Isomerization reactions on commercial zirconium sulfate catalyst are investigated in order to determine influence of hydrogen/feed ratio, space velocity and temperature on n-hexane conversion. Investigated range of inlet parameters includes values that are applied in the industrial practice of the isomerization process. Box-Behnken experimental design was carried out in order to optimize n-hexane isomerization process. Statistical analysis of experimental data was performed to obtain second order polynomial model and the optimum conditions were determined: hydrogen/feed ratio of 6, space velocity of 2 h(-1) and temperature of 170 degrees C. At optimum conditions conversion of n-hexane was 70 wt.%. In addition, temperature dependency of product composition was investigated at optimum values of hydrogen/feed ratio and space velocity. Obtained results show that methylpentanes greatly depend on temperature, unlike dimethylbutanes, in the studied range from 130 to 170 degrees C. Isomer that was produced in highest quantities was 2-methylpentane, while 3-methylpentane forms in somewhat smaller amounts. 2,2- and 2,3-dimethylbutanes, which contribute the most to the octane number value, are formed in relatively small quantities, amounting to less than 10 wt.% of the total amount of isomers formed. (C) 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.