Patent GB-1063201-A (GB)
Title: Improvements in and relating to three dimensional crystalline materials
IPC: B01J20/18
Filed: 1963-08-19
Abstract: A crystalline aluminosilicate material has the composition expressed in terms of mole ratios of oxides as follows xA2/n(1 - x)M2/nO: Al2O3: ySiO2 . . . (I) wherein n is the valence of A or M, M is at least one alkali or alkaline earth metal, x is from 1 to 0.1, y is from 9.0 to 25 where x is greater than 0.5 when y is from 9.0 to 10.5, and A is a hydrogen or a hydronium H3O+ ion incapable of being ion-exchanged and wherein said crystalline material contains from 0 to 20% by weight water, and has a given X-ray powder diffraction pattern.  This substance may be prepared by treating with an aqueous mineral acid a natural or synthetic material containing a crystalline alumino-silicate material having a composition expressed in terms of mole ratios of oxides as (1 - x) M2/nO: Al2O3: y.SiO2: 2H2O, wherein n is the valence of M, M is at least one alkali or alkaline earth metal, x is from 0 to 0.9, y is from 6 to 25 and 2 is from 0 to 7 and having an X-ray pattern the same as the material (I) above; until at least 0.1 moles of M is extracted from the starting material.  The temperature of treatment may vary from ambient to 100 DEG  C. and the concentration of the acid may vary from 4 to 10 normal.  After being formed, material (I) may be activated by heating if desired until all the hydrogen and hydronium ions have been removed therefrom to give a material having the formula expressed as mole ratios of (I - x)M2/nO: Al2O3: ySiO2, where n, M, x and y, have the same significance as in Formula I and the activated material has, substantially, the same X-ray pattern as the material before activation.  The activation step may be carried out at a temperature of 100-800 DEG  C., preferably 350 DEG  to 400 DEG  C. The M ions remaining in the material (I) above may be exchanged with ammonium, hydrogen transition metal ions by contacting the material preferably at a temperature of 20-100 DEG C., with an aqueous solution of the desired cation. The materials of the invention may be used as a desiccant or absorbent or as a catalyst in polymerisation or liquid phase alkylation processes, e.g. for sweetening natural gas, by removal of S compounds for purifying or drying feed streams containing acid components.ALSO:Isobutylene or propylene is polymerized (see Example E) by contacting it with a catalyst obtained by heating a material having the formula xA2/n(1 - x)M2/nO: Al2O3:ySiO2, where n is the valence of A or M, M is at least an alkali or alkaline earth metal, x is from 1 to 0.1, y is from 9.0 to 25 wherein x is greater than 0.5 when y is from 9.0 to 10.5, and A is hydrogen or hydronium H3O+ ion incapable of being ion-exchanged, said material containing 0-20% by weight water and having a given X-ray pattern; at a temperature of 100-800 DEG  C. preferably until all the H3O+ or hydrogen ions have been removed.  The initial material may be obtained by treating a natural or synthetic mordenate type material with an aqueous mineral acid. In the example the material used was activated at 350 DEG  C. and had a SiO2/Al2O3 ratio of 9.1 with 0.39 moles Na2O per mole of Al2O3, e.g. it was 0.39 Na2O:Al2O3:9.1 SiO2; and the reaction temperature for the polymerization was either ambient or 100 DEG  C.ALSO:An alumino-silicate material having a composition expressed in terms of mole ratios of oxides as X A2/n (1-x)M2/nO: Al2O3. YSiO2.. I wherein n is the valence of A or M, M is at least one alkali or alkaline earth metal, x is from 1 to 0.1, y is from 9.0 to 25 where x is 0.5 when y is from 9.0 to 10.5 and A is hydrogen or hydronium H3O+ ion incapable of being ion exchanged and wherein said material contain 0-20% by weight of water and has a given x-ray pattern is activated by heating at 100-800 DEG C.  Preferably so as to remove all H+ and H3O+ ions and the product used as a desiccant or adsorbent in drying a feed stream having an acid component, in removing 5 compounds from a natural gas stream or in drying a feed stream containing a halogen or halogen compound.