measured data is also shown. Fig.2 indicates that the total
CO conversion exceeds 95% at a recycling ratio of approximately 1.7, and that the once-through CO conversion
maintains a relatively constant value.
The process is commercially viable provided the gas
recycling system is designed to handle recycling of a
volume of gas approximately twice the volume of the synthesized make-up gas. Under the same reaction conditions,
the process is considerably more compact than the methanol synthesis process.

from the reactor system as off gas. The total CO conversion was 94%.
Table 2

Materials balance in LPG plant operation

Raw
material

Flow rate
[Nm3/h]

LP gas
CO2

Product

Flow rate
[kg/h]

Production
[t/d]

124.1

DME

238.2

5.72

66.8

MeOH

26.3

0.63

Steam

241.9

water

3.7

0.09

O2

85.9

CO2

111.4

CO

22.9

H2

15.9

Total CO conversion

94.0 [%]

The ratio of hydrogen atoms to carbon atoms in propane

(C3H8), which is the primary component of the LPG raw
material, is less than that for methane (CH4), so all of the
CO2 produced as a by-product of DME synthesis cannot be
reconverted in the reformer. However, approximately 60%
of the 111Nm3/hr of CO2 generated is reused as a secondary raw material in the production of synthesis gas.
The product selectivity is shown in Table 3. A feature
of this DME direct synthesis method is that it has a very
high once-through conversion synthesis gas, along with a
DME product selectivity of higher than 90%. In addition to
the CO2 and methanol produced, the only other by-product of
the process is a very small amount of methane.
The process produces no by-products such as heavy oils
and not even trace quantities of toxic materials. These
characteristics eliminate the need for complex separation
and refining of generated products and guarantee a simple
synthesis process, leading to reduced plant costs and operating expenses.
The CO2 produced as a by-product when natural gas
(methane) is used as the primary raw material is recirculated to the reformer. The methanol produced has value as
a product, but it is recycled to the reactor and may be finally converted to DME because it is an intermediate
product of the DME synthesis reaction. The DME product
selectivity shown in Table 3 is the carbon selectivity to
DME without CO2 and DME contained in recovered
methanol.
Table 3

1.0

Total CO conversion , %

0.8

Selectivity [C-mol%]
DME

CO2

MeOH

DME product
selectivity [C-mol%]

LPG100%

64.7

33.8

1.6

97.6

CBM85% + LPG15

64.8

32.4

2.8

95.8

CBM100%

63.4

30.9

5.7

91.8

0.0
0.8

1.0

1.2

1.4

1.6

1.8

2.0

Gas recycle ratio , -

Fig.2

(CBM = Coal bed methane)

NKK TECHNICAL REVIEW No.85 (2001)

0.4

0.2

Product selectivity (once-through basis)

Raw material

Total CO conversion
Per-pass CO conversion

0.6

26

Total CO conversion as a function of recycling ratio

Slurry Phase Synthesis and Utilization of Dimethyl Ether

5. DME utilization technology

5.1 Use as an LPG alternative
DME is already used as an aerosol propellant, and it is
expected that, in the future, it will also be used in such applications as fuel for power generation, diesel vehicles,
and consumer applications, as a raw material for chemical
processes, and as a cooling medium2-4). The prospect of
DME as an alternative fuel to LPG in consumer applications stimulated experiments to investigate DME combustion in existing mass-produced combustion equipment in
order to gain an understanding of its combustion characteristics.
DME has a WI (Wobbe Index, which is the higher calorific value/(specific gravity)1/2 and is used as a basic
measure of heat input for gas appliances) of 51.91 MJ/Nm3
and an MCP (an index of the rate of gas combustion) of 48
to 50. The WI for DME is close to that of 13A and 12A
municipal gases, but its MCP is outside the corresponding
range. DME is equivalent to a gas classification of 12C, a
type not currently used.
Combustion tests of DME were conducted using standard domestic cooking stoves designed for LPG or municipal gas 13A. Combustion of DME using the LPG stove
shown in Photo 2(a) is clearly unsatisfactory. No significant improvement in combustion was observed, even when
the air adjustment damper, which is normally fixed, was
closed down to approximately 80%. This lack of improvement is due to the fact that the diameter of the main
nozzle on the LPG stove is very small (0.9 mm), thus preventing a sufficient supply of DME and resulting in insufficient heat of combustion.
Combustion of DME with the municipal gas 13A stove
is shown in Photo 2 (b). Combustion was relatively
satisfactory, but the flame tended to be shorter than is the
case when 13A is burned. Changing the opening of the
variable air adjustment damper from 8/10 to 5/10 reduced
the primary air supply and resulted in good combustion, as
shown in Photo 2(c). Changing the gas pressure from 1 to
3.3 kPa did not result in any significant difference in
combustion.
JIS combustion testing (JIS S 2093) to determine the
suitability of the gas combustion equipment for DME resulted in passes in all items on the test schedule, from tests
in no-wind conditions to tests with large pots, and certification was granted (see Table 4). JIS thermal efficiency
testing (JIS S 2093) to determine the performance of gas
combustion equipment in use showed a thermal efficiency

