Patent GB-593940-A (GB)
Title: Improved process for the catalytic synthesis of normally liquid hydrocarbons
IPC: C07C1/04
Filed: 1945-06-20
Abstract: Liquid hydrocarbons are synthesized from CO and H2 using a catalyst prepared by impregnating a mineral acid-activated bentonitic clay in aqueous suspension with a major portion of a water soluble salt of a Group 8 hydrogenating metal such as Fe, Co, or Ni, and a minor portion of a water-soluble salt of a metal which forms a difficulty reducible oxide such as Th, Mg, U, Mn or Al, drying, heating to convert the salts to oxides, and reducing the Group 8 oxide to the metal.  Such a catalyst is resistant to attrition and can be prepared as a powder of the desired apparent density and particle size for "fluidized" operation. "Super-Filtrol," a mineral acid-treated "Filtrol" (R.T.M.) may be used, and may be further treated with H2 Si F6 or HF, for example with a 10 per cent. solution for half-an-hour. Bentonite may be treated with 75 per cent. by weight of 12 per cent. H2 SO4 for 6 hours followed by aluminium sulphate and then ammonia to give a precipitate of 5 per cent. alumina after calcining, or a bentonitic clay may be acid-activated, extruded, calcined, and finely ground, and then reformed with the use of a binder to a particle size of 20-60 microns.  The acid activation may be effected with sulphuric, hydrochloric or nitric acid.  Water-soluble salts such as nitrates, acetates or oxalates of the catalytic metals may be mixed with the activated clay in aqueous suspension, and the product dried and calcined at about 400-600 DEG F.  Alternatively, an alkaline carbonate may be added to precipitate the metal carbonates prior to the drying.  The product may be pilled before or after reduction with hydrogen at 600-900 DEG  F.  The final catalyst generally contains about 25-40 per cent Group 8 metal, and 3-10 per cent. promoting oxide, e.g., Co 32 or 25 per cent., Th or Mg oxide 5 or 4 per cent. Examples describe the preparation of catalysts containing Co with Ni as an impurity, thoria, and, as carrier, a bentonite activated with sulphuric acid and further treated with HF or with aluminium sulphate and ammonia.ALSO:Liquid hydrocarbons are synthesized from CO and H2 using a catalyst prepared by impregnating a mineral acid-activated bentonitic clay in aqueous suspension with a major portion of a water-soluble salt of a Group 8 hydrogenating metal such as Fe, Co or Ni, and a minor portion of a water-soluble salt of a metal which forms a difficultly reducible oxide such as Th, Mg, U, Mn or Al, drying, heating to convert the salts to oxides, and reducing the Group 8 oxide to the metal.  Such a catalyst is resistant to attrition and can be prepared as a powder of the desired apparent density and particle size for "fluidized" operation. "Super-Filtrol," a mineral acid-treated "Filtrol" (Registered Trade Mark) may be used, and may be further treated with H2SiF6 or HF, for example with a 10 per cent solution for 1/2 hr.  Bentonite may be treated with 75 per cent by weight of 12 per cent H2SO4 for 6 hrs., followed by aluminium sulphate and then ammonia to give a precipitate of 5 per cent alumina after calcining, or a bentonitic clay may be acid-activated, extruded, calcined and finely ground, and then reformed with the use of a binder to a particle size of 20-60 microns.  The acid activation may be effected with sulphuric, hydrochloric or nitric acid. Water-soluble salts such as nitrates, acetates or oxalates of the catalytic metals may be mixed with the activated clay in aqueous suspension, and the product dried and calcined at about 400-600 DEG F.  Alternatively, an alkaline carbonate may be added to precipitate the metal carbonates prior to the drying.  The product may be pilled before or after reduction with hydrogen at 600-900 DEG  F.  The final catalyst generally contains about 25-40 per cent Group 8 metal, and 3-10 per cent promoting oxide, e.g. Co 32 or 25 per cent, Th or Mg oxide 5 or 4 per cent.  Synthesis is effected at 325-550 DEG  F. with Ni or Co or 375-700 DEG  F. with Fe as catalyst using a Co : H2 ratio of 0.5-5 : 1 and pressures up to 50 atm.  Using fluidized catalyst of a particle size of 20-150 microns, the reactants may be passed at a space velocity of 100-3000 vols./vol./hr., the operation being conducted either downflow, i.e. withdrawing catalyst by gravity from the bottom of the reactor while reactants flow upwardly, or upflow. Examples describe the preparation and use of catalysts containing Co with Ni as an impurity, thoria and, as carrier, a bentonite activated with sulphuric acid and further treated with HF or with aluminium sulphate and ammonia