Process for absorbing olefines having three or more carbon atoms in the molecule by means of sulphuric acid, phosphoric acid or strong sulphonic acids, and for the manufacture of the corresponding esters, ethers, alcohols or other compounds

摘要

336,604. Elkington, H. D., (Naamlooze Venootschap de Bataafsche Petroleum Maatschappij). June 4, 1929. Sulphates, sulphonates, and phosphates, ethereal; alcohols; ethers.-Olefines having more than two carbon atoms and one or more double bonds in the molecule are absorbed in sulphuric acid, phosphoric acid, or strong sulphonic acids in the presence of catalysts comprising one or more of the metals copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or platinum, or one or more compounds thereof. When the metals themselves are employed, they should preferably be brought into very finely divided form, for example, colloidally precipitated on a carrier such as carbon black, silica gel, or decolorizing clay. When compounds are used, those such as cuprous cyanide which are soluble in the acids may be added thereto originally, and the solution used as an absorbtion medium; or such compounds, also those which are insoluble, for example, potassium platinochloride, cuprous sulphate, cupric sulphate, cuprous chloride, cupric chloride, cuprous oxide, and ferrous sulphate, may be converted into soluble complex compounds within the acid by passing carbon monoxide, nitric oxide, or ethylene therethrough. Soluble compounds of such of the metals as are attacked by the acids may be formed by adding the metals themselves thereto. Metal compounds may be used which have the metal either in the higher or lower valency state, for example, both platinic and platinous compounds are suitable. The reaction may be carried out at ordinary, reduced, or increased pressures or temperatures. Solvents such as ethyl alcohol, acetic acid, nitobenzene, or ether may be added to the acids, and substances known to accelerate the absorbtion such as frothforming substances or emulsifying agents may also be present. The olefines may be dissolved in suitable solvents before being brought into contact with the acids. The method may be applied to crude gases containing olefines with more than three carbon atoms in the molecule, for example, natural gas or cracking gases. The liquid containing the absorbed olefines is hydrolyzed, distilled, or otherwise treated in known manner for the production of compounds such as esters, alcohols, or ethers therefrom. According to examples (1) propylene is absorbed in 90 per cent sulphuric acid containing platinum deposited on carbon black, (2) propylene is absorbed in sulphuric acid containing cuprous cyanide dissolved therein, (3) cuprous oxide is added to sulphuric acid and converted into a soluble complex compound by passing carbon monoxide through the liquid, which is then used to absorb propylene, (4) propylene is absorbed in a solution of cuprous cyanide in orthophosphoric acid, (5) propylene is absorbed in a solution of cuprous cyanide in benzenesulphonic acid, (6) diallyl is stirred with sulphuric acid and cuprous cyanide at 10‹ C.; ice is added, and on stirring the oil which separates with water a precipitate is formed containing the inner sulphuric ester of 2, 5-hexanediol, (7) propylene is absorbed in sulphuric acid containing the complex compound formed by adding cuprous cyanide and passing carbon monoxide through the solution, (8) cuprous chloride is suspended in sulphuric acid and converted into a soluble complex compound by passing nitric oxide therethrough; propylene is then absorbed in the solution. Specifications 323,748 and 324,897 are referred to.