Steam reforming (SR) and autothermal reforming (ATR) of n-butanol was studied over 0.5 wt% Rh/ZrO2 catalyst at 500, 600 and 700 degrees C, atmospheric pressure, steam to carbon (S/C) molar ratio of 4 and oxygen to carbon (O-2/C) molar ratio of 0.1. The influence of the O-2/C ratio on performance was also carried out at 500 degrees C. Catalyst performance, i.e. conversion, product distribution and short-term stability, was compared with plain ZrO2 support to derive a reaction network, including contributions of reactions in the gas phase, on the support and on Rh. At 500 and 600 degrees C the catalyst deactivated very rapidly for WGS and hydro-isomerization reactions, slightly less rapidly for reforming and significantly slower for dehydration and dehydrogenation reactions. Increasing temperature and oxygen concentration improved catalyst stability. Rh/ZrO2 showed promising performance at 700 degrees C with complete conversion and hydrogen yield, 70% of theoretical maximum, decreasing over 21 h with not more than 8 and 1% for SR and ATR, respectively. Deactivation of the catalyst for reforming is caused by carbon deposition on and near the Rh particles. At 700 degrees C, coke forms via gas phase reactions, while catalytic reactions on the surface mainly contribute at 500 and 600 degrees C. (C) 2014 Elsevier B.V. All rights reserved.