Journal of Natural Gas Chemistry 12(2003)219227

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 elds 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 nished with about 400 tons DME production. Key words: dimethyl ether, DME, slurry reactor, natural gas, syn-gas, coal, clean fuel, diesel engine

1. Introduction Future energy demand especially in the pacic 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 recognized as a new clean fuel and is synthesized from natural gas, will give a solution of secure energy supply and environmental conservation. DME is a colorless gas at an ambient condition and easily liqueed 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

natural gas is converted to DME, it will provide a new competitive route to transport natural gas compared with the LNG chain. DME is now manufactured with two processes, which are methanol synthesis and methanol dehydration 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 [35]. 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 [69]. 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 (Center for Coal Utilization, Japan), nished a project of 5 ton-DME/day (5TPD) pilot plant in 2001 very successfully [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) demoplant project at Hokkaido Japan in 2002.

Corresponding author. Tel: +81-1547-5-9245; Fax: +81-1547-5-9247 E-mail: ogawa@dme-development.com

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Table 1. Physical properties of DME and other fuel Properties Chemical Boiling formula point (K) DME Propane Methane Methanol Diesel CH3 OCH3 C 3 H8 CH4 CH3 OH 247.9 231 111.5 337.6 180370 Liquid density Specic Heat of (kJ/kg) 467 426 510 1,097 Vapor (atm)a 6.1 9.3 Ignition (K) 623 777 905 743 3.417 2.19.4 515 5.536 0.66.5 5560 (5)b 0 5 4055 Explosion Cetane limit number b Net caloric value 59.44 91.25 36.0 Net caloric value 28.90 46.46 50.23 21.10 41.86 gravity vaporization pressure temperature

(g/cm3 )a (vs. air) 0.67 0.49 0.79 0.84 1.59 1.52 0.55

a: at 293 K; b: estimated value

Synthesized DME contains neither sulfur nor nitrogen. A toxicity study of DME has conrmed that its toxicity is very low, similar to LP gas, far much lower than Methanol. DME does not corrode any metals. Some articial rubbers swell in liquid DME, but, for example, NBR (Nitric rubber) is durable and can be used in liquid and gas conditions. Since DME is decomposed in a troposphere in dozens of hours, it does not cause ozone layer depletion [11]. DMEs caloric value of 28.90 106 J/kg is 1.37 times higher than that of methanol. Its caloric value of 59.44 106 J/Nm3 as a gas is 1.65 times higher than that of methane. Although DME has about 65% of propanes caloric value, a same size of DME tank can store or carry 85% energy of propane because DMEs liquid density is 1.37 times heavier than that of propane. DME ame is visible blue like that of natural gas. A cooking oven for natural gas can be used for DME with very small modication. Cetane number of DME is very high so that it can be used as diesel substitute, and DME combustion exhaust gas is far much cleaner than that of diesel [1]. 3. Direct DME synthesis process 3.1. Direct DME synthesis from hydrogen and carbon monoxide Table 2 shows reactions concerning with direct

DME synthesis and their reaction heats. There are mainly two overall reaction routes that synthesize DME from synthesis gas (syn-gas: H2 +CO gas), reaction (a) and (b). The reaction (a) synthesizes DME in three steps, which are methanol synthesis reaction (c), dehydration reaction (d) and water-gas shift reaction (e). When the shift reaction does not take place, reaction (c) and (d) are combined to the reaction (b), which is the other DME synthesis route. Haldor Topsoe A/S and some other direct DME syntheses follow reaction (b) [3]. JFE direct DME synthesis follows reaction (a).
Table 2. Reaction formulas concerning DME synthesis Reaction (a) (b) (c) (d) (e) 3CO+3H2 CH3 OCH3 +CO2 2CO+4H2 CH3 OCH3 +H2 O 2CO+4H2 2CH3 OH 2CH3 OH CH3 OCH3 +H2 O CO+H2 O CO2 +H2 Reaction heat (kJ/mol) -246 -205 -182 -23 -41

Since both reaction (a) and (b) generate two molecules of products from six molecules of syn-gas, the higher reaction pressure gives higher syn-gas conversion. In consideration of process design, JFE Direct DME Synthesis reaction pressure is around 3 to 7 MPa, and its standard pressure is 5 MPa. Table 3 shows reaction conditions. A catalyst loading ratio,

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

combustion characteristics of DME and other relating fuels. DME is a colorless gas at an ambient condition. As its vapor pressure is about 0.6 MPa at 25 , DME is easily liqueed under light pressure. Its physical properties are similar to those of propane and butane, which are the principal constituents of LP gas.

