Patent GB-669382-A (GB)
Title: Improvements in or relating to the hydrogenation of carbon oxides
IPC: C07C1/04
Filed: 1945-09-11
Abstract: Liquid hydrocarbons are produced by continuously flowing hydrogen and a carbon oxide upwardly in a reaction zone at a velocity effective to suspend in a fluidized condition a finely-divided contact material comprising either freshly reduced or used cobalt catalyst on <PICT:0669382/IV (b)/1> bentonite, the mixture being maintained at an equilibrium temperature not below 350 DEG  F. at substantially all times, any time of contact of catalyst and gases at below 350 DEG  F. not exceeding a time in which less than an amount equivalent to 15 parts by weight of carbon oxide is in contact with 1 part of reduced metal catalyst, whereby excessive formation of solids such as wax is prevented, the reaction members being cooled to maintain the desired reaction temperature, and being withdrawn from the reaction zone to recover the liquid products therefrom.  Reduced cobalt catalyst which may be fresh or revivified by hydrogenation is used with twice its weight of a bentonite support and, preferably, small amounts of promoters.  The particles are, preferably, principally of 40-400 microns, and the space velocity of the reactants 0.2-10 standard litres per hour per gram of cobalt or 50-2000 standard vols. per hour per vol. of fluidized dense phase, the temperature being 350-450 DEG F.  The contact mass may be heated above 350 DEG  F. by a stream of inert gas or by reduction just prior to passing in the reactants. The reactor 1 has an enlarged extension 5 to facilitate disengagement of catalyst, and conduits 7, 8 with filters 9, 10.  A jacket 15 may contain liquid for temperature control.  In an example, a solution of cobalt and magnesium nitrates is added to sodium carbonate solution, "Superfiltrol" (Registered Trade Mark) added, the mixture filtered, dried, reduced in hydrogen at up to 700 DEG  F., and ground.  This catalyst is introduced into the reactor in CO2 and heated by means of a water jacket to 400 DEG  F., aeration being effected first with CO2, then H2, and fuel gas being introduced when 360 DEG  F. is reached.  Pressure varies up to 50 lbs. gauge.  In another example, the catalyst is reduced in the reactor by heating in hydrogen up to 700 DEG  F., the temperature then being lowered to 300 DEG  F., and raised rapidly to 360 DEG  F. while passing fuel gas.  Reaction temperatures up to 460 DEG  F. are used. Specifications 568,913 and 647,155 are referred to.  The Specification as open to inspection under Sect. 91 comprises the use instead of carbon oxides of any compound having a carbonyl group to produce also oxygenated compounds, the use of other catalysts such as nickel or iron and supports such as keiselguhr, and the injection of vaporizable liquids to control reaction temperature.  This subject-matter does not appear in the Specification as accepted.ALSO:<PICT:0669382/III/1> Liquid hydrocarbons are produced by continuously flowing hydrogen and a carbon oxide upwardly in a reaction zone at a velocity effective to suspend in a fluidized condition a finely-divided contact material comprising either freshly reduced or used cobalt catalyst on bentonite, the mixture being maintained at an equilibrium temperature not below 350 DEG F. at substantially all times, and time of contact of catalyst and gases at below 350 DEG F. not exceeding a time in which less than an amount equivalent to 15 parts by weight of carbon oxide is in contact with 1 part of reduced metal catalyst, whereby excessive formation of solids such as wax is prevented, the reaction mixture being cooled to maintain the desired reaction temperature, and being withdrawn from the reaction zone to recover the liquid products therefrom.  Reduced cobalt catalyst which may be fresh or revivified by hydrogenation is used with twice its weight of a bentonite support and, preferably, small amounts of promoters.  The particles are, preferably, principally of 40-400 microns, and the space velocity of the reactants 0.2-10 standard litres per hour per gram of cobalt or 50-2000 standard vols. per hour per vol. of fluidized dense phase, the temperature being 350-450 DEG F.  The contact mass may be heated above 350 DEG F. by a stream of inert gas or by reduction just prior to passing in the reactants.  The reactor 1 has an enlarged extension 5 to facilitate disengagement of catalyst, and conduits 7, 8 with filters 9, 10.  A jacket 15 may contain liquid for temperature control.  In an example, a solution of cobalt and magnesium nitrates is added to sodium carbonate solution, "Superfiltrol" (R.T.M.) added, the mixture filtered, dried, reduced in hydrogen at up to 700 DEG F., and ground. This catalyst is introduced into the reactor in CO2 and heated by means of a water-jacket to 400 DEG F., aeration being effected first with CO2, then H2, and feed gas being introduced when 360 DEG F. is reached. Pressure varies up to 50 lbs. gauge.  In another example, the catalyst is reduced in the reactor by heating in hydrogen up to 700 DEG F. the temperature then being lowered to 300 DEG F., and raised rapidly to 360 DEG F. while passing feed gas.  Reaction temperatures up to 460 DEG F. are used.  Specifications 568,913 and 647,155 are referred to.  The Specification as open to inspection under Sect. 91 comprises the use instead of carbon oxides of any compound having a carbonyl group to produce also oxygenated components, the use of other catalysts such as nickel or iron and supports such as keiselguhr, and the injection of vaporizable liquids to control reaction temperature.  This subject-matter does not appear in the Specification as accepted.