Patent GB-417582-A (GB)
Title: Improvements in or relating to the catalytic production of alcohols and alcoholic derivatives
IPC: C07C29/19
Filed: 1933-01-02
Abstract: Catalysts for the production of alcohols from carbocyclic (other than aromatic) or heterocyclic compounds containing a carboxylic acid group or derivative thereof by treatment with excess of hydrogen at elevated temperature and pressure comprise: (1) copper, cadmium, nickel, cobalt, tin, zinc oxide, magnesium oxide and manganese oxide, which may be activated by the addition of difficulty-reducible oxides such as chromium oxide, (2) chromites of hydrogenating metals prepared by heating double chromates of ammonium and the metal, (3) a composition consisting of zinc chromite with a small addition of the chromates or chromites of copper and cadmium.  In the examples the following methods of preparation of the catalyst are described:--(1) ammonium hydroxide is added to a solution of zinc and copper nitrates until the precipitate dissolves, kieselguhr is added, air is passed through until the excess of ammonia is discharged, and the precipitated product then slowly reduced with hydrogen; (2) a solution of chromic anhydride in ammonium hydroxide is added to a solution of zinc, cadmium and copper nitrates, and the resulting chromate precipitate ignited to the chromite stage; (3) copper ammonium chromate is ignited to form copper chromite; (4) nickel chromate is reduced with hydrogen giving a nickel-chromium oxide mixture.ALSO:Alcohols are prepared by the catalytic hydrogenation of carbocyclic (other than aromatic) or heterocyclic compounds containing a carboxylic acid group or its ester, halide, amide, anhydride or salt, at elevated temperature and pressure. Temperatures of 300--400 DEG  C. and pressures of 100--250 atmospheres are preferably employed.  The catalysts specified are copper, cadmium, nickel, cobalt, tin, zinc oxide, magnesium oxide and manganese oxide, which may be activated by the addition of difficultly-reducible oxides such as chromium oxide; also chromites of hydrogenating metals prepared by heating double chromates of ammonium and the metal, and a composition consisting of zinc chromite with a small addition of the chromates or chromites of copper and calmium.  The hydrogenation is effected with excess of hydrogen and may take place in an autoclave or by the continuous flow of the compound in the liquid or dissolved state over the heated catalyst.  According to the examples: (1) hexahydro-o-toluic acid ethyl ester is heated with hydrogen in an autoclave in the presence of a catalyst prepared by adding ammonium hydroxide to a solution of zinc and copper nitrates until the precipitate dissolves, kieselguhr added, air passed through until the excess of ammonia is discharged, and the precipitated product then slowly reduced with hydrogen; ethanol and 2-methylcyclohexylcarbinol are produced; similarly hexahydroethylbenzoate is reduced to cyclohexylcarbinol and the hydrogenated naphthoates and anthroates to the corresponding alcohols; (2) a catalyst is prepared by adding a solution of chromic anhydride in ammonium hydroxide to a solution of zinc, cadmium and copper nitrates, and the resulting chromate precipitate ignited to the chromite stage; a solution of naphthenic acids in benzene is forced with hydrogen over the heated catalyst giving rise to naphthenic alcohols; (3) cyclohexylcarbinol results when an alcoholic solution of hexahydrobenzoic acid is passed with hydrogen under pressure over a copper chromite catalyst prepared by igniting copper ammonium chromate; camphonic acid or the hexahydrophthalic acids may be similarly reduced; (4) hydroabietic acid is hydrogenated in an autoclave with the aid of a nickel-chromium oxide catalyst prepared by reducing nickel chromate with hydrogen and gives rise to an alcoholic product; ethylabietate and glyceryl abietate (ester gum) can be hydrogenated in the same way.