Nanocomposite nafion and heteropolyacid incorporated mesoporous catalysts for dimethyl ether synthesis from methanol

Çiftçi, Ayşegül
The need for alternative transportation fuels is rising with the rapid depletion of oil reserves and the simultaneous growth of the world’s population. Production of dimethyl ether, a non-petroleum derived attractive fuel-alternate for the future, is a challenging research area. Different routes and various solid-acid catalysts are being developed in order to achieve the most efficient way of synthesizing this potential diesel alternative fuel. The focus of heterogeneous catalysis is to convert renewable feed stocks to valuable chemicals. Nafion resin and heteropolyacid compounds are active acidic catalysts with significantly low surface areas, which act as a strong barrier limiting their catalytic activity. Synthesizing solid-acid catalysts by incorporation of nonporous active compounds into mesoporous silicate structured materials opens a door to producing valuable chemicals by heterogeneous catalysis. The objective of this work was to synthesize and characterize nafion and heteropolyacid incorporated nanocomposite catalysts and to catalyze DME synthesis by dehydration of methanol at different temperatures. The interactions of methanol and DME with these catalysts were also investigated by in situ FT-IR. Silicotungstic acid (STA)/Silica and Tungstophosphoric acid (TPA)/Silica catalysts were synthesized by following a one-pot hydrothermal route. These mesoporous catalysts had surface area values of 143-252 m2/g. The STA/SiO2 nanocomposite catalyst having a W/Si atomic ratio of 0.33 showed the highest activity, with a DME selectivity approaching to 100% and a methanol conversion of 60% at 250°C at a space time of 0.27 Effects of W/Si atomic ratio and the synthesis procedure on the performance of these novel materials were investigated. Nanocomposite Nafion/SiO2 solid-acid catalysts having high surface area values (595-792 m2/g) and narrow pore size distributions (4.3 nm) were successfully synthesized by a one-pot hydrothermal procedure. Effects of the modifications in the synthesis procedure concerning the surfactant removal, nafion loading, etc. were investigated based on the characterization results and activity tests. Nafion was observed to be uniformly distributed within these mesoporous catalysts. Nafion resin was also impregnated into aluminosilicate and α-alumina, but one-pot synthesis was concluded to be better for obtaining well dispersed, nafion incorporated active catalysts. The Nafion/Silica catalyst synthesized by a nafion/silica weight ratio of 0.15 and washed with 2M sulfuric acid-ethanol solution exhibited the highest activity due to its highest Brönsted, as well as Lewis acidity. A methanol conversion of 40% at 300°C, 0.27 and DME selectivity values approaching to 100% over 180°C were very promising for the synthesis of this green fuel alternate over the new catalysts synthesized.


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Citation Formats
A. Çiftçi, “Nanocomposite nafion and heteropolyacid incorporated mesoporous catalysts for dimethyl ether synthesis from methanol,” M.S. - Master of Science, Middle East Technical University, 2009.