Patent GB-191402306-A (GB)
Title: Improvements in, and relating to, Hydrogenisation and Dehydrogenisation.
Inventor: JOHNSON JAMES YATE
Filed: 1914-01-28
Granted: 1915-07-29
Abstract: 2306. Johnson, J. Y., [Badische Anilin & Soda Fabrik]. Jan. 28. Catalytic agents, preparation of; dehydrogenated organic compounds, catalytic production of; hydrogenated fats, oils and other organic compounds, catalytic production of.- The hydrogenation or dehydrogenation of compounds containing carbon is effected in the presence of a catalyst consisting of iron, nickel, cobalt, or copper, intimately mixed with one or more of the following ' promoters ' : oxides or oxygen-containing salts of earth metals, rareearth metals, beryllium, magnesium, manganese, uranium, vanadium, niobium, tantalum, chromium, titanium, or boron; difficultlysoluble phosphates, molybdates, tungstates, or selenates, of the alkaline earths or of lithium, or oxygen - containing reduction products of these compounds. The intimate mixture of the catalytic metal with the promoter may be obtained by precipitating mixtures of the hydroxides, oxides, or carbonates, from solutions of the salts, or by fusing mixtures of salts such as the nitrates, or by mechanical 1 operations, such as grinding or kneading the components together; the catalytic metal is reduced to the metallic state, preferably by means of hydrogen at as low a temperature as possible, and excess of hydrogen being removed after the reduction by means of an indifferent gas, such as carbon dioxide. The catalytic metal may be prepared from carbonaceous salts, such as carbonates or formates, or the metal may be employed in a state of fine division, or in the form of netting, wool, sheets, &c. There may be added to the catalytic mixtures, alkali compounds, such as caustic soda, or inorganic or organic substances which act as carriers or binding-agents, or increase the porosity of the mass, for example asbestos, charcoal, or pumice. The presence of contact poisons, such as chlorine, sulphur arsenic, and lead, should be voided, although in some cases oxygen salts containing these elements, for instance basic aluminium sulphate, may be used. The proportion of the promoter in the catalytic mixture may be as small as 1 per cent or less. The catalytic mixtures may be employed, for example in 'the hydrogenation of fats or fatty acids, the conversion of phenol into cyclohexanol. the reduction of nitrobenzene to aniline, and the conversion of carbon oxides into hydrocarbons; these processes may be effected under ordinary or increased pressure. According to examples: a solution containing nickel and beryllium nitrates is precipitated with caustic soda, the nickel oxide is reduced by means of a mixture of carbon monoxide and hydrogen, or hydrogen alone, and the product is employed for the conversion of a mixture of carbon monoxide and hydrogen into methane; solutions containing nickel nitrate and zirconium or thorium nitrate may be similarly treated; nickel oxalate is mixed with aluminium nitrate solution, and the mixture is dried and reduced by hydrogen and employed, in the hydrogenation of fish oil; cerium nitrate or cerium ammonium nitrate may replace the aluminium nitrate; a solution containing nickel and aluminium nitrates is precipitated by potassium carbonate, and the product is reduced by hydrogen and employed in the hydrogenation of soya-bean oil in an autoclave under pressure; iron nitrate may be employed instead of nickel nitrate; a mixture of nickel and magnesium hydroxides cr carbonates is converted into formates by treatment with formic acid, and the' product is reduced by hydrogen and employed in the hydrogenation of olive oil; carriers, such as pieces of clay, may be soaked in a melt. or solution of nickel salts, such as nickel ammonium formate, or ammoniacal nickel carbonate, together with the salt of the promoter, and treated similarly; spheres, rolls, &c. of nickel wire netting are moistened with aluminium nitrate solution, dried, treated with hydrogen, and employed in the hydrogenation of linseed oil; a solution of nickel nitrate and titanium lactate, is precipitated by. caustic soda, and the product is re- - duced by hydrogen and employed in the hydrogenation of cotton-seed oil, the hydrogenation being effected if desired under a pressure of, say, 100 atmospheres; nickel carbonate is mixed with ammonium or potassium borate solution, and the mass is suitably shaped, dried, reduced, and employed in the hydrogenation of oils or fats; chromium oxide may be obtained for use as a promoter by precipitation from chromium nitrate or soluble chromates; the oxide or carbonate of the catalytic metal may be mixed with solid or dissolved boric acid, and the product be heated and reduced; a salt of the catalytic metal, for instance the nitrate, may be mixed with a borate of the same or another metal, and the mixture be calcined and reduced; solutions of potassium aluminate, nickel nitrate, calcium nitrate, and sodium carbonate are mixed, the precipitate is dried and reduced; nickel carbonate is mixed with solutions of magnesium nitrate, ammonium phosphate, and caustic soda, the precipitate is dried and reduced; the two mixtures last-described may be used in the hydrogenation of oil resulting from cracking petroleum residues, the hydrogenation being effected at 100‹ C. under a pressure of 80 atmospheres; calcium vanadate, barium chromate, aluminium borate, barium tungstate, or lithium phosphate, or the reduction compounds of these bodies, may also be used as promoters ; a solution of nickel and manganese or chromium nitrates is precipitated by sodium carbonate, and the product is reduced by hydrogen and may be employed in the hydrogenation of pignut oil or soya-bean oil respectively; nickel carbonate, ammonium tungstate solution, and barium nitrate solution are mixed, and the product is reduced and may be employed for hydrogenating sesame oil; nickel carbonate is mixed with calcium nitrate and ammonium phosphate solutions, and the product is reduced and may be used for hydrogenating fish oil; nickel carbonate is mixed with strontium nitrate and ammonium selenite solutions, and the product is reduced and used for hydrogenating cottonseed oil; when alumina, is used as the promoter, it may be obtained by heating the acetate in the presence of the catalytic metal or compound thereof. Specifications 731.5/09 and 13,382/13 are referred to.