152a.    ----------------. [BASHKIROV, A. N., KRYUKOV, Y. B., AND KAGAN, Y. B.] [Mechanism of the Synthesis of Hydrocarbons From Carbon Monoxide and Hydrogen.]  Doklady Akad. Nauk S.S.S.R., vol. 78, 1951, pp. 275-276; Chem. Abs., vol. 45, 1951, p. 7,861.

                   Assumption (abs. 152) that the primary act in the Fischer-Tropsch synthesis is CO+2H₂→CH₂+H₂O, and not 2CO+H₂→CH₂+CO₂, and that CO₂ is formed only as a result of the secondary reaction CO+H₂O→CO₂+H₂, was confirmed directly by flow experiments in which a very short contact time prevented the secondary reaction from taking place to any appreciable extent in 1 single pass, and the H₂O formed in each pass was removed by condensation between passes in repeated recirculation.  The experiments were conducted with a CO:H₂=1:2 mixture at 300° under 20 atm., at a gaseous space velocity of 150,000 1. per 1. catalyst per hr., practically complete conversion was ensured by repeated recycling, with the fresh gas admitted at the rate of 44 1. per hr.  Under these conditions, 290 1. gas save, after several hr., liquid hydrocarbons 22.5 gm. per m.³, gaseous hydrocarbons (C₃+C₄) 44.2. CH₄ 100.0. H₂O 252.2 gm. per m.³, and no CO₂.  This results excludes the direct reaction 2CO+H₂→CH₂+CO₂ and demonstrates that on Co, Ni, and Fe catalysts alike, CO₂ is formed only through a secondary reaction between CO and H₂.