Patent GB-109983-A (GB)
Title: A Process for the Manufacture of Products of Condensation and Oxidation from Acetylene.
IPC: C07C47/06
Filed: 1916-07-17
Abstract: 109,983. Chemische Fabrik Rhenania, Stuer, B. K., and Grol, W. July 17, 1916. Acetaldehyde; acetic acid and its homologues; acetone; alcohol; furane derivatives; hydrocarbons; mericaptan; phenols; pyridine and its homologues; pycrole derivatives; thiophene and its homologues.-Condensation and oxidation products are obtained by passing acetylene, pure or diluted with neutral gases, or acetylene mixed with steam, ammonia, or sulphuretted hydrogen, or with mixtures of steam with ammonia or sulphuretted hydrogen, at a high temperature over catalysts consisting of metal compounds capable of reduction by acetylene and containing water of hydration. Hydrated iron oxide or other hydrated iron compounds, for example bog-iron ore, bauxite or hydrated iron-aluminium silicates are particularly suitable, but oxides or compounds of copper, nickel, cobalt, manganese, chromium, cerium, or vanadium, or mixtures thereof, may be used. The efficiency of the catalysts is improved by the addition of substances containing water of hydration, such as aluminium or magnesium hydroxide or hydrated silicates such as fuller's earth or zeolites. These mixtures of catalyst and activating substance may be made, for example, by precipitating a mixture of iron and aluminium hydroxides from salt solutions, or by precipitating iron hydroxide in the presence of an hydrated silicate. The contact masses may be submitted to a partial reduction by means of hydrogen, carbon monoxide, or mixtures thereof, before use, but such reduction should not, except in the case mentioned below, be carried to the stage of giving the metal. Oxidizing-agents, such as chromic acid, chromates, or mitrates, may be added to the contact mass, or oxygen or oxygen-containing gases, preferably moist, may be added to the reacting gases; alkali, alkalineearth, or magnesium compounds also may be added to the contact mass. When the contact masses have become inactive through use, they may be regenerated by treatment at a high temperature with oxygen or oxygen-containing gases, preferably moist, and may be subsequently hydrated by treatment with water. According to examples :-(1) A mixture of acetylene and steam is passed at 400-420‹ C. over bog-iron ore, the resulting gases are condensed by cooling, washing, etc.; the product is mainly acetaldehyde, with some higher products of condensation and acetic acid; (2) a mixture of acetylene and steam is passed over bog-iron ore which has previously been submitted to a partial reduction by hydrogen; the products are acetaldehyde, higher aldehydes, acetone and other hetones, alcohol, acetic acid and its homologues, furane derivatives, phenols, hydrocarbons, etc.; (3) acetylene is passed over bauxite which has previously been submitted to a partial reduction by hydrogen; the product is a mixture of aromatic and aliphatic hydrocarbons, principally the former; (4) a mixture of acetylene and ammonia are passed over partially-reduced bauxite; the products are nitriles, mainly acetonitriles, picoline and other pyridine bases, pyrroles, etc.; (5) acetylene mixed with sulphuretted hydrogen is passed over a mass of nickel hydroxide mixed with cement; the products are mercaptan, thiophene, ethylthiophene etc.; (6) acetylene mixed with sulphuretted hydrogen is passed over partially-reduced bauxite; the product is mainly thiophene. When mixtures of acetylene and sulphuretted hydrogen are treated, it is also possible to use the abovementioned contact-masses completely reduced to the metallic state, or compact or finely-divided metals, such as nickel, copper, or iron; the passage of the acetylene over these metals converts them into carbon-like bodies of high activity.