2711.     ---------------.  [PLOTNIKOV, V. A., AND IVANOV, K. N.]  [Synthesis of Methanol From Carbon Monoxide and Hydrogen Under Pressure.]  Jour. Chem. Ind. (U.S.S.R.), vol. 7, 1930, pp. 1136-1145; Chem. Zentralb., 1931, I, p. 2143; Chem. Abs., vol. 25, 1931, p. 4218.

        Object of the investigation was the preparation of MeOH from CO and H₂ under high pressure with the use of catalysts.  The synthesis was carried out in a circulating system with a pressure decreasing from 170 atm. in an apparatus presenting no novel mechanical features.  The activity of Zn-Cr catalyst begins at 315°-320° and attains a practical speed of condensation at 330°.  The highest activity was displayed by Zn-Cr in the proportion of 4:1, while any decrease in Cr reduced the efficiency of the catalyst.  The results obtained with various thicknesses of the layers of catalyst do not snow any regularity, from which is inferred that such changes, besides influencing the speed of condensation, also affect the character of the process.  Dilution of the reacting gas mixtures with H₂ reduces the speed of reaction.  Increase of temperature accelerates the general course of the process:  At 360° CH₄ predominates, while at 400° higher hydrocarbons take its place.  The Zn-Cr catalyst becomes readily poisoned.  Precipitated on asbestos, it seems to possess a more highly active surface, tending also to an excessive formation of higher hydrocarbons.  ZnO is less active than Zn-Cr.  Addition of UO₂ to ZnO does not change the activity of the latter.  All catalysts containing Zn tend to the formation of gaseous products, such as CH₄ and higher hydrocarbons with separation of H₂O and contamination of the gases with CO₂.  Some CO is reduced to C with formation of soot.  The liquid condensate consisted of oil and water layers, the former comprising up to 10% of the bulk.  The aqueous layer condensate consisted of oil and water layers, the former comprising up to 10% of the bulk.  The aqueous layer contained up to 12% of MeOH, 15% EtOh, MeCOEt, and iso-BuCHO.  With a Cu catalyst obtained by precipitation of Cu(NO₃)₂ and reduction to Cu, the activity begins at 280°, drops at higher temperatures, and becomes again stable at 305°-310°.  Addition of 5% of Ag increases the activity of Cu, while addition of Zn-Cr increases the activity very highly, the reaction beginning at 240°.  Of all the composite catalysts containing 3 elements, Cu-ZnO-Cr₂O₃ in the proportion of 91:8:1 proved most active, supporting the reaction with enough speed at 250°.  Precipitation of a mixed solution of all 3 salts and subsequent reduction of the hydroxides produces a much more active catalyst than a mixture of separately prepared metals.  Increase of temperature speeds up the process, while dilution of the reacting gas with H₂ reduces the speed.  The Cu catalyst with decreased temperature tends to increase the formation of liquid products, however, without any oil.  The condensate contains 85% MeOH, EtOH, and H₂O, while the gas is mostly CH₄.  No formation of free C was observed.  At 250°-265°, the process proceeds to complete conversion of CO.  In these tests under the condition of falling pressure, the yield based on CO reached up to 70% when the condensate contained about 85% of MeOH.