Direct synthesis of dimethyl ether (dme) from synthesis gas using novel catalysts

Arınan, Ayça
Increasing prices of crude oil derived transportation fuels ascended the researches on seeking alternative fuels, in last decades. Moreover, the increasing rate of global warming, because of high greenhouse gas emissions initiated new research for environment-friendly clean alternative fuels. Due to its low NOx emission, good burning characteristics and high cetane number, dimethyl ether (DME) attracted major attention as a transportation fuel alternative. Two possible pathways have been proposed for DME production. One of these pathways is DME synthesis through conventional methanol dehydration. More recently, direct DME synthesis in a single step has attracted significant attention of researchers and fuel producers. Catalysts having two active sites are required for direct DME synthesis from synthesis gas. The aim of this work was to synthesize novel bifunctional direct DME synthesis catalysts and test their activity in a high pressure fixed bed flow reactor. Bifunctional mesoporous catalysts were synthesized by using one-pot hydrothermal synthesis, impregnation and physical mixing methods. These materials were characterized by XRD, EDS, SEM, N2 physisorption and diffuse reflectance FT-IR (DRIFTS) techniques. Characterization results of the catalysts synthesized by one-pot hydrothermal synthesis procedures in basic and acidic routes showed that pH value of the synthesis solution was highly effective on the final physical structure and chemical nature of the catalysts. Increase in the pH value promoted the incorporation of Cu, Zn and Al into the mesoporous MCM-41 structure. Also, effects of Na2CO3 addition on the catalyst structure during the hydrothermal synthesis procedure were investigated. The characterization results showed that metals were incorporated into the catalyst structure successfully. However, surface area results showed that loaded metals blocked the pores of MCM-41 and decreased the surface area of the catalysts. Effects of zirconium (Zr) metal with different weight ratios were also investigated. Results showed that Zr loading increased the surface area of the catalyst. A high pressure fixed bed flow reactor was built and the catalyst testing experiments were performed between the temperature range of 200-400°C, at 50 bars. The activity results of the catalyst synthesized by impregnation method showed that no DME was formed over this catalyst; however it showed promising results for production of methanol and ethanol. Selectivity values of these alcohols were between 0.35 and 0.2. Formation of methane and CO2 indicated the occurrence of reverse dry reforming reaction. Incorporation of Zr into the catalyst structure at neutral synthesis condition caused significant activity enhancement, giving CO conversion values of about 40% at 400°C. Product distribution obtained with this catalyst indicated the formation of DME, ethanol, methanol as well as CH4 and CO2. Highest DME selectivity (60%) was observed with the catalyst prepared by physical mixing of commercial methanol reforming catalyst with silicotungstic acid incorporated methanol dehydration catalyst having W/Si ratio of 0.4.


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Citation Formats
A. Arınan, “Direct synthesis of dimethyl ether (dme) from synthesis gas using novel catalysts,” M.S. - Master of Science, Middle East Technical University, 2010.