An indirect route containing methanol dehydrogenation, DME carbonylation, and methyl acetate hydrogenolysis was used for ethanol synthesis from methanol and syngas. DME was produced stably from the methanol dehydrogenation with a 90% yield over H-ZSM-5 at 453 K under 1 MPa. A cold trap was set behind the methanol dehydrogenation to collect the formed water and unreacted methanol. Rh/Cs2H2SiW12O40 was an excellent catalyst for the DME carbonylation to methyl acetate at 473 K. The selectivity for methyl acetate was very high (>90%) and raising CO/DME ratio improved the DME conversion. A reaction intermediate similar to the homogeneous Rh-I system could be formed on the Rh/Cs2H2SiW12O40 surface. Cu/CeO2 was an excellent catalyst for the methyl acetate hydrogenolysis to methanol and ethanol at 523 K. Both active Cu-0 species and active Cu+ species could be stabilized in the Cu/CeO2 catalyst. When three fixed-bed reactors and one cold trap were linked together to achieve the ethanol synthesis from methanol and syngas, an ethanol selectivity of 91.1% was obtained at a methanol conversion of 47.2% under 1 MPa. (C) 2013 Elsevier B.V. All rights reserved.