(106 J/Nm3 ) (106 J/kg)

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W/F, is dened as a ratio of catalyst weight (kg) to

reactant gas ow rate ((kgmol)/h).

Table 3. Reaction conditions of direct DME synthesis Experimental Standard 240280 260

Reaction condition

Temperature/

Pressure/MPa 3.07.0 5.0

Fed syn-gas H 2 /CO ratio 0.52.0 1.0

W/F/((kgh)/kg) 3.08.0 4.0

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

Figure 2. Equilibrium conversion of synthesis gas vs. H2 /CO ratio

Figure 1. Stoichiometric equilibrium conversion of DME and methanol synthesis

Compared DME synthesis reaction (a) with reaction (b), reaction (a) gives much higher syn-gas conversion in all temperature conditions. Figure 2 also shows syn-gas conversions of the two overall DME syntheses, (a) and (b), and the methanol synthesis (c), as a function of H2 /CO ratio of syn-gas. In each reaction, the equilibrium conversion reaches its maximum point when the H2 /CO ratio is equal to its stoichiometric number, which are 1.0 for (a) and 2.0 for both (b) and (c). The maximum equilibrium conversion of (a) is higher than (b) by more than 10 points.
Unit (ATR) (DME synthesis reactor) (DME plant total)

Reaction (a) has some other process advantages compared with reaction (b). In overall reaction (a), reaction (e) simultaneously converts by-product water, therefore the water does not accumulate near the synthesis catalyst. Water leads the catalyst to degradation. To bring longer catalyst life, its important to avoid water accumulation over time. By-product of reaction (a) is CO2 . Separation or distillation of DME from CO2 is much ecient and not energy consuming compared with separation from water (in the case of reaction (b)). Because of these reasons, JFE direct DME synthesis focused the development of the catalyst system and its reaction process on the reaction (a). In the process of direct DME synthesis from natural gas, the natural gas will be converted to syn-gas of H2 /CO=1 at rst with O2 and by-product CO2 of the reaction (a) in an auto-thermal reformer (ATR) by the following overall reaction (f). Then the total reaction follows overall reaction (g), and eventually natural gas (methane) is converted DME and water via reaction (g), just like via natural gas steam reforming plus DME synthesis reaction (b).

Table 4. DME synthesis from natural gas in the direct DME synthesis plant Reaction 2CH4 +O2 +CO2 3CO+3H2 +H2 O 3CO+3H2 CH3 OCH3 (DME)+CO2 2CH4 +O2 CH3 OCH3 (DME)+H2 O (f) (a) (g)

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3.2. A liquid phase slurry reactor The reaction of DME synthesis is highly exothermic, and catalyst is gradually deactivated at high temperature (over 300 ). Then it is very crucial to remove the reaction heat and to control the reactor temperature even. The direct DME synthesis reactor is specialized with a liquid phase reactor (DME slurry reactor) and newly developed catalyst system that realizes the reaction (a) eciently. Figure 3 shows an image of the DME slurry reactor.

perature in the reactor is homogenized so that it is easily controlled at a high syn-gas conversion (very exothermic condition). The catalyst was modied to promote the three reactions (c), (d) and (e) simultaneously in the slurry reactor. There are much fewer restrictions to the catalyst shape and strength in the slurry reactor than in a xed bed reactor. 3.3. JFE direct DME synthesis process Figure 4 shows a schematic process ow diagram of the direct DME synthesis process from natural gas. The process consists of mainly three sections, syn-gas preparation (auto-thermal reformer), DME synthesis (slurry reactor), and separation/purication (CO2 , DME, methanol distillation columns). Natural gas is converted to syn-gas with O2 (steam) and by-product CO2 in an auto-thermal reformer (ATR). The syn-gas is compressed and fed to the DME slurry reactor. The euent 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 remove 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 puried. CO2 is recycled to the ATR and converted to syn-gas. Methanol is also recycled to the DME reactor and nally converted to DME.

Figure 3. Concept of slurry reactor for direct DME synthesis

Catalyst is present as a ne powder slurried in inert high-boiling-point oil. Syn-gas is fed from the bottom 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 ow diagram of JFE direct DME synthesis process

4. Process development 4.1. 5TPD project JFE started the DME synthesis process development with a 50 kg/d bench plant in 1994 [8]. 5TPD pilot plant project started in 1997 at Kushirocity in Hokkaido Japan, collaborating with Taiheiyo Coal Mining Co., Sumitomo Metal Industry LTD and CCUJ (Center for Coal Utilization, Japan). This

project was funded by METI. After nishing the construction of the plant, its operation started in September 1999 and very successfully nished in December 2000. During the one and half years, six plant operation runs were conducted. Total plant operation time reached 4,300 hours (syn-gas production: about 4,100 h, DME production: about 3,000 h). Total amount of produced DME was about 400 tons.

