Patent GB-672259-A (GB)
Title: Process for hydrocarbon synthesis
IPC: B01J23/78
Filed: 1949-06-22
Abstract: In the synthesis of hydrocarbons, which may be admixed with oxygenated derivatives, from CO and H2 in the presence of catalysts containing iron, alkali metal compounds, and difficultly reducible non-volatile reactive acid anhydrides, i.e. oxides capable of reacting at elevated temperature with alkali metal carbonates or hydroxides to form salts, the ratio by weight of alkali metal compound, calculated as oxide, to said acid anhydride is between 1 : 2.5 and 1 : 7.0.  The acid anhydride may be silicic or titanic acid or mixtures such as silicic with tungstic or titanic acid, and is added in reactive form, e.g. as precipitated silicic acid or a sol, or transformed into a reactive form during preparation of the catalyst, e.g. with the aid of alkali, and by fusion at high temperature.  The alkali metal is preferably potassium, and carbonates, nitrates or hydroxides are suitable.  The usual promoters, e.g. copper, alkaline earths, thoria, alumina or zinc oxide, and carriers may be present.  The hydrogen consumption increases with pressure but decreases with alkali content.  Thus, a CO : H2 consumption of 1 : 1.4 at 10 atm. becomes 1 : 1.7 at 20 atm., using a catalyst wherein K2O : SiO2 is 11 : 45.  Where this ratio is 14-17 : 45, the consumption ratio 1 : 1.7 falls to 1 : 1.3 - 1.4 with a higher paraffin yield.  With the ratio CO : H2 of 1 : 1.8 - 2.0, production of CO2 is negligible, which facilitates multi-stage operation or the use of both iron and cobalt catalyst stages. Preferred high molecular paraffinic products are obtained if the iron is reduced to metal to the extent of 10 - 50 per cent and temperatures are 190 - 250 DEG  C.  Lower boiling products such as gasoline and Diesel oil are obtained with, say, 55 - 99 per cent reduction, and higher temperatures.  In examples, iron, copper, and zinc are precipitated from a solution of the nitrates, impregnated with potassium nitrate or carbonate and silicic acid, precipitated or sol, and reduced in hydrogen at 320 DEG  C., giving a catalyst containing per 100 parts iron, 20 per cent as free metal, 11 parts K2O and 45 SiO2.  This is used for synthesis at 220 DEG  or 230 DEG C. and 10 or 20 atm.  Other catalysts contain ratios of K2O : SiO2 of 8.5 : 40 and 7.5 : 45, the reduction of the iron to metal being 26.8, 15.6 or 55 per cent.  Titanic acid made by boiling titanium nitrate solution is used in place of silica, and another catalyst is prepared by fusing reduced iron, ground quartz, potassium nitrate, and zinc and copper oxides, granulating the product, and reducing in hydrogen at 450 DEG  C.ALSO:In the synthesis of hydrocarbons, which may be admixed with oxygenated derivatives, from CO and H2 in the presence of catalysts containing iron, alkali metal compounds, and difficulty reducible non-volatile reactive acid anhydrides, i.e. oxides capable of reacting at elevated temperature with alkali metal carbonates or hydroxides to form salts, the ratio by weight of alkali metal compound, calculated as oxide, to said acid anhydride is between 1 : 2.5 and 1 : 7.0.  The acid anhydride may be silicic or titanic acid, or mixtures such as silicic with tungstic or titanic acid, and is added in reactive form, e.g. as precipitated silicic acid or a sol, or transformed into a reactive form during preparation of the catalyst, e.g. with the aid of alkali, and by fusion at high temperature.  The alkali metal is preferably potassium, and carbonates, nitrates or hydroxides are suitable.  The usual promoters, e.g. copper, alkaline earths, thoria, alumina or zinc oxide, and carriers may be present.  The hydrogen consumption increases with pressure but decreases with alkali content.  Thus, a CO : H2 consumption of 1 : 1.4 at 10 atm. becomes 1 : 1.7 at 20 atm. using a catalyst wherein K2O : SiO2 is 11 : 45.  Where this ratio is 14-17 : 45, the consumption ratio 1 : 1.7 falls to 1 : 1.3-1.4 with a higher paraffin yield.  With the ratio CO : H2 of 1 : 1.8-2.0, production of CO2 is negligible which facilitates multi-stage operation or the use of both iron and cobalt catalyst stages. Preferred high molecular paraffinic products are obtained if the iron is reduced to metal to the extent of 10-50 per cent and temperatures are 190-250 DEG C.  Lower boiling products such as gasoline and Diesel oil are obtained with, say, 55-99 per cent reduction, and higher temperatures.  In examples, iron, copper and zinc are precipitated from a solution of the nitrates, impregnated with potassium nitrate or carbonate and silicic acid, precipitated or sol, and reduced in hydrogen at 320 DEG C. giving a catalyst containing per 100 parts iron, 20 per cent as free metal, 11 parts K2O and 45 SiO2.  This is used for synthesis at 220 DEG  or 230 DEG C. and 10 or 20 atm.  Other catalysts contain ratios of K2O : SiO2 of 8.5 : 40, and 7.5 : 45, the reduction of the iron to metal being 26.8, 15.6 or 55 per cent. Titanic acid made by boiling titanium nitrate solution is used in place of silica, and another catalyst is prepared by fusing reduced iron, ground quartz, potassium nitrate, and zinc and copper oxides, granulating the product, and reducing in hydrogen at 450 DEG C.