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Syngas to DME (Direct Route)

Background JFE Group developed a direct synthesis process of DME which has advantages in economics. Construction of a demonstration plant with 100 t/d capacity was finished in Nov. 2003. The first demonstrating operation (Run 100) through Dec. 2003 to Jan. 2004 and the second operation (Run 200) through June 2004 to Aug. 2004 were completed successfully. Reaction Equation (4) is the overall equation, and is materialized from three step reactions: the methanol synthesis reaction in Eq. (1), the methanol dehydration reaction in Eq. (2), and the water-gas shift reaction in Eq. (3). Eq. (4) has activity which synthesizes DME at a high conversion from a synthesis gas with a 1:1 molar ratio of CO and H2. 2CO + 4H2 2CH3OH 2CH3OH CH3OCH3 + H2O H2O + CO H2 + CO2 3CO + 3H2 CH3OCH3 + CO2 Reaction Condition T = 260oC P = 5 Mpa Conversion and Selectivity The conversion of synthesis gas, the selectivity to DME and the purity of DME reached to 96% (Target: more than 95%), 93% (Target: more than 90%) and 99.6% (Target: more than 99%), respectively. By-products By-product of reaction (1) is CO2, actually with methanol and a very small amount of water, separation of liquid product and unreacted synthesis gas is efficiently done at chilled temperature. By produced CO2 can be removed by dissolving in produced DME. Separation sequence The separation sequence is the the synthesis gas-product separation, the DME purification and the methanol-water separation and by this sequence three distillation columns are required. Why produce DME As an oxygenated compound, DME has excellent combustion characteristics, and because it has no carbon-carbon bonds in its chemical structure, it does not generate particulate matter (PM) in the combustion process. Furthermore, as it contains no sulfur, it does not generate SOx. [1] [2] [3] [4] H = -180.58 kJ mol-1 H1023 = -23.41 kJ mol-1 H1023 = -40.96 kJ mol-1 H1023 = -246.02 kJ mol-1 Methanol synthesis Methanol Dehydration Water Gas Shift Overall Reaction

Process

Direct(JFE Process) Reaction pressure (MPa) 5 Reaction Temperature (oC) 240-280 Single pass conversion (%) 50 Reaction by-product CO2 (water + MeOH)/DME molar 0.1 ratio Reactor Slurry Phase

Indirect (two steps) Methanol synthesis 8-10 180-270 38 Fixed bed

Methanol dehydration 1-2 300-340 70 Water 1.9 Fixed bed

Process Factors Weighting Economic Potential Operational safety Carbon footprint Technology feasibility Innovation Size footprint Environmental Impact of chemicals (waste disposal) Index

Reference [1]http://www.chemistry.fudan.edu.cn/usr2000/tangyi/paper/2004CatalLett_xiajianchaoOnestep%20synthesis%20of%20dimethyl%20ether%20from%20syngas%20with%20Fe-modified.pdf [2] New Direct Synthesis Technology for DME (Dimethyl Ether) and Its ApplicationTechnology: http://www.jfe-steel.co.jp/en/research/report/008/pdf/008-06.pdf

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