797. ------. [GESSMANN, W., AND SHADLER, E. W.] Hydrocarbons. British Patent 487,250, June 17, 1938. Chem. Abs., vol. 32, 1938. p. 9095.

Patent Abstracts

In the synthesis of hydrocarbons from CH₄ and CO or CO₂ under high pressure, a mixture of these reactants that would give rise to an endothermic reaction (“fundamental reaction”) is modified by replacing part of the CH₄ by a mixture of H₂ or H₂O and CO and/or CO₂ that will form CH₄ exothermically by a so-called “steering reaction” The fundamental reaction and the steering reaction are combined in such a ratio that the resulting free energy of the net reaction, calculated according to the method of Lewis and Randall, foes not exceed 5,500 gm.-cal. per mol. of the product and may be negative. The molecular proportion of CH₄ to C oxides in the reaction mixture is at least 0.25. Among examples, the fundamental reaction of 17 CH₄+7 CO=3 C₈H₁₈+7 H₂O, which is strongly endothermic, is combined with the exothermic reaction 15 H₂+5 CO=5 CH₄+5 H₂O, with a free energy of –849 cal. per mol.: a mixture of H₂, 38%: CO, 31%: and CH₄, 31% is forced at 1,000 cu. m. per hr. through a contact tube filled with Fe-Mo catalyst at 850 atm. and 250º; the product is 315 kg. of hydrocarbons, mainly C₈H₁₅, per hr.