2110.     LEWIS, W. K., GILLILAND, E. R., AND REED, W. A.  Reaction of Methane With Copper Oxide in a Fluidized Bed.  Ind. Eng. Chem., vol. 41, 1949, pp. 1227-1237; Chem. Abs., vol. 43, 1949, p. 7199.

        Reaction between CH₄ and CuO deposited on silica gel, when stoichiometrically controlled to give a molal O₂:C ratio of 1.0 or slightly greater, is an effective means of producing CO and H₂ in a molal ratio of about 1:2.  Reaction rates are high enough so that there is no reason for temperatures to be far in excess of those required by equilibrium.  In a fluidization unit with a 4-ft. bed at 1,640° F. and 1 atm., 94% CH₄ decomposition was obtained with a selectivity of 92%.  Higher conversions could be obtained with a higher temperature or a greater bed depth.  The data were correlated on the assumption that the limiting factor is the reaction of CO₂ and water vapor with CH₄.  The CH₄-CuO reaction occurs in 2 steps:  An initial step that results in the rapid reduction of Cu and the simultaneous complete oxidation of part of the CH₄ and a 2d step that is rate-controlling and consists of the reforming of the remaining CH₄ with CO₂ and H₂O produced by the 1^st step to form CO and H₂.  the rates of the reforming reactions over Cu on silica gel are controlled by chemical reaction and not by gaseous diffusion.