Patent GB-1070906-A (GB)
Title: Crystalline aluminosilicate zeolite containing a metal, and a method of preparing the same
IPC: B01J29/06
Filed: 1963-11-01
Abstract: A metal-containing aluminosilicate zeolite, prepared by crystallization of an aqueous reaction mixture containing a minor amount of a water-soluble compound of the metal, followed by dehydration of the product, may be used for:-(a) selective hydrogenation of hydrocarbons, e.g. (i) n-butene in the presence of iso-butene, (ii) butadiene and piperylene in the presence of isoprene; (b) cracking of hexane to give a gas mixture containing ethylene, propylene, and minor amounts of higher olefins.  The metal may be Cu, Ti, V, Cr, Mo, Mn, Fe, Co, or Ni, and may be added as a simple salt, a metal-containing anion, or a complex. The zeolite may be A, X, T, or E, and is prepared by conventional methods.  The product may be calcined, optionally in H2 to produce free metal. Alkali metal ions in the zeolite may be replaced, e.g. by Ca, Ba, Zn, Ni, Co, or rare earth ions.ALSO:An aluminosilicate zeolite containing a metal (other than a Pt group metal) in its structure is prepared by crystallization of an aqueous reaction mixture which contains a minor amount of a water-soluble compound of the metal, followed by dehydration of the product.  The metal may be Cu, Ti, V, Cr, Mo, Mn, Fe, Co, or Ni.  The alumino-silicate may be zeolite A, X, T, or E, and is prepared by conventional methods, e.g. from Na aluminate and Na metasilicate. The metal may be added to either reactant or to the mixture, in amounts to give a content of 0.001-5% in the product. A simple salt or a cationic, anionic or neutral complex may be used. The Na salt of such an anionic complex may replace part of the alkali metal aluminate in the reaction mixture. Crystallization is effected at 21-150 DEG  C., and after drying at 100-140 DEG  C. the product may be calcined at 250-1100 DEG  F., and simultaneously or subsequently heated in H2 to obtain at least some free metal.  The product may be washed prior to drying with a solution of pH 10.5-11.5 which contains the same ions as the aluminosilicate, e.g. 2-4 equ. Na+ per litre, and may contain small amounts of the Na aluminate and silicate. The alkali metal ions in the zeolite may be wholly or partly replaced with other metal cations, e.g. Ca, Ba, Zn, Ni, Co or rare earths, e.g. La, Ce, Pr, Gd, Sm, Y, Yb, or Sc, by contacting with a solution of the metal salt of pH greater than 10.5 containing 2-4 equ. metal cation per litre.  Examples 1-19, 26-39 and 53 describe the use of alkali metal salts of complex anions containing Mn, Fe, V, Cr, Mo and Ti, and Examples 20-25 and 40-45 the use of the simple salts FeCl3, TiCl3, NiCl2, CoCl2 and CrCl3.  Examples 1-25 relate to the preparation of a zeolite of faujasite structure with pores 13 <\>rA in diameter, and Examples 26-45 relate to zeolite 4A. Example 52 describes the use of a Cu ethylene diamine complex.ALSO:An aluminosilicate zeolite containing a metal (other than a Pt group metal) in its structure is prepared by crystallisation of an aqueous reaction mixture which contains a minor amount of a water-soluble compound of the metal, followed by dehydration of the product.  The metal may be Cu, Ti, V, Cr, Mo, Mn, Fe, Co, or Ni.  The aluminosilicate may be zeolite A, X, T, or E, and is prepared by convential methods, e.g. from Na aluminate and Na metasilicate.  The metal may be added to either reactant or to the mixture, in amounts to give a content of 0.001-5% in the product. A simple salt or a cationic, anionic or neutral complex may be used.  The Na salt of such an anionic complex may replace part of the alkali metal aluminate in the reaction mixture. Crystallisation is effected at 21-150 DEG C, and after drying at 100-140 DEG C the product may be calcined at 250-1100 DEG F, and simultaneously or subsequently heated in H2 to obtain at least some free metal.  The product may be washed prior to drying with a solution of pH 10.5-11.5 which contains the same ions as the aluminosilicate, e.g. 2-4 equ. Na\sW per litre, and may contain small amounts of the Na aluminate and silicate.  The alkali metal ions in the zeolite may be wholly or partly replaced with other metal cations e.g. Ca, Ba, Zn, Ni, Co or rare earths, e.g. La, Ce, Pr, Gd, Sm, Y, Yb, or Sc, by contacting with a solution of the metal salt of pH greater than 10.5 containing 2-4 equ. metal cation per litre.  Examples 1-19, 26-39 and 53 describe the use of alkali metal salts of complex anions containing Mn, Fe, V, Cr, Mo and Ti, and Examples 20-25 and 40-45 the use of the simple salts Fe Cl3, Ti Cl3, Ni Cl2, Co Cl2 and Cr Cl3.  Examples 1-25 relate to the preparation of a zeolite of faujasite structure with pores 13  in diameter, and Examples 26-45 relate to zeolite 4A.  Example 52 describes the use of a Cu ethylene diamine complex.