Patent GB-1036411-A (GB)
Title: Synthetic zeolite and method for preparing same
IPC: B01J29/70
Filed: 1963-02-13
Abstract: A catalyst for the cracking of n-hexane is a hydrogen aluminosilicate material derived from the synthetic zeolite ZK-5 and having the composition <FORM:1036411/C4-C5/1> wherein R is hydrogen and/or a nitrogen-containing cation derived from N,N1 - dimethyltriethylenediammonium ion and m is the valence of R, M is a metal and n the valence of M, Y is 6-10 and wherein the metallic cation M has been replaced to the extent of at least 96% by hydrogen ions (see Division C1); the catalyst is activated by heating for 1-48 hours at 400-1500 DEG F. and may be supported in a silica- or alumina-containing single or plural gel matrix, and promoted by Ce, Cr, Co, W, U, Pt, Pb, Zn, Ca, Mg, Li, Ag, Ni or compounds thereof.ALSO:A synthetic crystalline aluminosilicate designated zeolite ZK-5, has the composition 0.3-0.7 <FORM:1036411/C1/1> YH2O, wherein R is hydrogen and/or a nitrogen-containing cation derived from N,N1-dimethyl-triethylenediammonium ion and m is the valence of R, M is a metal and n the valence of M, and Y is 6-10, and has the X-ray powder diffraction pattern set out in Table A of the Specification; the zeolite is prepared from a reaction mixture whose composition in terms of oxide mole ratios falls within the ranges SiO2: Al2O3, 2.5-15.0: 1; Na2O: (Na2O+C8H18N2O), 0.01-0.25: 1; H2O: (Na2O+C8H18N2O), 25-50: 1; (Na2O+C8H18N2O): SiO2, 1-2: 1, by maintaining the mixture at 20-120 DEG  C., preferably in aqueous solution at 100 DEG  C., until the said crystalline material is formed (usually 2-250 hours).  The invention also provides a hydrogen aluminosilicate material derived from zeolite ZK-5, wherein the metal content is less than 4% by weight, the metallic cations M having been replaced by hydrogen ions or ions capable of conversion thereto; this material is prepared by treating ZK-5 with a fluid medium containing the said ions.  The sodium form of zeolite ZK-5 may be made by reacting in aqueous media, at atmospheric or superatmospheric pressure, sodium aluminate and 1,4 - dimethyl - 1,4 - diazoniabicyclo[2.2.2] octane silicate. The product which crystallizes from the hot reaction mixture is separated, washed until the effluent wash water is of pH 8-12, and thermally activated in an inert atmosphere, preferably air or a gas containing molecular oxygen, at 200-600 DEG  C., under which conditions the nitrogen-containing cation is degraded to hydrogen or hydronium ion. Sodium zeolite ZK-5 when activated or the activated zeolite in which sodium is partially or wholly replaced by other cations is used as a selective adsorbent for hydrocarbons; such cations include Li, Mg, K, Ag, Ca, Sr, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Ru, Rh, Pd, Hf, Ta, W, Re, Os, Ir, Pt, Ce, La, Pr, Nd, Sm, NH4 and H.  As an adsorbent the zeolite may be the pure powder, pelleted with clay, or supported in an inorganic ioxide gel matrix, e.g. SiO2, Al2O3, MgO, ZrO2, TiO2 or mixtures thereof.  The hydrogen derivative of zeolite ZK-5 shows high catalytic activity in hydrocarbon conversions when activated for 1-48 hours at 400-1500 DEG  F., and may be used in powder, granular or moulded state, particularly in a silica- or alumina-containing single or plural gel matrix.ALSO:1,4 - Dimethyl - 1,4 - diazoniabicyclo - [2.2.2] octane diiodide (N,N1-dimethyltriethylene-di-ammonium diiodide) is prepared by complete methylation of 1,4 - diazoniabicyclo - [2.2.2] octane (triethylene diamine) with methyl iodide, is then converted to the dihydroxide by reaction with aqueous silver nitrate, and further converted to 1,4 - dimethyl - 1,4 - diazoniabicyclo - [2.2.2] octane silicate (N,N1-dimethyltriethylene-diammonium silicate) by reaction with silica gel.ALSO:A synthetic crystalline aluminosilicate, designated zeolite Zk-5 of composition 0.3-0.7 R2O/m 0.3-0.7 M2O/n : Al2O3 : 4.0-6.0 S1O2 : YH2O wherein R is hydrogen and/or a nitrogen-containing cation derived from N, N1-dimethyltriethylenediammonium ion and m is the valence of R, M is a metal and n the valence of M and Y is 6-10, functions after thermal activation at 200-600 DEG C. as a selective adsorbent for hydrocarbons.  M is sodium which may be partially or wholly replaced by other metals (listed).  The zeolite selectively adsorbs straight chain molecules of more than 3 carbon atoms from admixture with non-straight chain hydrocarbons e.g. n-hexane from cyclohexane and 3-methylpentane; it may be used as a column of pure powder, or pelleted with clay, or supported in a silica, alumina, magnesia, zirconia, titania or mixed gel matrix.  The invention also provides a hydrogen aluminosilicate material derived from zeolite ZK-5 wherein the metal content is less than 4% by weight the metallic cations M having been replaced by hydrogen, the said material after activation at 400-1500 DEG F. for 1-48 hours being catalytically active for hydrocarbon conversions. Catalyst compositions comprise the hydrogen aluminosilicate in a siliceous or aluminous single or plural gel matrix e.g. 55-100 weight per cent silica with 0-45 weight per cent magnesia, alumina, zirconia, beryllia or thoria optionally promoted by Ce, Cr, Co, W, U, Pt, Pb, Zn, Ca, Mg, Li, Ag, Ni or compounds thereof.