Highly effective hybrid catalyst for the direct synthesis of dimethyl ether from syngas with magnesium oxide-modified HZSM-5 as a dehydration component

A series of HZSM-5 zeolites modified with various contents of magnesium oxide (0–10 wt%) were prepared with an incipient impregnation technique and characterized by X-ray diffraction, N2 adsorption, temperature-programmed desorption of NH3 and CO2, 27Al MAS NMR, and FT-IR. The modified HZSM-5 zeolites were mixed physically with methanol synthesis components (CuO–ZnO–Al2O3) to perform the direct synthesis of dimethyl ether (DME) from syngas under pressurized fixed-bed continuous-flow conditions. The results indicated that modification of HZSM-5 with a suitable amount of MgO significantly decreased the selectivities for undesired by-products like hydrocarbons and CO2 from 9.3 and 37.1% to less than 0.4 and 31%, respectively, through the removal of unselective strong Brønsted acid sites and hence enhanced the selectivity for DME from 49% to more than 64%, whereas the conversion of carbon monoxide was scarcely affected. However, when the MgO contents were equal to or higher than 5 wt%, both the conversion of CO and selectivity for DME decreased markedly because of the decreased activity for methanol dehydration. A mechanism for methanol dehydration to DME involving both acidic and basic sites on the HZSM-5 zeolites modified with MgO has been proposed based on the results obtained.