Reaction pathways for oxygenates, acetic acid, ethylene glycol (EG), 2-ethoxyethanol (2-EE) and 1,2-diethoxyethane (1,2-DEE) added during Fischer-Tropsch synthesis (FTS) over a doubly promoted fused iron catalysts were studied. The addition of acetic acid, EG and 2-EE affected only slightly the CO conversion but resulted in a significant reduction in H-2 conversion while addition of 1,2-DEE results in slight increase in both H2 and CO conversion. Addition of these oxygenates caused a large decrease in the alkene ratio for C-2 hydrocarbons as compared to an increase for the C-3 and C-4 hydrocarbons suggesting a direct formation pathway of ethane from added oxygenate molecules. The 1-alkene/2-alkene fraction was found to increase significantly when these oxygenates were added and then return to the original value once the addition is terminated, indicating inhibition of secondary reactions of 1-alkene by added oxygenates. Added acetic acid reversibly increased the CO2 production rate while EG, 2-EE and 1,2-DEE reversibly decreased the CO2 selectivity. Addition of these oxygenates reduced the production rate of methane. Addition of acetic acid and 1,2-DEE decreased methanol selectivity significantly while added EG results in a significant increase in methanol production. In the case of 2-EE addition, methanol selectivity was nearly constant. Reaction of acetic acid during FTS was found to produce products such as ethyl butanoate, ethylene glycol and its ether, 1,2-diethoxyethane, which are not generally observed in the normal FTS product spectrum. Addition of EG results in a significant increase in the production rate of 1,2-DEE only and no measurable amount of 2-EE was found. While addition of 2-EE caused a significant increase in the production rate of glycol, the addition of 1,2-DEE indicated a significant increase in 2-EE production rate without any measurable change in EG selectivity. The results suggest that acetic acid undergoes some C-C bond rupture while 2-EE and 1,2-DEE undergoes cleavage of the ether linkage (C-O-C bond). On the contrary, EG undergoes fast and equally probable C-O-C chain growth in both terminal positions. The results indicate that neither of these oxygenates is a significant intermediate in FTS with an iron catalyst. Product distribution in most of the oxygenate compounds are consistent with hydrogenation of the added oxygenate to acetaldehyde and/or ethanol as primary products followed by secondary reaction of these two primary oxygenate products. (c) 2008 Elsevier B.V. All rights reserved.