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.