Patent GB-469332-A (GB)
Title: Improvements in or relating to the production of glycol derivatives
IPC: C08G65/28
Filed: 1936-01-24
Abstract: Olefine oxides are condensed with water and/or organic hydroxy-compounds, e.g. monohydric alcohols or phenols, in the presence of a dehydrating metal oxide catalyst under conditions of temperature and pressure suited to maintain the liquid phase during the reaction.  Suitable catalysts are the oxides of aluminium, thorium, tungsten, titanium, vanadium, molybdenum and zirconium.  The liquid phase is maintained for example in the case of an ethylene oxide-ethyl alcohol mixture by reaction at 80--120 DEG  C. under a pressure of 5--15 atmos.  Concentrations of from 20 to 100 grms. ethylene oxide per litre are suitable.  In examples, products containing mainly ethylene glycol monoethyl ether, and higher boiling compounds such as diethylene glycol monethyl ether are obtained by passing mixtures of ethylene oxide and ethyl alcohol preheated to 80--100 DEG  C. over the following catalysts contained in a tubular reactor heated in an electric furnace: (1) a body obtained by precipitating aluminium nitrate solution with ammonia, filtering, extruding and drying at 100 DEG  C., then at 300 DEG  C.; (2) a titania catalyst prepared by mixing precipitated titanium hydroxide with ethyl alcohol, silicon ester and ammonia (density ,880), the resulting mass being allowed to set hard, broken into granules and baked at 300 DEG  C.; (3) a body obtained by precipitating zirconium nitrate solution with ammonia, filtering, extruding and drying at 100 DEG  C., then at 300 DEG  C.; (4) Yellow tungstic acid prepared by decomposing a strong aqueous solution of sodium tungstate or suspension of ammonium tungstate with a mixture of strong hydrochloric and nitric acids; the precipitate is washed, dried at 100 DEG  C., for several days, and granulated or formed into tablets. The granules may be used as such, or treated with an equimolecular mixture of hydrogen, alcohol and steam in a silica tube successively at 150, 175, 200 and 250 DEG  C.  The bluish mass is cooled in hydrogen.  Reference is also made to the treatment of the tungstic acid with alcohol vapour, alcohol vapour and steam or with other reducing gases the following solutions are passed at 90--95 DEG  C. and 10--12 atmos. over a yellow tungstic oxide prepared as above, but rendered mechanically more stable by mixing with silicon ester, alcohol and water prior to drying at 100 DEG  C.: (1) ethylene oxide in isopropyl alcohol; (2) ethylene oxide in n-butanol; (3) ethylene oxide in ethylene glycol monoethyl ether; (4) an aqueous solution of ethylene oxide.  In addition to unspecified higher boiling compounds, the products are, respectively, ethylene glycol, mono-isopropyl ether; ethylene glycol mono-n-butyl ether; diethylene glycol monoethyl ether; ethylene- and diethylene glycol.  The reaction may be so effected that the temperature gradient of the reaction vessel rises as the concentration of the olefine oxide in the solution passing along it falls.  According to the Provisional Specification, the condensation may be effected in the gaseous phase.ALSO:Dehydrating metal oxide catalysts are used in the condensation of olefine oxides with water and/or organic hydroxycompounds under conditions of temperature and pressure suited to maintain the liquid phase during the reaction.  Suitable catalysts are the oxides of aluminium, thorium, tungsten, titanium, vanadium, molybdenum and zirconium.  The preparation of the following catalysts is described: (1) a body obtained by precipitating aluminium nitrate solution with ammonia, filtering, extruding and drying at 100 DEG C., then at 300 DEG  C.; (2) a titania catalyst prepared by mixing precipitated titanium hydroxide with ethyl alcohol, silicon ester and ammonia (density ,880), the resulting mass being allowed to set hard, broken into granules, and baked at 300 DEG  C.; (3) a body obtained by precipitating zirconium nitrate solution with ammonia, filtering, extruding, and drying at 100 DEG  C., then at 300 DEG  C.; (4) yellow tungstic acid prepared by decomposing a strong aqueous solution of sodium tungstate or suspension of ammonium tungstate with a mixture of strong hydrochloric and nitric acids; the precipitate is washed, dried at 100 DEG  C. for several days and granulated or formed into tablets. The granules may be used as such, or treated with an equimolecular mixture of hydrogen, alcohol and steam in a silica tube, successively at 150, 175, 200 and 250 DEG  C.  The bluish mass is cooled in hydrogen.  Reference is also made to the treatment of the tungstic acid with alcohol vapour, alcohol vapour and steam, or with other reducing gases or vapours up to 300 DEG  C.  The tungstic acid may be rendered mechanically more stable by mixing with silicon ester, alcohol and water prior to drying at 100 DEG  C.