Patent GB-229715-A (GB)
Title: The synthetic manufacture of methanol
IPC: C07C29/156
Filed: 1923-08-23
Abstract: Methyl alcohol is prepared by the interaction of oxides of carbon with hydrogen at elevated temperature and pressure in the presence of a catalytic material consisting of one or more of the hydrogenating elements copper, silver, gold, zinc, cadmium and lead, associated with one or more of the following elements titanium, vanadium, chromium, manganese, zirconium, cerium, thorium, niobium, tantalum, molybdenum, tungsten, uranium, or boron, or compounds thereof.  The catalysts should be free from alkali metals and from iron, nickel and cobalt.  Examples of the preparation of the catalytic material are as follows:- (1) asbestos wool is introduced into a boiling solution of copper nitrate and chromium acetate, sodium carbonate is added, and the product filtered off, washed, dried and reduced with hydrogen; (2) copper chromate is precipitated on asbestos by adding copper nitrate to asbestos immersed in a solution of potassium dichromate, and the product washed, dried and reduced with hydrogen; the copper chromate may be mixed with silver chromate, or be replaced by the molybdates or tungstates of silver or copper or other hydrogenating element or by similar salts derived from others of the associated elements; (3) asbestos wool is immersed in a solution of neutral copper acetate and silver nitrate, chromic acid is added and the product reduced with hydrogen after drying; or potassium chromate is decomposed with copper acetate and lead nitrate in the presence of asbestos; (4) asbestos is added to a solution of copper nitrate and uranium nitrate and the hot solution precipitated with caustic potash; (5) copper, uranium and manganese are deposited together upon a carrier as hydroxides or carbonates; (6) a mixture of manganese oxide, copper oxide, cobalt oxide and silver oxide is precipitated upon asbestos and reduced with hydrogen; the reduction products of copper or silver vanadate or manganate may also be used; (7) asbestos is immersed in a solution of copper nitrate and thorium nitrate and after precipitation with caustic potash, the mass is filtered, washed, dried and reduced with hydrogen; uranyl nitrate may also be present, in which case cerium nitrate may replace the thorium nitrate.  Reference has been directed by the Comptroller to Specification 20488/13.ALSO:Methyl alcohol is prepared by the interaction of oxides of carbon with hydrogen at elevated temperature and pressure in the presence of a catalytic material consisting of one or more of the hydrogenating elements copper, silver, gold, zinc, cadmium and lead, associated with one or more of the following elements titanium, vanadium, chromium, manganese, zirconium, cerium, thorium, niobium, tantalum, molybdenum, tungsten, uranium, or boron, or compounds thereof.  The catalysts should be free from alkali metals and from iron, nickel and cobalt.  When using mixtures of zinc with the oxides of chromium, manganese, molybdenum, titanium or cerium, it is essential that the gaseous mixture should contain more hydrogen in volume than oxides of carbon, and this condition is also desirable in the case of the other catalysts.  Examples of the preparation of the catalytic material are as follows:-(1) asbestos wool is introduced with a boiling solution of copper nitrate and chromium acetate, sodium carbonate is added, and the product filtered off, washed, dried and reduced with hydrogen; (2) copper chromate is precipitated on asbestos by adding copper nitrate to asbestos immersed in a solution of potassium dichromate, and the product washed, dried and reduced with hydrogen: the copper chromate may be mixed with silver chromate, or be replaced by the molyddates or tungstates of silver or copper or other hydrogenating element or by similar salts derived from others of the associated elements; (3) asbestos wool is immersed in a solution of neutral copper acetate and silver nitrate, chromic acid is added and the product reduced with hydrogen after drying; or potassium chromate is decomposed with copper acetate and lead nitrate in the presence of asbestos; (4) asbestos is added to a solution of copper nitrate and uranium nitrate and the hot solution precipitated with caustic potash; (5) copper, uranium and manganese are deposited together upon a carrier as hydroxides or carbonates; (6) a mixture of manganese oxide, copper oxide, cobalt oxide and silver oxide is precipitated upon asbestos and reduced with hydrogen; the reduction products of copper or silver vanadate or manganate may also be used; (7) asbestos is immersed in a solution of copper nitrate and thorium p  nitrate and after precipitation with caustic potash, the mass is filtered, washed, dried and reduced with hydrogen; uranyl nitrate may also be present, in which case cerium nitrate may replace the thorium nitrate. Examples are given of the application of the above catalysts for the manufacture of methyl alcohol, using temperatures of 200-260 DEG  C., pressures of 35-150 atmospheres, and gas velocities of 1-250 cubic metres, calculated on atmospheric pressure, per hour for each kilogram of contact mass.  Reference has been directed by the Comptroller to Specification 20488/13.