Patent GB-477030-A (GB)
Title: Improvements in and relating to the treatment of solid, liquid or gaseous hydrocarbon-containing materials for the production of valuable compounds
IPC: B44F11/02
Filed: 1936-05-15
Abstract: Solid, liquid, or gaseous hydrocarbons are converted into valuable products, e.g. petrol, by treatment at elevated temperatures, e.g. above 400 C., and preferably under pressure, in presence of solid hydrogenation catalysts which comprise or form part of solid electrically-conducting bodies firmly positioned in electrically-conducting manner between two or more electrodes whereby direct or alternating current is passed through the bodies. Conducting bodies specified comprise (1) finely-divided metals, e.g. iron, nickel, cobalt, tin, silicon and their alloys, e.g. ferrosilicon, ferrochrome, nickel alloys; (2) oxides, hydroxides, carbonates &c. which are reduced to metallic form under the reaction conditions; (3) salts which behave electrolytically in molten form such as chromium fluoride, zinc chloride, stannous chloride, aluminium chloride, iron boride, zinc bromide, antimony fluoride, aluminium silicofluoride, zinc borofluoride, titanium potassium fluoride, and complex antimony and tin salts; sulphates, borates and phosphates; (4) salts of alkaline reaction e.g. hydroxides, sulphides, carbonates and silicates of alkalies with other salts, e.g. potassium bromide, iodide, zinc oxide, tin hydrate, aluminium hydrate &c., dissolved therein.  The contact bodies may be mixed with binding materials to obtain a mouldable mass which may be heated to 1000 DEG  C. in a reducing atmosphere.  The reaction is preferably carried out in an upright reaction vessel lined with porcelain and provided with two electrodes arranged in lattice form of strips of ferrochrome nickel steel material welded together, the contact material consisting of fragments of 5 to 10 mm. cross section which completely surround the electrodes.  60 parts of iron powder, 30 parts tin hydrate, 10 parts boric acid, 20 parts aluminium hydrate, 5 parts phosphoric acid are treated with a solution comprising tin chloride, aluminium chloride zinc bromide and chromium fluoride to form a plastic mass which is dried and after further impregnation with salts or solutions of pitch or bitumen in benzol is broken up into bodies of bean or ring shape.  The bodies are filled into a reactor lined with ceramic material and provided with upper and lower electrodes.  An alternating current of 25 volts is applied to the electrodes and a mixture of 1 kg. crude oil and 120 gs. water is pumped through with water gas under 200 atmos. pressure the materials being preheated to 420 DEG  C. From an oil boiling between 220 and 360 DEG  C. 97 per cent by weight of a product is obtained which commences to boil at 43 DEG  C. and contains 32 per cent benzine.  A contact mass for refining oils comprises 12 parts lignite coke, 6 parts tin dioxide, and 3 parts aluminium silicate pasted with a solution of caustic potash in which potassium bromide or chromite and tin hydroxide are dissolved, the dried material being embedded in wood-charcoal powder and heated to 900 DEG  C.  Diesel oils may be refined and worked up with coke oven gas.  Gaseous hydrocarbons, e.g. cracking gases, water gas, coke oven gas, may be treated with water vapour to obtain olefines, zinc chromate being added to the contact mass to improve the conversion of carbon monoxide.ALSO:Solid, liquid, or gaseous hydrocarbons are converted into valuable products e.g. petrol by treatment at elevated temperatures, e.g. above 400 DEG  C. and preferably under pressure, in presence of solid hydrogenation catalysts which comprise or form part of solid electrically-conducting bodies firmly positioned in electrically-conducting manner between two or more electrodes whereby direct or alternating current is passed through the bodies. Conducting bodies specified comprise (1) finely-divided metals, e.g. iron, nickel, cobalt, tin, silicon and their alloys, e.g. ferrosilicon, ferrochrome, nickel alloys; (2) oxides, hydroxides, carbonates which are reduced to metallic form under the reaction conditions; (3) salts which behave electrolytically in molten form such as chromium fluoride, zinc chloride, stannous chloride, aluminium chloride, iron boride, zinc bromide, antimony fluoride, aluminium silicofluoride, zinc borofluoride, titanium potassium fluoride, and complex antimony and tin salts; sulphates, borates and phosphates; (4) salts of alkaline reaction, e.g. hydroxides, sulphides, carbonates and silicates of alkalis with other salts, e.g. potassium bromide, iodide, zinc oxide, tin hydrate, aluminium hydrate &c. dissolved therein.  The contact bodies may be mixed with binding materials to obtain a mouldable mass which may be heated to 1000 DEG C. in a reducing atmosphere. The reaction is preferably carried out in an upright reaction vessel lined with porcelain and provided with two electrodes arranged in lattice form of strips of ferrochrome nickel steel welded together, the contact material consisting of fragments of 5 to 10 mm. cross section which completely surround the electrodes. 60 Parts of iron powder, 30 parts tin hydrate, 10 parts boric acid, 20 parts aluminium hydrate, 5 parts phosphoric acid are treated with a solution comprising tin chloride, aluminium chloride, zinc bromide, and chromium fluoride to form a plastic mass which is dried and after further impregnation with salts or solutions of pitch or bitumen in benzol is broken up into bodies of bean or ring shape. The bodies are filled into a reactor lined with ceramic material and provided with upper and lower electrodes.  An alternating current of 25 volts is applied to the electrodes and a mixture of 1 kg. crude oil and 120 gms. water is pumped through with water gas under 200 atmos. pressure, the materials being preheated to 420 DEG  C.  From an oil boiling between 220 and 360 DEG  C., 97 per cent by weight of a product is obtained which commences to boil at 43 DEG  C. and contains 32 per cent benzine.  A contact mass for refining oils comprises 12 parts lignite coke, 6 parts tin dioxide, and 3 parts aluminium silicate pasted with a solution of caustic potash in which potassium bromide or chromite and tin hydroxide are dissolved, the dried material being embedded in wood-charcoal powder and heated to 900 DEG  C.  Diesel oils may be refined and worked up with coke-oven gas. Gaseous hydrocarbons, e.g. cracking gases, water gas, coke-oven gas may be treated with water vapour to obtain olefines, zinc chromate being added to the contact mass to improve the conversion of carbon monoxide.