Patent GB-452095-A (GB)
Title: Improvements in carrying out catalytic reactions
IPC: C10G45/04
Filed: 1935-02-27
Abstract: In the conversion of organic compounds containing oxygen or sulphur into hydrocarbons by hydrogenation, e.g. the conversion of phenol or cresol into the corresponding hydrocarbons or their hydrogenation products, and also in reactions such as the conversion of cresol into phenol, use is made of catalysts comprising metals or their compounds which have been activated by treatment with fluorine or its compounds as described in Specification 452,158.  Specified metals are iron, cobalt, nickel, molybdenum, tungsten, chromium, vanadium, tin, titanium, lead, manganese, particularly finely divided iron, cobalt, or manganese in the presence of alkaline substances; compounds in particular the oxides, hydroxides, carbonates, phosphates or nitrates of aluminium, zinc, magnesium tin, lead, vanadium, chromium, manganese, iron, cobalt, nickel, rare earths, zirconium may be similarly activated.  The activated metals may be boiled with an alkaline solution or the solid or liquid organic reaction materials may be mixed with alkaline substances or impregnated with solutions of the same.  Other substances such as halogens, hydrogen sulphide and metalloids (other than silicon) may be present during the activation treatment.  The activated materials particularly after washing may be subjected to after-treatment with hydrogen, hydrogen halides or hydrogen sulphide at elevated temperature.  Liquid initial materials liable to form deposits on the catalysts during the reaction are preferably pretreated in presence of strongly hydrogenating catalysts, e.g. metal sulphides of Groups 4--8 or oxides of Group 6.  Specification 325,234, [Class 1 (i)], is referred to.ALSO:Catalysts for the hydrogenation of carbonaceous materials comprising metals or their compounds are activated by treatment with fluorine or its compounds in the manner described in Specification 452,158.  Specified metals are iron, cobalt, nickel, molybdenum, tungsten, chromium, vanadium, tin, titanium, lead, manganese, particularly finely divided iron, cobalt, or manganese in the presence of alkaline substances; compounds, in particular the oxides, hydroxides, carbonates, phosphates or nitrates, of aluminium, zinc, magnesium, tin, lead, vanadium, chromium, manganese, iron, cobalt, nickel, rare earths, zirconium, may be similarly activated.  The activated metals may be boiled with an alkaline solution or the solid or liquid organic reaction materials may be mixed with alkaline substances or impregnated with solutions of the same.  Other substances such as halogens, hydrogen sulphide and metalloids (other than silicon) may be present during the activation treatment. Catalysts containing a constituent having a hydrogenating action, e.g. tungsten sulphide and a constituent having a cracking action, e.g. alumina, rare earths, and zirconium compounds, and which has been activated according to the present invention, are particularly suitable. The activated materials particularly after washing may be subjected to after-treatment with hydrogen, hydrogen halides or hydrogen sulphide at elevated temperature.  Liquid initial materials liable to form deposits on the catalysts during the reaction are preferably pretreated in presence of strongly hydrogenating catalysts e.g. metal sulphides of Groups 4--8 or oxides of Group 6.  Alumina grains of 3--4 mm. diameter are treated at room temperatures for 15 mins. with 10 per cent strength hydrofluoric acid.  The treated material is dried, impregnated with ammonium thiotungstate, and heated to 400 DEG  C. in a current of hydrogen.  The product obtained is used in the treatment of gas oil with hydrogen at 400 DEG  C., and 200 atms. Specification 325,234, [Class 1 (i)], is referred to.