The catalytic performance of FexMn1-xWO4 as novel wolframite-type nanocatalysts for the selective dehydration of methanol into dimethyl ether

Abstract

Selective production of dimethyl ether (DME), as a second-generation biofuel, under mild green conditions is still a challenge. Herein, FexMn1-xWO4 wolframite-type materials were proposed for the first time as efficient, selective, and stable catalysts towards methanol dehydration into DME. A simple one-step co-precipitation approach was used to fabricate the nanocomposites, and their catalytic performances were evaluated in comparison to earlier studies and to the commercial γ-Al2O3 in terms of activity. The catalysts’ structure, morphology, and porosity were identified by XRD, XPS, FTIR, TEM, and N2-sorption analyses. Results of XRD and XPS confirmed the successful synthesis of FexMn1-xWO4 catalysts. Acidity of these nanocomposites were greatly influenced with the variation in x-value, calcination temperature, and doping with SO42−. The Brønsted characters of the acid sites and their weak and medium strength were investigated from PY-FTIR, chemisorption of basic probes and pyridine-TPD. The variation of the catalytic activities of these nanocomposites was strongly correlated to the variation in the catalyst acidity. The catalytic activity results indicated that Fe0.5Mn0.5WO4 catalyst calcined at 500 °C and modified with 5 wt.% of SO42- is the most effective nanocomposite with conversion values of 86 and 90% at reaction temperatures of 250 and 275 °C, respectively and all of 100% DME selectivity. The remarkable enhancement in the catalytic activity due to the doping with SO42- is attributed to the inductive effect of S = O group created on the catalyst surface. This nanocomposite could be regenerated many times with nearly the same efficiency and selectivity. Moreover, it offered a long-term stability (∼120 h) towards DME production.