Supported nickel sulfate was proved to be an efficient catalyst for gas-phase dehydration of glycerol to acrolein at 340 degrees C in the presence of oxygen. At a GHSV of glycerol of 873 h(-1), glycerol conversion over 17NiSO(4)-350 was still higher than 90% even after 10 h of reaction, with selectivity to acrolein always higher than 70 mol.%. It was demonstrated that Lewis acid sites were responsible for heavy compounds formation, and that Bronsted acid sites with medium and high strength were active sites for acrolein production from glycerol dehydration. The acidity of supported nickel sulfate was associated with one meta-stable structure, NiSO4 center dot xH(2)O (0 < x < 1). Furthermore, not only nickel cations but also sulfate groups exhibited oxidizability during reactions, and loss of sulfur was the main reason for irreversible deactivation of supported nickel sulfate. (C) 2013 Elsevier Inc. All rights reserved.