Patent GB-371804-A (GB)
Title: Improvements in or relating to the synthetic production of higher alcohols
IPC: C07C29/154
Filed: 1930-10-23
Abstract: Catalysts for the synthesis of higher alcohols by the catalytic interaction of hydrogen with an oxide of carbon at elevated temperature and pressure comprise a mixture of at least one irreducible oxide with a small amount of an alkali metal oxide. Reducible oxides, such as copper oxide, may also be present.  The oxides of manganese, zinc, chromium, and vanadium are mentioned as suitable irreducible oxides.  Examples of catalysts are oxides of manganese, copper, and potassium; oxides of zinc, chromium, and potassium; oxides of chromium, manganese, and potassium; oxides of copper, zinc, and potassium; oxides of zinc, manganese, and potassium; oxides of manganese, copper, chromium, and potassium. Preferably the catalyst comprises manganese oxide and an alkali metal oxide.  In the examples, the catalysts employed are prepared by (1) adding ammonium chromate solution to a solution of copper and manganese sulphates, washing and drying the precipitate, mixing it with potassium carbonate and reducing with hydrogen; (2) mixing solutions of zinc sulphate and ammonium bichromate, moistening the dried precipitate with potassium chromate and reducing the dried product with hydrogen.  The apparatus employed comprises an electrically-heated copperlined nichrome tube.ALSO:Higher alcohols are synthesized by passing a mixture of hydrogen and an oxide of carbon, the proportion of the latter not exceeding 10 per cent of the total volume, over an alcohol-forming catalyst at a temperature exceeding 300 DEG  C. and a pressure of at least 100 atmospheres. Preferably the velocity of the gases is such that the proportion of carbon monoxide in the reacting gases does not exceed 8 per cent. The catalyst may comprise a mixture of at least one irreducible oxide with a small amount of an alkali metal oxide; reducible oxides, such as copper oxide, may also be present.  The oxides of manganese, zinc, chromium irreducible oxides.  Examples of catalysts are oxides of manganese, copper and potassium; oxides of zinc, chromium and potassium; oxides of chromium, manganese and potassium; oxides of copper, zinc and potassium; oxides of zinc, manganese and potassium; oxides of manganese, copper, chromium and potassium.  Preferably the catalyst comprises manganese oxide and an alkali metal oxide. According to the examples, (1) a catalyst is prepared by adding ammonium chromate solution to a solution of copper and manganese sulphates, washing and drying the precipitate, mixing it with potassium carbonate and reducing with hydrogen; the catalyst is mounted in an electrically-heated copper-lined nichrome tube and a mixture of hydrogen (75 per cent), carbon monoxide (5 per cent) and nitrogen under a pressure of 900 atmospheres and a space velocity of 60,000 is passed through the catalyst heated to 450 DEG  C.; the gaseous products, which contain about 1 per cent carbon monoxide, are cooled to give a mixture of isobutanol with amyl, hexyl and heptyl alcohols; (2) a mixture of hydrogen (80 per cent), carbon monoxide (8 per cent) and nitrogen is passed under a pressure of 900 atmospheres over a catalyst prepared by mixing solutions of zinc sulphate and ammonium bichromate, moistening the dried precipitate with potassium chromate and reducing the dried product with hydrogen; the gaseous reactants are passed at a space velocity of about 50,000 over the catalyst heated to 450-525 DEG  C.