Patent GB-469959-A (GB)
Title: Improvements in the manufacture and production of hydrocarbons and their derivatives containing oxygen from carbon monoxide and hydrogen
IPC: C07C29/153
Filed: 1936-02-05
Abstract: The production of hydrocarbons, and if desired, derivatives containing oxygen, e.g. methanol or other alcohols, aldehydes or, ketones or carboxylic acids, from carbon monoxide and hydrogen is carried with the addition of small amounts of volatile metal compounds capable of being decomposed at temperatures preferably up to 500 DEG  C., either continuously or intermittently and during or after discontinuing the conversion.  The only other catalysts present may be etched metal apparatus surfaces, as described in Specification 458,035, in which case the volatile metal compounds serve to reactivate the etched surfaces.  Suitable compounds are metal carbonyls, e.g. of nickel, cobalt, molybdenum and particular of iron, and the apparatus surfaces when unetched, may consist of iron, copper, aluminium or ceramic materials such as glass, porcelain, quartz or enamelled metals.  The reaction is carried out at increased pressures, especially above 20 atmospheres, and at temperatures between 150 and 500 DEG  C., preferably between 250 and 400 DEG  C. The concentrations of the initial gases may vary between 10 and 0,3 parts, preferably between 2 and 0,5 parts of hydrogen for each part of carbon monoxide.  The volatile metal compound may be added as such or in solution.  According to an example, a mixture of 40 per cent carbon monoxide and 60 per cent hydrogen is passed at 100 atmospheres and at a temperature between 330 and 400 DEG  C. past the outside of a spiral iron tube, which has been previously etched with an aqueous solution of magnesium nitrate, potassium nitrate and uranyl nitrate and glacial acetic acid, followed by treatment with hydrogen.  The products are hydrocarbons, alcohols, esters and acids, and the catalytic surface is reactivated by the repeated addition of small quantities, e.g. 25 to 70 c.c. of iron carbonyl at intervals of several days Superheated steam at 330 DEG  C. is led through the interior of the pipe.ALSO:The production of hydrocarbons, and if desired, derivatives containing oxygen, from carbon monoxide and hydrogen is carried out with the addition of small amounts of volatile metal compounds capable of being decomposed at temperatures preferably up to 500 DEG  C., either continuously or intermittently and during or after discontinuing the conversion.  The only other catalysts present may be etched metal apparatus surfaces, as described in Specification 458,035, in which case the volatile metal compounds serve to reactivate the etched surfaces.  Suitable compounds are metal carbonyls, e.g. of nickel, cobalt, molybdenum and particularly of iron, and the apparatus surfaces when unetched, may consist of iron, copper, aluminium or ceramic materials such as glass, porcelain, quartz or enamelled metals.  The volatile metal compound may be added as such or in solution.  According to an example, a mixture of carbon monoxide and hydrogen is fed past the outside of a spiral iron tube which has been previously etched with an aqueous solution of magnesium nitrate potassium nitrate and uranyl nitrate and glacial acetic acid, followed by treatment with hydrogen. The catalytic surface is reactivated by the repeated addition of small quantities, e.g. 25 to 70 cc. of iron carbonyl at intervals of several days.