Direct dimethyl ether synthesis from synthesis gas: The influence of methanol dehydration on methanol synthesis reaction

• Cu-based catalyst performance was studied in methanol and direct DME syntheses.
• Methanol dehydration affects methanol formation kinetics negatively.
• Water, formed by methanol dehydration, can be the cause of the observed effect.
• DME is practically inert over the methanol synthesis catalyst.
• Addition of water to the feed decreases methanol formation rate significantly.

Direct dimethyl ether (DME) synthesis from synthesis gas is studied with regard to potential effects of methanol dehydration on methanol formation and copper-based catalyst performance. For this, the influence of the operating conditions (space velocity, temperature, pressure, time-on-stream and syngas composition) on activity, selectivity and stability of the catalyst was studied and compared for methanol synthesis and direct DME synthesis. The advantage of the direct over the two-step DME synthesis is apparent at conditions where syngas conversion to methanol is thermodynamically limited. However, under the applied operating conditions, results suggest that combining methanol synthesis and dehydration has a negative effect on the methanol formation kinetics. The origin of the observed phenomena is investigated by varying dehydration catalyst and by introducing dehydration products (DME and water) into the methanol synthesis feed. Choice of the solid acid catalyst does not seem to affect methanol formation, and DME is also found to be practically inert over the methanol synthesis catalysts. Water injection, on the other hand, led to a significant decrease in the methanol synthesis rate. Thus, formation of an additional amount of water through methanol dehydration might be an explanation for the lower methanol formation rate in the direct DME synthesis.

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