Patent GB-452158-A (GB)
Title: Improvements in carrying out catalytic reactions
IPC: C10G1/08
Filed: 1935-02-27
Abstract: In the conversion by treatment with hydrogenating gases of oxygen--or sulphur--containing organic compounds into the corresponding hydrocarbons, e.g. the conversion of phenols or cresols into cyclic hydrocarbons, and also in reactions such as the conversion of cresol into phenol, the process is carried out in the presence of contact agents comprising compounds of silicon, or materials containing the same in substantial amounts, the activity of which has been increased by treatment prior to the reaction with fluorine, hydrogen fluoride or other compounds of fluorine capable of corroding silicates, e.g. acid ammonium fluoride, fluosilicic acid or its ammonium salt.  The activation may be carred out in the liquid phase with solutions of hydrogen fluoride, the substance to be activated being treated in the form of a paste or suspension, or in the gas phase at about 500 DEG C. The activated material may itself act catalytically and may be employed alone or as a carrier for or with the addition of catalysts. The material may contain, as well as the compounds of silicon, metals or their compounds or alloys, e.g. the oxides hydroxides, carbonates, sulphides, phosphates or halides of aluminium, zinc, magnesium, tin, lead, vanadium chromium, manganese, iron, cobalt, nickel, rare earths, e.g. zirconium. Silicates are particularly suitable, e.g. bleaching earth, fuller's earth, bentonite, diatomaceous earth &c. The materials may also be treated before or after the activation (a) with acids, (b) with gases at high temperature.  The activated materials may be impregnated with metals of the 4th to 8th group of the periodic system e.g. molybdenum, tungsten, chromium, vanadium, zinc, tin, titanium, manganese, iron, cobalt or nickel or their compounds, e.g. thio salts, nitrates, oxides or their phosphates, sulphates, chromates, oxalates, molybdates, tungstates &c.  The activated carrier may be impregnated with the catalysts (1) by precipitation from solution or (2) by absorption from colloidal solution.ALSO:In the production of valuable hydrocarbon, by the catalytic treatment of distillable carbonaceous materials particularly in the presence of hydrogenating gases, the process is carried out in the presence of contact agents comprising compounds of silicon or materials containing same in substantial amounts the activity of which has been increased by treatment prior to the reaction with fluorine, hydrogen fluoride or other compounds of fluorine capable of corroding silicates, e.g. acid ammonium fluoride, fluosilicic acid or its ammonium salt.  The activation may be carried out in the liquid phase with solutions of hydrogen fluoride the substance to be activated being treated in the form of a paste or suspension, or in the gas phase at about 500 DEG  C. The activated material may itself act catalytically and may be employed alone, as a carrier for, or with the addition of catalysts.  The material may contain, as well as the compounds of silicon, metals or their compounds or alloys, e.g. the oxides, hydroxides carbonates, sulphides, phosphates or halides of aluminium, zinc, magnesium, tin, lead, vanadium, chromium, manganese, iron, cobalt, nickel, rare earths, e.g. zirconium. Silicates are particularly suitable, e.g. bleaching earth, fuller's earth, bentonite, diatomaceous earth &c. The materials may also be treated before or after the activation (a) with acids (b) with gases at high temperature.  The activated materials may be impregnated with metals of the 4th to 8th group of the periodic system, e.g. molybdenum, tungsten, chromium, vanadium, zinc, tin, titanium, manganese, iron, cobalt or nickel, or their compounds, e.g. thiosalts, nitrates, oxides, phosphates, sulphates, chromates, oxalates, molybdates, tungstates, &c.  The activated carrier may be impregnated with the catalysts (1) by precipitation from solution (2) by absorption from colloidal solution.  The expression "treatment with hydrogenating gases" includes destructive hydrogenation, purification of oil from nonhydrocarbon impurities, conversion of oxygen-or sulphur - containing organic compounds, e.g. phenols and cresols, into the corresponding hydrocarbons, the conversion of cresol into phenol and of phenol into cyclohexanol, and the improvement of motor fuels &c. by aromatizing and hydroforming treatments.  The catalysts are also suitable for cracking oils and reforming treatments and in the production of hydrocarbons from oxide of carbon and hydrogen.  Examples are given of the hydrogenation of oils in presence of bleaching earth activated with hydrofluoric acid used either alone or impregnated with ammonium thiotungstate and ammonium sulphide.