Patent GB-463791-A (GB)
Title: Production of higher boiling hydrocarbons from olefines
IPC: C07C9/16
Filed: 1935-08-01
Abstract: Hydrocarbons suitable for fuels, lubricants, resin production, &c. are made by treating hydrocarbons containing secondary and tertiary olefines which may be obtained from various sources, by selectively absorbing the tertiary olefines, and then polymerizing the absorbed olefine or the remaining secondary olefine and hydrogenating the polymer.  The absorption of the tertiary olefine may be effected in the vapour or liquid state in sulphuric, p  phosphoric, pyrophosphoric, arsenic, hydrochloric or benzene-sulphonic acid or in acid liquors in which olefines of the same or less reactivity have been absorbed, or in solutions or suspensions of salts such as silver or lead sulphate, bismuth oxychloride, or copper phosphate, which absorbents also act as polymerizing agents; but the polymerization may also be effected by Friedel-Crafts reagents such as aluminium, zinc, or magnesium chlorides.  Higher polymers may be obtained by increasing the concentration of the acid or adding another polymerization agent such as aluminium chloride; and in the latter case the operation is preferably carried out in steps, the acid polymerization product, preferably rectified, being treated with the more active agent.  The hydrogenation of the polymers is effected by any known method.  Suitable catalysts are metals of groups 1, 6, and 8 of the Periodic table, such as copper, tungsten, platinum black, copper chromite, copper and nickel with zinc or cobalt, nickel on pumice or alumina, also the oxides, sulphides and phosphates of these metals, especially of group 6, such as chromic oxide gel, molybdenum phosphate, or tungsten disulphide.  Various temperature and pressure conditions may be employed; thus colloidal palladium effects hydrogenation of di-isobutylene at room temperature, but nickel requires over 100 DEG  C. and 10 atmospheres pressure.  In an example for the production of iso-octane (2.2.4-trimethyl pentane) a butane-butene hydrocarbon fraction is treated with sulphuric acid of 50--75 per cent strength at 50 DEG  C. and the absorption product is heated to 80--110 DEG  C. in a closed vessel with stirring or by passage through a coil.  The polymer is rectified to separate di-isobutylene from tri-isobutylene, and the former is hydrogenated. The preferred nickel catalyst is prepared by heating nickel formate suspended in oil at 300 DEG  C. in hydrogen. The hydrogenation may be effected in an autoclave with stirring or in the vapour phase by passing over active nickel on pumice at 200--300 DEG  C. and 10,5--17,5 atmospheres.  Preferably, the initial hydrocarbon mixture or the polymer is freed from sulphur; for this purpose the polymer may be refluxed with an oxidizing agent such as hydrogen peroxide, washing with mercuric nitrate or absorption with active nickel or silica gel.  When a sulphide catalyst is employed, the removal of sulphur is unnecessary, and hydrogen sulphide may be added.  A table of hydrocarbons that may be obtained from butane-butene and pentane-pentene fractions is given.  The Specification as open to inspection under Sect. 91 includes in the table products that may be obtained from an ethylene-propylene fraction; and the subject-matter of Specification 465,459.  This does not appear in the Specification as accepted.ALSO:Polymers of tertiary or secondary olefines are hydrogenated to obtain saturated hydrocarbons.  The hydrogenation may be effected by any known method.  Suitable catalysts are metals of Groups 1, 6 and 8 of the Periodic table such as copper, tungsten, platinum black, copper chromite, copper and nickel with zinc or cobalt, nickel on pumice or alumina; also the oxides, sulphides and phosphates of these metals, especially of Group 6 such as chrome oxide gel, molybdenum phosphate, or tungsten disulphide.  Various temperature and pressure conditions may be employed; thus colloidal palladium effects hydrogenation of di-isobutylene at room temperature, but nickel requires over 100 DEG  C. and 10 atmospheres pressure.  A preferred nickel catalyst is prepared by heating nickel formate suspended in oil at 300 DEG  C. in hydrogen. The hydrogenation may be effected in an autoclave with stirring, or in the vapour phase by passing over nickel on pumice at 200--300 DEG  C. and 10,5--17,5 atmospheres.  Preferably, the hydrocarbon to be hydrogenated or the initial material from which it is prepared is freed from sulphur, processes for this purpose being described.  When a sulphide catalyst is employed this removal of sulphur is unnecessary, and hydrogen sulphide may be added.  The Specification as open to inspection under Sect. 91 includes the subject-matter of Specification 465,459.  This does not appear in the Specification as accepted.