(a) LPG specification, damper opening : fixed

(b) 13A specification, damper opening : 8/10

(c) 13A specification, damper opening : 5/10

Photo 2

Combustibility of DME

of 47.9% with DME, approximately 2% less than with

municipal gas 13A. DME is well within the JIS standards,
which require a thermal efficiency of at least 40%.

Table 4

DME combustion test results

Item

Test under
windless
condition

JIS standard

Result

Ignition

No explosiveignition

None

Flame stability

Steady flame

Passed the standard

Back fire

No back fire

None

Combustion noise

60 dB or less

Within the standard

Fire extinguish

No explosive noise

Within the standard

CO concentration

0.14% or less

0.05

Soot emission

No emission of soot

Within the standard

Oversized pot test

Total evaluation

Steady flame / no odor

Passed the standard

Passed the standard

Conditions : Japanese municipal gas 13A specifications. damper opening 5/10

5.2 Use as a diesel fuel alternative

DME has the same or higher cetane value as diesel fuel
and is therefore ideal for use in diesel engines. However,
modifications to the fuel supply system are required because both the boiling point and viscosity of DME are less
than those of diesel fuel.
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NKK TECHNICAL REVIEW No.85 (2001)

Slurry Phase Synthesis and Utilization of Dimethyl Ether

hicles. It is therefore hoped that the use of such vehicles

will become widespread in the near future.

Smoke Bosch , %

14

Diesel

30

12

DME

25

10

NOx

20

15

10

Smoke

0
105

BSFC , MJ/kWh

35
NOISE

30

100

25

95

20

90
85

15
BSFC

10

80

75
7

15

22

29

37

44

Power , kW

Fig.3

DME and diesel fuel performance comparison

(at 2000rpm)

References
1) Ogawa, T. et al. NKK Technical Review, No.81, pp.1317(1999).
2) Fleisch, T. et al. SAE Paper, 950061 (1995).
3) Sorenson, S. C. et al. SAE Paper 950064 (1995).
4) Ikizawa, et al. Motor Vehicle Technology Conference, Autumn Lectures, 13 (1998).
5) Jidousha Kougaku, July 2001, pp.6073.

<Please refer to>

Yotaro Ohno
Environmental Solution Center
Tel. 03 (3217) 3266
E-mail address : Yotaro_Ohno@ntsgw.Tokyo.nkk.co.jp
Takashi Ogawa
Engineering Research Center
Tel. 044 (322) 6241
E-mail address : Takashi_Ogawa@ntsgw.Tokyo.nkk.co.jp

Photo 3

DME diesel truck

An oxidation catalyst is sufficient for purifying the exhaust gas because the engine does not emit black exhaust
smoke, and the CO and HC emissions are greatly reduced.
The modifications to a diesel engine to permit the use of
DME are minimal, consisting only of changes to the fuel
supply system. With these minimal changes, the highly
energy-efficient diesel engine may be converted to a relatively clean-burning engine, providing an effective method
to resolve the environmental problems posed by diesel veNKK TECHNICAL REVIEW No.85 (2001)

NOx , g/kWh

35

NOISE , dB(A)

NKK employed its diesel engine test bench, which has

been in use since 1997, to investigate both the characteristics of DME when used in diesel engines and the fuel supply system required for this application. In 1998, a light
truck was operated on DME, which was a world first4).
A description of the modifications of diesel engines to
use DME and the associated combustion characteristics are
presented below.
The use of DME, with its low boiling point and low
viscosity, does not require modifications to the diesel engine itself. Nevertheless, in contrast to diesel fuel, DME
must be supplied to the fuel injection pump under pressure.
In initial experiments, gas pressure from a nitrogen bottle
was used for pressurization, but this installation resulted in
supply equipment of considerable size, and nitrogen gas
dissolved into the liquid DME. A small fuel supply pump
was therefore developed5) to overcome these problems.
The DME diesel truck employed in the experiment is
shown in Photo 3. The original diesel fuel tank was used
to contain the DME.
As shown in Fig.3, the combustion characteristics of the
DME diesel engine include a thermal efficiency that is
similar to that of diesel, but without soot emission and
with greatly reduced NOx emissions and noise levels. This
is due to the fact that DME is an oxygenated fuel without
carbon bonding and to the greater ignitability in comparison to diesel.

28