Patent GB-347593-A (GB)
Title: Improvements relating to the production of ketones
IPC: C07C45/54
Filed: 1930-01-22
Abstract: Catalysts for use in the production of ketones by the action of water vapour at elevated temperatures on aliphatic monohydric alcohols, aldehydes or their polymers, acids, esters, acetates, and aldols containing two or more carbon atoms comprise the oxides or carbonates of nickel or cobalt or mixtures thereof, if desired in admixture with other oxygen compounds of metals, for example, those of the sixth, seventh, or eighth groups of the periodic system, or oxides of metals having a specific gravity less than 5,5, particularly the alkaline earths, and also, if desired, metals such as iron, which may be employed as carriers.  A suitable catalyst may be prepared by saturating rusted iron sponge, preferably first moistened with acetic acid, with a solution of nickel carbonate in acetic acid, drying, and heating, for example, to 500 DEG  C.  Catalysts prepared in this way with nickel and/or cobalt acetate may be wholly or partly oxidized before use by means of air, oxygen, or water vapour at elevated temperatures.  Mixed catalysts may be prepared by mixing the oxides and pressing into pellets or other forms.  Examples of methods of carrying out the reaction are given.  Specification 313,897, [Class 2 (iii), Dyes &c.], is referred to.ALSO:The production of ketones by the action of water vapour at elevated temperatures on aliphatic monohydric alcohols, aldehydes or their polymers, acids, esters, acetals, and aldols containing two or more carbon atoms is carried out in the presence of catalysts comprising the oxides or carbonates of nickel or cobalt or mixtures thereof, if desired in admixture with other oxygen compounds of metals, for example, those of the sixth, seventh, and eighth groups of the periodic system, or oxides of metals having a specific gravity less than 5,5, particularly the alkaline earths, and also, if desired, metals such as iron, which may be employed as carriers.  A suitable catalyst may be prepared by saturating rusted spongy iron, preferably first moistened with acetic acid, with a solution of nickel carbonate in acetic acid, drying, and heating, for example, to 500 DEG  C.  Catalysts prepared in this way with nickel and/or cobalt acetate may be wholly or partly oxidized before use by means of air, oxygen, or water vapour at elevated temperatures.  Mixed catalysts may be prepared by mixing the oxides and pressing into pellets or other forms. The reaction may be carried out at temperatures of 420-490 DEG  C. According to examples (1) acetone is obtained by passing ethyl alcohol and steam at 420 DEG  C. over a catalyst prepared from rusted spongy iron and nickel carbonate as described above, (2) instead of the catalyst used in (1) one consisting of 80 per cent ferric oxide, 15 per cent magnesium carbonate, and 5 per cent of basic cobalt carbonate is employed at 430 DEG  C., (3) instead of the catalyst used in (1) one obtained by depositing 5 per cent of nickel acetate on manganese is employed at 450 DEG  C., (4) methylethyl ketone is obtained by passing ethyl propionate and steam at 470 DEG  C. over a catalyst containing the oxides of nickel and manganese deposited on iron sponge from a solution of their acetates, (5) acetone is obtained by passing methyl acetate and steam at 430 DEG  C. over a pressed mixture of the oxides of iron, nickel and cobalt, (6) dipropyl ketone is obtained by passing p  butyraldehyde and steam over a mixture of nickel and iron oxides at 460 DEG  C., (7) the same catalyst is used for producing acetone from paraldehyde and steam, and also (8) for producing diethyl ketone from normal propyl alcohol and steam.  As starting materials these may also be used mixtures of alcohols, aldehydes, or acids with esters, aldols, or polymers of aldehydes, or raw materials such as crude ethyl alcohol, propyl alcohol, or paraldehyde containing esters &c., or first runnings of spirit rectification. When esters of higher fatty acids are used as starting materials, mixed ketones are produced.  Specification 313,897, Class 2 (iii), Dyes &c.], is referred to.