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4.2. Process ow of 5TPD pilot plant Figure 5 shows the process ow of 5TPD pilot plant. Picture 1 shows the plant. Since natural gas was not available at Kushiro-city (the plant site)

during the operation period, LP gas and Coal Bed Methane were used as feedstock. Basic process ow 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.

Figure 5. Process ow of the 5TPD DME pilot plant

Picture 1. The 5TPD DME pilot plant

4.3. Experimental results (1) Eect 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

from the selectivity calculation. Figure 6 shows that the CO conversion increased with pressure, corresponding to the higher equilibrium conversion at the higher pressure. The once-through CO conversion reached higher and 5 MPa. The converthan 50% at 260 sion increased kinematically with temperature but has

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its maximum because the equilibrium conversion restricts 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 content in the syn-gas was controlled under 1.0106 to avoid poisoning the catalyst. The degradation of the CO conversion was conrmed 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 xed 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 (gh)/mol, molar ratio of H2 to CO is 1.0

Figure 7. Product selectivity vs. tions

reaction condi-

(3) Process material balance Figure 9 shows a typical example of the material balance of 5TPD pilot plant. Steam and recycled CO2 were both fed to the ATR to control the reforming 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 balance.

Figure 9. Typical material balance of 5TPD pilot plant

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(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 ow in the reactor, the range of W/F is depends on the reactor dimensions and catalyst concentration.

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 selectivity 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 overall reaction well followed the DME synthesis reaction (a). Table 6 shows typical product DME quality of the plant. This quality was sucient for IEAs recommended 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%.
Figure 10. Eect of W/F on once-through CO conversion Table 6. Product DME quality of 5 ton/day Plant Product content 99.9% < 0.01%

Figure 11 shows CO conversion as a function of recycle ratio. Recycle ratio was a ratio of recycled unreacted gas ow rate to make-up syn-gas ow rate. While recycle ratio was changed, W/F was kept at 3.8, then once-through CO conversion was almost constant.

DME Methanol + H2 O

5. Engineering of the DME slurry reactor When the DME slurry reactor is scaled-up, both catalyst activities and hydrodynamics of the catalyst slurry must be well considered. JFE started the study of high pressure DME slurry reactor with a (9 cm-diameter2 meter-height) reactor and a (4 cmdiameter4 meter-height) reactor. Eects of reaction conditions and products yields were studied with these reactors. The size of the reactor of the 5TPD pilot plant was 0.55 meter-diameter15 meter-height. Axial slurry mixing, gas-hold-up as well as the temperature controllability were tested with this reactor. The reactor has 30% to 50% of gas-hold-up, which is very typical 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 conditions. Figure 12 shows stability and homogeneousness

Figure 11. Total CO conversion as a function of recycle ratio (W/F=3.8 (gh)/mol, 260 , 5 MPa)

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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 200220 , temperature of the lower part of the reactor was slightly lower than 260 . As shown in Figure 12, most of reactor temperature in the slurry phase was even. The temperature dierence 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. Eect of gas residence time RTg on CO conversion

6. Conclusions JFE direct DME synthesis technology successfully nished 5TPD pilot plant project with achieving sufcient 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 production of 100 tons of DME per day will start in 2004. Acknowledgements The authors would like to express sincere appreciation for Agency of Natural Resources and Energy, Coal Division (METI) for their long term nancial support to the DME research Project. References
[1] Fleisch T. SAE 950 061, 1995 [2] Kikkawa Y, Aoki I. Oil Gas J, 1998(Apr,6), 96, 55 [3] Air products and Chemicals. DOE/PC/90018-T7, 1993 [4] Hansen J B, Voss B, Joensen F et al. SAE 950 063, 1995

Figure 12. Temperature stability of 5TPD DME reactor

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 eect of RTg on once-through CO conversion. RTg was dened as the ratio of actual fed gas ow rate to the slurry volume. RTg=[slurry volume]/[actual gas ow 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 sucient. 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.

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of the AIChE 2001 Spring National Meeting, (USA, Huston, Mar.22-26) 2001. Oxygenated Fuels [9] Ohono Y, Ogawa T, Shikada T et al. Oil Gas European Magazine, 2001, 2: 35 [10] Ogawa T, Inoue N, Shikada T et al. In: Wahab D H ed. Proceedings of GASEX 2002, (Brunei Darussalam, May27-30) 2002. Break Out Session C: Application and NGV [11] Bohnen L J. Soap Perfume Cosmet, 1979, 6: 300