Patent GB-446114-A (GB)
Title: Process for the production of valuable hydrocarbons by heat treatment with hydrogenating gases of distillable carbonaceous materials
IPC: C10G1/08
Filed: 1934-12-11
Abstract: The production of hydrocarbons by the hydrogenation of oxygen- or sulphur-containing organic compounds, e.g. the conversion of phenols or cresols into cyclic hydrocarbons, is carried out in the presence of catalysts comprising germanium or a compound thereof together with an additional substance selected from the halogens or their compounds, acid acting substances, basic substances, sulphur or compounds of sulphur.  The germanium compounds specified include sulphides (particularly as obtained by decomposition of thio salts) oxides, hydroxides, halides or organic compounds, e.g. the oxalate. The halogen compounds specified include organic halogen compounds, ammonium chloride, and compounds of halogens with the metalloids. Acidic compounds include sulphuric, nitric, phosphoric, and sulphonic acids, while the alkaline reacting substance specified include the oxides, hydroxides, carbonates and sulphides of the alkali or alkaline earth metals, ammonia and bases such as quinoline.  When applying sulphur as additional substance, the sulphur or sulphur compounds are mixed with the germanium compound or they may be arranged in the reaction space.  Alternatively, a germanium compound of sulphur may be used, e.g. germanium sulphide or a thiopyrogermanate.  Germanium sulphide is preferably produced by decomposition of ammonium thiogermanate with acids or by thermal treatment in the presence of ammonia hydrogen sulphide &c., or by the reduction of germanium disulphide with hydrogen. Specification 312,043, [Class 1 (i)], is referred to.ALSO:The production of valuable hydrocarbons by the treatment of carbonaceous materials with hydrogenating gases under elevated conditions of temperature and pressure which expression includes destructive hydrogenation, purification (by hydrogenation) of mineral oils, conversion of oxygen and sulphur containing organic compounds into the corresponding hydrocarbons or hydrogenated hydrocarbons, e.g. the conversion of phenols or cresols into cyclic hydrocarbons, and the improvement of motor fuels and lubricating oils by aromatization, or hydroforming treatments is carried out in the presence of catalysts comprising germanium or a compound thereof together with an additional substance selected from halogens or their compounds, acids, acid acting substances, basic substances, sulphur or compounds of sulphur.  The germanium compounds specified include sulphides (particularly as obtained by decomposition of thio salts) oxides, hydroxides, halides or organic compounds, e.g. the oxalate.  The halogen compounds specified include organic halogen compounds, ammonium chloride, and compounds of halogens with the metalloids.  Acidic compounds include sulphuric, nitric, phosphoric, and sulphonic acids, while the alkaline reacting substances specified include the oxides, hydroxides, carbonates and sulphides of the alkali or alkaline earth metals, ammonia and bases such as quinoline.  When applying sulphur as additional substance the sulphur or sulphur compounds are mixed with the germanium compound or they may be arranged in the reaction space.  Alternatively, a germanium compound of sulphur may be used, e.g. germanium sulphide or thiapyrogermanate.  Germanium sulphide is preferably produced by decomposition of ammonium thiogermanate with acids or by thermal treatment in the presence of ammonia hydrogen sulphide &c., or by the reduction of germanium disulphide with hydrogen.  When germanium compounds other than sulphides are used these may be converted into the sulphide under the reaction conditions excess sulphur or compounds thereof being added to the reacting materials.  Examples are given of the conversion of coal pastes or petroleum residues in the presence of (1) germanium oxide acid chlorine, (2) germanium disulphide with the addition of 0,8 per cent hydrogen sulphide to the hydrogenating gases, (3) germanium disulphide and carbon disulphide.  Specification 312,043, [Class 1 (i)], is referred to.