Methanol dehydration on carbon-based acid catalysts

Abstract

Methanol dehydration to produce dimethyl ether (DME) is an interesting process for the chemical industry since DME is an important intermediate and a promising clean alternative fuel for diesel engines. Pure or modified γ-aluminas (γ-Al2O3) and zeolites are often used as catalysts for this reaction. However, these materials usually yield non desirable hydrocarbons and undergo fast deactivation. In this work, we study the catalytic conversion of methanol over an acid carbon catalyst obtained by chemical activation of olive stone with H3PO4. A significant amount of phosphorus remains over the catalyst surface after the activation process, mostly in form of C-O-PO3 and C-PO3 groups, which provide the carbon a relatively high surface acidity and oxidation resistance. Methanol decomposition on this catalyst yields selectivities to DME higher than 82% at 623K and methanol conversion of 34%, under the operating conditions studied. The activated carbon catalytic activity and stability, under inert and oxidant atmospheres, as well as different regeneration procedures, were studied. In the absence of oxygen, the catalyst suffers a progressive deactivation by coke deposition on the active acid sites (Fig. 1). The presence of oxygen modifies the carbon surface chemistry, probably through oxygen spillover on the catalyst surface, where the availability of labile oxygen avoids catalyst deactivation. A reaction mechanism has been proposed where methanol dehydration seems to proceed through an Eley-Rideal mechanism, which assumes the adsorption of water and oxygen spillover on the acid active sites, avoiding coke deposition.