Patent GB-703739-A (GB)
Title: Process for preparing high molecular weight hydrocarbons
IPC: C08G61/04
Filed: 1952-01-15
Abstract: Polymethylenes are prepared by heating carbon monoxide with hydrogen at a temperature of from 125 DEG -300 DEG C. under a pressure of at least 200 atmospheres in the presence of a metal tungstite catalyst, preferred catalysts being nickel and/or cobalt tungstite or a mixed nickel tungstite-molybdite.  The reaction is preferably carried out in an inert liquid medium such as water, a hydrocarbon, e.g. xylene or cyclohexane, or an alcohol, and the initial mol. proportion of carbon monoxide and hydrogen is preferably 1 : 2.  The process may be a batch, semi-continuous or continuous operation and there may be incorporated into the reaction medium an acid material such as phosphoric acid or an alkyl acid phosphate or an alkaline material such as an alkali metal carbonate or hydroxide.  The catalysts may contain modifiers or promoters such as barium, cadmium, chromium, thorium, cobalt or copper and may be employed as pellets or finely divided powders or extended on inert supports such as charcoal, alumina and silica. Pellets of copper, aluminium or iron may be incorporated with the catalyst to act as heat transfer media.  The surface of the reactor in contact with the reactants should preferably be of silver, copper or stainless steel.  The products may be used for the production of films or fibres, which may be oriented.ALSO:Macromolecular essentially hydrocarbon compositions are prepared by heating carbon monoxide with hydrogen at a temperature of from 125 DEG -300 DEG C. under a pressure of at least 200 atmospheres in the presence of a metal tungstite catalyst, preferred catalysts being nickel and/or cobalt tungstite or a mixed nickel tungstite molybdite.  The reaction is preferably carried out in an inert liquid medium such as water, a hydrocarbon, e.g. xylene or cyclohexane, or an alcohol, and the initial mol. proportion of carbon monoxide and hydrogen is preferably 1:2.  The process may be a batch, semi-continuous or continuous operation and there may be incorporated into the reaction medium an acid material such as phosphoric acid or an alkyl acid phosphate or an alkaline material such as an alkali metal carbonate or hydroxide.  The catalysts may contain modifiers or promoters such as barium, cadmium chromium, thorium, cobalt or copper and may be employed as pellets or finely divided powders or extended on inert supports such as charcoal, alumina and silica.  Pellets of copper, aluminium or iron may be incorporated with the catalyst to act as heat transfer medium. The surface of the reactor in contact with the reactants should preferably be of silver, copper or stainless steel.ALSO:In a process for the preparation of nickel tungstite a 10 per cent. aqueous solution containing 4 mols. of ammonium tungstate is added to 4 mols. of nickel nitrate in a 16 per cent. solution and the resulting slurry adjusted to pH 7 by adding ammonia.  The resulting precipitate is washed, filtered, dried and calcined at 400 DEG  C., after which it is heat treated at 400 DEG C. in a stream of nitrogen, cooled to room temperature and then reduced for 24 to 47 hours at 450 DEG  C. to 480 DEG  C. in hydrogen. The reduced product corresponds by analysis to nickel tungstite (Ni WO2) containing a slight excess of W2 O3.  A mixed tungstite-molybdite catalyst is prepared by adding an aqueous solution containing ammonium paramolybdate, ammonium paratungstate and ammonium hydroxide to an aqueous solution of nickel nitrate and the pH of the resulting slurry adjusted to 7 by addition of ammonium hydroxide; the precipitate is washed, filtered and dried, and the dry cake calcined at 400 DEG  C. and reduced in hydrogen at 450 DEG  C. The catalyst is used in a reaction for the production of macromolecular essentially hydrocarbon compositions by heating carbon monoxide with hydrogen and the catalyst may contain modifiers or promoters such as barium, cadmium, chromium, thorium, cobalt or copper and may be employed as pellets or finely divided powders or extended on inert supports such as charcoal, alumina and silica.