Effects of Cu–ZnO Content on Reaction Rate for Direct Synthesis of DME from Syngas with Bifunctional Cu–ZnO/γ-Al2O3 Catalyst

Abstract

The effects of Cu–ZnO content on the performance of bifunctional Cu–ZnO/γ-Al2O3 catalysts for dimethyl ether (DME) synthesis from syngas were investigated by varying the weight ratios of Cu–ZnO/γ-Al2O3 prepared by the coprecipitation of Cu–ZnO in a slurry of γ-Al2O3. A higher rate of DME production with CO conversion of 47.6 % and DME selectivity of 61.1 % was observed with the bifunctional catalyst at an optimal weight ratio of CuO/γ-Al2O3 of two, providing a higher surface area of metallic copper and an abundance of weak acid sites. The number of acidic sites on solid-acid γ-Al2O3 is a more crucial factor to enhance DME yield, due to the faster dehydration rate of methanol to DME than that of CO hydrogenation to methanol. Although the first step of methanol synthesis on active copper sites is a rate-limiting step with a low equilibrium value, the second step of the dehydration of methanol to DME on acid sites adjusts the overall rate by enhancing the forward reaction rate of CO hydrogenation to methanol with a simultaneous formation of surplus hydrogen by a water–gas shift reaction. Therefore, the proper design of a high surface area of metallic copper with larger acid sites on the bifunctional CuO–ZnO/γ-Al2O3 catalysts at an optimal ratio, produced by adjusting the weight ratio of CuO/γ-Al2O3, is an important factor for improved catalytic performance.