Patent GB-937749-A (GB)
Title: Metal loading of molecular sieves
IPC: B01J37/02
Filed: 1959-09-23
Abstract: A metal loaded zeolitic molecular sieve is prepared by contacting a dehydrated zeolite with a decomposable compound of Cu, Ag, Au, Pt, Ir, Os, Pa, Rh, Ru, Zn, Cd, Al, Sn, Pb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ti, Zr, Hf and V, and thereafter decomposing the metal compound to the elemental metal.  The decomposable compound may be applied as a vapour, as a liquid or as an aqueous or organic solvent solution, particularly in the form of metal carbonyl, carbonyl hydride, acetylacetonate, alkyl or a volatile metal halide.  The zeolites to be treated include the natural zeolites faujasites and erionite and the synthetic zeolites X, Y, L and T as set forth in Specifications 777,233, 909,264, 909,266 and 912,936 respectively.  Such sieves are activated by heating to a temperature of 350 DEG C. in an inert dry gas or in vacuum before contacting with the decomposable metal compound.  Decomposition may be thermal or chemical.  According to Examples (1) zeolite in sodium form, activated at 350 DEG C., was treated with iron pentacarbonyl vapour under reduced pressure until adsorption ceased.  On heating the treated material at 250 DEG C. under nitrogen, 8% by weight of iron was left in the pores of the zeolite.  On contact with air the iron content oxidized.  The nickel loaded zeolite may be similarly prepared.  (3) Activated zeolite X was treated with copper acetylacetonate dissolved in chloroform and the powder after filtering was purged with dry hydrogen to remove the solvent, then heated to 400 DEG C. under hydrogen to decompose the copper salt. (4) Zeolite X was treated with bis (cyclopentadienyl) nickel dissolved in n-heptane in an argon atmosphere thereafter transferred to a pressure vessel under 1,200 psig. of hydrogen.  The temperature was thereafter raised slowly to hydrogenate the cyclopentadienyl compound leaving a nickel-containing zeolite product. (5) Zeolite X was treated with a platinumethylenic complex which was prepared by refluxing anhydrous sodium hexachlorplatinate in ethanol and adding ammonium chloride to precipitate unreacted hexachloroplatinate; the resulting complex is dissolved in chloroform and the zeolite X powder added.  After filtering and drying the zeolite was treated with hydrogen at 150 DEG C. to reduce the complex to free platinum metal.  (6) Zeolite Y powder, activated at by heating to 350 DEG C., was mixed with bistoluene chromium and heated in a closed tube at 95 DEG C.  It was thereafter heated at 375 DEG C. in flowing argon to leave 5% metallic chromium in the zeolite.  (7) Sodium zeolite X was passed through a cycle which consisted of adsorption of nickel carbonyl vapours at 25 DEG C. followed by heating to decompose the carbonyl and evacuate the evolved carbon monoxide.  A weight increase of 212% was obtained when 80% of the estimated pore volume was filled with metallic nickel.  The product was ferromagnetic.  (10) Sodium zeolite X was heated in argon to 125 DEG C. and sodium was added whilst stirring; titanium tetrachloride was added slowly to the resulting dispersion and a product containing 6% titanium was obtained.  (11) Sodium zeolite X was contacted with a chloroform solution of cobalt acetylacetonate and the treated zeolite was then reduced in hydrogen at 350 DEG C. to leave a product containing 0,3% of cobalt metal.  Further examples relate to molybdenum and chromium deposition in sodium zeolite X from the metal hexacarbonyl. Specifications 937,748 and 937,750 also are referred to.