Patent GB-1074130-A (GB)
Title: Synthetic zeolite
Inventor: WADLINGER ROBERT LOIS
IPC: B01J29/70
Filed: 1963-12-04
Abstract: A base exchanged form of a zeolite of composition 0.2-0.5 R2O:0.5-0.8 Na2O:Al2O3; 4-7 SiO2:0-8 H2O, where R is methyl ammonium, is used as catalyst in cracking a mid-continent gas oil (b.pt. 230-510 DEG  C.) to gasoline (see Examples 10 and 11).ALSO:Zeolite alpha has composition 0.2-0.5 R2O : 0.5-0.8 Na2O : Al2O3: 4-7 SiO2 : 0-8 H2O where R is methyl ammonium.  It has the X-ray pattern of zeolite A and is prepared by heating a reaction mixture of composition .SiO2/Al2O3.15-60 .Na2O/Na2O+R2O.0.01-0.3 .H2O/Na2O+R2O.30-60 .Na2O+R2O/SiO2.0.5-1.0 at 20-90 DEG  C. for 15 minutes to 90 hours and washing the crystalline product to an effluent pH of 9-12. Suitable starting materials are Na aluminosilicate gel (NaAlO2. 0.5-20 SiO2, obtained, e.g. from Si(OEt)4 and Na aluminate), a solution of Al turnings in NaOH, silica gel or hydrosol (e.g. of particle size 0.017 m ), silicate esters, tetramethyl-ammonium silicate (obtained, e.g. from the hydroxide and silica), and Na aluminate.  The product may be activated in an inert atmosphere, e.g. air or N2, at 200-600 DEG  C. under atmospheric or reduced pressure, or at room temperature under vacuum (this causes decomposition of the methylammonium ions to hydrogen).  At least 70% of the Na ions may be replaced by ions of ammonium, Ca, Mg, a transistion metal, or a rare earth metal by treating with a solution of a salt of the cation at temperatures up to the boiling point of the solution; or by hydrogen ions by treating with a fluid medium containing H ions, e.g. an organic or inorganic acid, or ions capable of conversion to H ions, e.g. ammonium; followed by washing to an effluent pH of 5-8. Treatment may be effected continuously by passing a gas, molten material, aqueous or organic solution (suitable solvents are listed) through a bed of zeolite or batchwise in a closed vessel.  The pH of the solution containing H or NH4 ions may be 3.8-7 or 4.5-20 respectively.  The product may be used as a powder of particle size <40m , or formed, e.g. by extrusion, into pellets of SiCl 2-500 mesh, or may be mixed with a binder before or after ion exchange to give a matrix containing 1-90% zeolite, which may then be formed into pellets of size 1/16 -\ba1/8 inch. It may be dried before or after pelleting at 65-315 DEG  C., calcined at 204-816 DEG C. in an inert atmosphere, e.g. air, N2, H2, He, or flue gas, and may then be treated in an atmosphere containing at least 5% steam at 204-800 DEG C. and at atmospheric to 500 p.s.i.g. pressure.  The binder may be an inorganic oxide gel, sol or sol-forming reactants, clay, metal powder, e.g. Al, or Fe alloys, kieselguhr, sintered Al2O3, mullite, bauxite, SiC, active carbon, charcoal, or graphite. The oxide binder may be of Si, Al, Cr, Mg, Hf, Th, Ti, B or Be, or their mixtures.  If a sol is used it may be shaped by allowing to gel in the holes of a perforated plate or by dropping into a water immiscible liquid, e.g. oil or by spray drying.  Up to 40% of other materials of particle size 1-40m  may be incorporated into the mixture, e.g. clay, Al2O3, zircon, barytes, carbon, wood flour, SiO2, catalyst fines, MgO, ores or minerals.ALSO:A catalytic or adsorbent composition comprises a zeolite of composition: 0.2 - 0.5 R2O: 0.5 - 0.8 M2O: Al2O3: 4-7 SiO2: 0-8 H2O, where R is methyl ammonium, or hydrogen (obtained by calcination), and M is Na or a base exchanged ion, e.g. H, NH4 Ca, Mg, a transition metal, or a rare earth metal [see Div. C1], alone or mixed with a binder.  Suitable binders are an inorganic oxide gel, sol or solfoming reactants (e.g. of Si, Al, Zr, Mg, Hf, Th, Ti, B, Be, or mixtures), clay, metal powder (e.g. Al or Fe alloys), kieselguhr, sintered Al2O3, mullite, bauxite, SiC, active carbon, charcoal, or graphite.  Other materials of particle size 1-40m  may be added, e.g. clay, Al2O3, zircon, barytes, carbon, wood flour SiO2, catalyst fines, MgO, ones, or minerals.  The zeolite may be used as a powder (e.g. < 40m ) or fomed e.g. by extrusion, into pellets of size 2-500 mesh or 1/16 -\ba1/8 inch.  It may be dried before or after pelleting at 65-315 DEG C, calcined at 204 - 816 DEG C in an inert atmosphere, e.g. air, N2 H2, He, or flue gas, and may then be treated in an atmosphere containing at least 5% steam at 204-800 DEG C and at atm. to 500 psig. pressure.  If asd is used as binder it may be shaped by allowing the gel in the holes of a perforated plate or by dropping into a water-immiscible liquid, e.g. oil, or by spray drying.  The composition may be used as a catalyst for hydrocarbon conversions and as an adsorbent for separating liquids and gases, e.g. straight chain hydrocarbons from branched chain hydrocarbons.