Patent GB-487384-A (GB)
Title: Process for the production of aliphatic alcohols and ethers
IPC: C07C29/04
Filed: 1936-12-17
Abstract: Aliphatic alcohols and ethers are produced by the hydration of the corresponding olefines or ethers in the presence of a heteropoly acid or salt of such acid, or an isopoly acid of molecular weight above 350.  The catalyst may be solid or in solution, and the pressure may be up to 5000 lb.  The nuclear element of the heteropoly compound may be phosphorus, silicon, boron or arsenic, surrounded by an oxide or oxides of tungsten, molybdenum, vanadium, chromium, sulphur, selenium or tellurium; these compounds, with their associated water have molecular weights near 3,000.  The heteropoly acids may be made by boiling an aqueous solution of a salt of a metal which occupies an outer position with an acid of the element, that occupies the nuclear position or vice versa; acid is added and the mixture is shaken with excess of ether, ethyl acetate or like solvent.  Thus silicotungstic acid is prepared by boiling sodium tungstate solution with silicic acid, acidifying with hydrochloric, sulphuric, or acetic acid, and shaking with ether, allowing the mixture to stratify, and separating the bottom layer which contains the product.  Suitable heteropoly acids and salts are silico-tungstic, borotungstic, phosphotungstic, phosphomolybdic, phosphomolybdotungstic, and tungstorasenic acids and salts thereof such as the thorium, aluminium, tungsten, chromium, cadmium and alkali metal salts.  The heteropoly compounds may be used alone or with other hydration catalysts, such as alumina or thoria, and may be used on carriers such as silica gel, adsorbent carbon or diatomaceous earth.  Suitable isopoly acids are the isopoly acids of tungsten, molybdenum, vanadium, and chromium.  The Specification as open to inspection under Sect. 91 includes the use for ether hydration of "decomposed and reduced" silicotungstic acid on alumina which may be prepared by heating the composite catalyst; and the isopoly acids of sulphur, selenium and tellurium are also mentioned as catalyst.  This subject-matter does not appear in the Specification as accepted.ALSO:Aliphatic alcohols and ethers are produced by the hydration of the corresponding olefines or ethers in the presence of a heteropoly acid or salt of such acid or an isopoly acid of molecular weight above 350.  The catalyst may be solid or in solution, and the pressure may be up to 5000 lb.  The nuclear element of the heteropoly compound may be phosphorus, silicon, boron or arsenic, surrounded by an oxide or oxides of tungsten, molybdenum, vanadium, chromium, sulphur, selenium or tellurium; these compounds, with their associated water have molecular weights near 3000.  The heteropoly acids may be made by boiling an aqueous solution of a salt of a metal which occupies an outer position with an acid of the element that occupies the nuclear position or vice versa; acid is added and the mixture is shaken with excess of ether, ethyl acetate or like solvent.  Thus silicotungstic acid is prepared by boiling sodium tungstate solution with silicic acid, acidifying with hydrochloric, sulphuric, or acetic acid, and shaking with ether, allowing the mixture to stratify, and separating the bottom layer which contains the product.  Suitable heteropoly acids and salts are silicotungstic, borotungstic, phosphotungstic, phosphomolybdic, phosphomolybdotungstic, and tungstoarsenic acids and salts thereof such as the thorium, aluminium, tungsten, chromium, cadmium and alkali metal salts.  The heteropolycompounds may be used alone or with other hydration catalysts such as alumina or thoria and may be used on carriers such as silica gel, adsorbent carbon or diatomaceous earth.  Suitable isopoly acids are the isopoly acids of tungsten, molybdenum, vanadium, and chromium.  Examples describe the hydration of ethylene to alcohol with aqueous solutions of phosphotungstic and silicotungstic acids and cuprous phosphotungstate respectively; the hydration of ethylene to ether with an aqueous solution of phosphotungstic acid; the hydration of propylene to isopropanol with aqueous solutions of silicotungstic acid, borotungstic acid, and cadmium borotungstate respectively; and the hydration of ethylene and propylene to the corresponding alcohols by means of alumina impregnated with silicotungstic acid.  The Specification as open to inspection under Sect. 91 states that ether may be hydrated to alcohol by means of "decomposed and reduced" silicotungstic acid on alumina which may be prepared by heating the catalyst of the last example; and the isopoly acids of sulphur, selenium and tellurium are mentioned as catalysts for the reactions.  This subject-matter does not appear in the Specification as accepted.