A non-stoichiometric thermodynamic analysis is performed on the adsorption-enhanced steam reforming of glycerol for hydrogen production based on the principle of minimising the Gibbs free energy. The effects of temperature (600-1000 K), pressure (1-4 bar), water to glycerol feed ratio (3:1-12:1), percentage of CO(2) adsorption (0-99%) and molar ratio of carrier gas to feed reactants (1:1-5:1) on the reforming reactions and carbon formation are examined. The results show that the use of a CO(2) adsorbent enhances glycerol conversion to hydrogen and the maximum number of moles of hydrogen produced per mole of glycerol can be increased from 6 to 7 due to the CO(2) adsorption. The analyses suggest that the most favourable temperature for steam-glycerol reforming is between 800 and 850 K in the presence of a CO(2) adsorbent, which is about 100 K lower than that for reforming without CO(2) adsorption. Although high pressures are favourable for CO(2) adsorption, a lower operating pressure gives a higher overall hydrogen conversion. The most favourable water to glycerol feed ratio is found to be similar to 9.0 above which the benefit becomes marginal. Carbon formation could occur at low water to glycerol feed ratios, and the use of a CO(2) adsorbent can suppress the formation reaction and substantially reduce the lower limit of the water to glycerol feed ratio for carbon formation. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.