Patent GB-320846-A (GB)
Title: Process for the manufacture and production of hydrocarbons of high boiling point
IPC: C10G50/00
Filed: 1928-05-18
Abstract: 320,846. Johnson, J. Y., (I. (G. Farbenindustrie Akt.-Ges.). May 18, 1928. - Hydrocarbons.-Mixtures of hydrocarbons such as the products obtained by the destructive hydrogenation 'of coal, oil shales, &c., by cracking oils and tars, or products obtained by the low temperature. carbonization of coal are converted into products of higher boiling point and increased viscosity by subjecting them to the action of fluorine, chlorine, bromine, iodine or halogenexchanging halogen compounds with simultaneous or subsequent addition of an element from the 3rd to the 8th group of the periodic system capable of existence in the metallic form, or a compound thereof or mixtures of these substances at catalysts. The products' may be subjected to a further condensation treatment in the presence of the said catalysts, preferably after removal of any halogen or halogen compounds present. Both operations must be conducted at temperatures below 150‹ C. and preferably below 100‹ C. so that little or no resinification takes place. Lubricating oils of the character of cylinder oils are obtained when employing initial materials containing a considerable amount of aromatic hydrocarbons. The halogen-exchanging substances may be methylene chloride, chloroform, carbon tetrachloride and the like. The speed of reaction can be regulated by the addition of oxygencontaining compounds so that no resinification occurs. When working under pressure it is sometimes advisable to bind the halogen hydride by the addition of metallic oxides or other basic substances. The halogen-exchanging compounds may be first formed by treating the starting material with halogen at a slightly elevated temperature and catalysts such as aluminium chloride, tin chloride, iron chloride, boron fluoride, phosphorus pentachloride, silicon tetrachloride, antimony chloride, chromium chloride, phosphorus pentoxide &c. alumina or the elements aluminium, iron, boron, tin, antimony, vanadium, chromium, molybdenum or tungsten. The aluminium chloride may be replaced by hydrochloric acid and activated metals such as aluminium prepared by acting on the latter with solutions of salts of metals ranging lower in the electromotive series than aluminium. Olefines such as ethylene, propylene, butylene may be employed in addition to the halogen-exchanging compounds and the catalytic condensing agents, and elements of the groups 1 and 2 of the periodic system such as alkali metals, magnesium, copper, silver, zinc, calcium, or the oxides, carbonates or halogenides thereof. Lubricating oils and products resembling rubber may be produced by this process. In' examples (1) a middle oil from Elwerath petroleum is treated with a mixture of methane chlorination products and aluminium chloride, a solvent such as benzine being added as required, giving a highly viscous product free from chlorine, and almost free from resins. The middle oil may also be first treated with chlorine. (2) A middle oil from brown-coal by hydrogenation under pressure is treated with chlorine and then polymerized with aluminium chloride, giving an oil of high viscosity. (3) A heavy benzine from the destructive hydrogenation of brown-coal is treated with chlorine and then mixed with a non-viscous product of higher boiling point from the same source. The mixture is heated with aluminium chloride to give an engine lubricating oil. (4) A heavy benzine is chlorinated and condensed by heating with aluminium chloride. The same heavy benzine is chlorinated after the addition of naphthalene giving a lubricating oil. (5) Crude naphthalene is acted upon with a halogenated mixture of hydrocarbons obtained by the destructive hydrogenation of brown-coal and warmed with aluminium chloride giving a lubricating oil. Chlorethylene may be used instead of the halogenated mixture . (6) Chlorinated heavy benzine from the hydrogenation of brown-coal heated with aluminium chloride and the first running from benzol distillation gives a cylinderoil. (7) Chlorinated heavy benzine by cracking American crude oil is heated with anthracene oil, zinc chloride and zinc oxide giving a lubricating oil. (8) Chlorinated heavy benzine from the hydrogenation of brown-coal is heated with aluminium chloride and a middle oil also from the hydrogenation of brown-coal giving a lubricating oil. (9) Chlorinated heavy benzine is condensed with a middle oil from hydrogenation of browncoal with ferric chloride and zinc dust, giving an engine oil. (10) A middle oil from the hydrogenation of brown-coal tar is treated with chlorine and heated with phosphorus pentoxide and iron filings previously activated with hydrochloric acid giving a light engine oil.