801.    [EIDUS, Y. T., ZELINSKII, N. D., AND PUZITSKII, K. V.]  [Catalytic Hydrocondensation of Carbon Monoxide With Olefins.  III.  Polymerization and Hydropolymerization of Ethylene Under the Conditions of Hydrocondensation Catalysis.]  Izvest. Akad. Nauk S.S.S.R., Otdel. Khim. Nauk, 1950, pp. 98-107; Chem. Abs., vol. 44, 1950, p. 6100.

     (1) C₂H₄ alone and in mixture with H₂ was passed at 190°, under atmospheric pressure, over catalyst (III) after it had been used for 120 hr. in hydrocondensation of 1CO:2H₂:3C₂H₄.  Its activity in that reaction is expressed by the production of 218-237 ml. per m.³ oil, or 21.1 ml. per l. per hr. at space velocity S=101-114; gas contraction, c=31.3%, H₂O yield, w=20.8-39.5 ml. per m.³.  In a subsequent run with C₂H₄ alone (86% pure), c was 12%, oil initially 62.7 ml. per m.³ (6.0 ml. per l. per hr.), falling to 32.8 (2.9), extent of reaction 13% of the C₂H₄ passed, w=15.7-32.8 ml. per m.³.  This shows that, in CO+H₂+C₂H₄ the liquid products cannot be due to a polymerization of C₂H₄ itself.  (2) in a subsequent run with 2C₂H₄:1H₂, the oil yield rose to 118.2 ml. per m.³ (9.7 ml. per l. per hr.), c to 32.2% extent of reaction 46.7% of the C₂H₄ passed, with 53.7% of the C₂H₄ reacted spent on formation of liquid and solid products; H₂ reacted to the extent of 71.8%, with 34.1% of the H₂ reacted spent in the formation of liquid and solid.  In a subsequent run with 1C₂H₄:  1H₂, the oil yield was 202.0 (20), c 48.3%, extent of reaction 87.7, and 72.7% of C₂H₄ and H₂ passed, respectively, with 45.4 and 28.5%, respectively, of the C₂H₄ and H₂ reacted gone into the liquid and solid product.  In two following runs with 1C₂H₄:1.2H₂, the C₂H₄ reacted completely (100%), but only 20-25% of it went into the oil the yield of which fell  to 49.6 (3.5).  The same results were obtained in an analogous series of runs, on catalyst (IV).  As a rule, the proportion of light oil in the liquid product is markedly higher with H₂+C₂H₄ than with CO+H₂+C₂H₄ and increases in consecutive runs.  (3) Passage of H₂ alone over a catalyst having been used in runs with CO+H₂+C₂H₄, produces no significant amounts of liquid and no light oil.  This proves that the hydrocondensation products obtained with H₂+C₂H₄ are not due to a hydrogenation of the solid deposit formed on the surface of the catalyst.  (4) Passage of 1H₂:1C₂H₄ on a fresh catalyst produced practically no oil, only hydrocarbons C₄, with a yield of 5.2-14.0% with respect to C₂H₄ passed, or 35-90.5 liquid ml. (at –80°) per m.³ gas passed.  The main mass of the C₂H₄ is hydrogenated to C₂H₆.  (5) These results are interpreted as being due to the presence of CH₂ radicals at certain points of the lattice of the metallic catalyst surface having been used with CO+H₂+C₂H₄.  Wherever a CH₂ group happens to be located in a suitable position between the ends of 2 molecules of C₂H₄ adsorbed on the same surface, it serves as a bridge linking the C₂H₄ molecules and leading to the formation of higher polymerization products.  Such CH₂ groups being absent at the surface of a fresh catalyst, the probability of higher polymerization is very slight and there can only be dimerization of adjacent C₂H₄ molecules into C₄ products.