Aluminosilicate compositions, preparation and use

Abstract

A method for preparing a metalloaluminosilicate, includes the steps of: providing a solution containing a silica source; providing a solution containing an alumina source; providing an aqueous acid solution containing a metal other than silicon or aluminum; mixing the silica source solution with the aqueous acid solution so as to form a silica source-metal containing mixture; mixing the silica source-metal containing mixture with the alumina source solution so as to provide a gel mixture; and hydrothermally crystallizing the gel mixture so as to provide a metalloaluminosilicate material having an aluminosilicate framework and having the metal incorporated into the aluminosilicate framework. A method for preparing aluminosilicate, and specific compositions, are also provided.

What is claimed is:  
     
         1 . A method for preparing a metalloaluminosilicate, comprising the steps of: 
 providing a solution containing a silica source;    providing a solution containing an alumina source;    providing an aqueous acid solution containing a metal other than silicon or aluminum;    mixing the silica source solution with the aqueous acid solution so as to form a silica source-metal containing mixture;    mixing the silica source-metal containing mixture with the alumina source solution so as to provide a gel mixture; and    hydrothermally crystallizing the gel mixture so as to provide a metalloaluminosilicate material having an aluminosilicate framework and having the metal incorporated into the aluminosilicate framework.    
     
     
         2 . A method according to  claim 1 , wherein the metal comprises at least one metal selected from the group consisting iron, zinc, zirconium, chromium, nickel, cobalt, magnesium, phosphorous, gallium and mixtures thereof.  
     
     
         3 . A method according to  claim 1 , wherein the metal is selected from the group consisting of iron, zinc and mixtures thereof.  
     
     
         4 . A method according to  claim 1 , wherein the gel mixture has a composition in molar ratios as follows: 
 SiO 2 /Al 2 O 3  from 5 to 80,    SiO 2 /DO x  from 10 to 1500,    SiO 2 /(Al 2 O 3 +DO x ) from 5 to 70,    Na 2 O/SiO 2  from 0.22 to 2.20,    OH/SiO 2  from 0.01 to 2.00,    H 2 O/SiO 2  from 14 to 40,    where D is the metal.    
     
     
         5 . A method according to  claim 1 , wherein the metalloaluminosilicate has a composition expressed in mole ratios of oxides according to an equation selected from the following:  
       
         
           
                 
                 
               
                     
                     
                 
                     
                     
                 
                     
                   1. - a(M 2 / n O) : b(Al 2 O 3 ) : c(E 2 O 3 ) : d(SiO 2 ) : e(H 2 O) 
                 
                     
                   2. - a(M 2 / n O) : b(Al 2 O 3 ) : c(FO 2 ) : d(SiO 2 ) : e(H 2 O) 
                 
                     
                   3. - a(M 2 / n O) : b(Al 2 O 3 ) : c(GO) : d(SiO 2 ) : e(H 2 O) 
                 
                     
                   4. - a(M 2 / n O) : b(Al 2 O 3 ) : c(H 2 O 5 ) : d(SiO 2 ) : e(H 2 O) 
                 
                     
                     
                 
                     
                     
                 
             
                
                
               
               
                
                
                
                
                
                
               
            
           
         
       
       where M is at least one ion-exchangeable cation having a valence of n; E is an element with valence 3+; F is an element with valence 4+; G is an element with valence 2+; H is an element with valence 5+; a is from >0 to 6; b is equal to 1, c is from >0 to 10; d is from 10 to 80; d/c is from 10 to 1500; e is from 0 to 100; a/(b+c) is from >0 to 5; and d/(b+c) is from 10 to 70.  
     
     
         6 . A method according to  claim 1 , wherein the hydrothermally crystallizing step is carried out at a temperature of between about 150° C. and about 220° C. under autogenous pressure for a period of at least about 24 hours.  
     
     
         7 . A method according to  claim 1 , wherein the hydrothermally crystallizing step is carried out at a temperature of between about 165° C. and about 185° C. under autogenous pressure for a period of at least about 24 hours.  
     
     
         8 . A method according to  claim 1 , wherein the step of hydrothermally crystallizing further comprises the steps of filtering and washing the metalloaluminosilicate material to provide a separated metalloaluminosilicate and drying the separated metalloaluminosilicate to provide a metalloaluminosilicate product.  
     
     
         9 . A method according to  claim 8 , wherein the drying step is carried out at a temperature of between about 80° C. and about 140° C.  
     
     
         10 . A method according to  claim 1 , wherein the step of providing the silica source solution comprises dissolving sodium silicate in distilled water.  
     
     
         11 . A method according to  claim 1 , wherein the step of providing the alumina source solution comprises dissolving sodium aluminate in distilled water.  
     
     
         12 . A method according to  claim 1 , wherein the step of providing the aqueous acid solution comprises the steps of providing an acid solution and dissolving a metal salt in the acid solution.  
     
     
         13 . A method according to  claim 12 , wherein the acid solution comprises an aqueous solution of an acid selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid and mixtures thereof.  
     
     
         14 . A method according to  claim 1 , further comprising the step of mixing the gel mixture so as to provide a substantially homogeneous gel mixture, and hydrothermally crystallizing the substantially homogeneous gel mixture.  
     
     
         15 . A method according to  claim 1 , wherein the step of mixing the silica source solution with the aqueous acid solution is carried out under continuous mixing so as to provide a substantially homogeneous silica source-metal containing mixture and wherein the step of mixing the silica source-metal containing mixture is carried out under continuous mixing for a period of time sufficient to provide a substantially homogeneous gel mixture.  
     
     
         16 . A method according to  claim 1 , further comprising the step of converting the metalloaluminosilicate material to protonic form.  
     
     
         17 . A method according to  claim 16 , wherein the converting step is an ion exchange step.  
     
     
         18 . A method for preparing an aluminosilicate composition comprising the steps of: 
 providing a solution containing a silica source;    providing a solution containing an alumina source; mixing the silica source solution with the aqueous acid solution so as to form a silica source acid mixture;    mixing the silica source acid mixture with the alumina source solution so as to provide a gel mixture; and    hydrothermally crystallizing the gel mixture so as to provide an aluminosilicate composition having an aluminosilicate composition having an aluminosilicate framework, wherein the composition is formed without organic additives.    
     
     
         19 . A method for preparing an aluminosilicate composition consisting essentially of the steps of: 
 providing a solution containing a silica source;    providing a solution containing an alumina source; mixing the silica source solution with the aqueous acid solution so as to form a silica source acid mixture;    mixing the silica source acid mixture with the alumina source solution so as to provide a gel mixture; and    hydrothermally crystallizing the gel mixture so as to provide an aluminosilicate composition having an aluminosilicate framework, wherein the composition is formed without organic additives.    
     
     
         20 . A metalloaluminosilicate composition comprising an aluminosilicate composition having an aluminosilicate framework and containing at least one metal incorporated into the aluminosilicate framework.  
     
     
         21 . A composition according to  claim 20 , wherein the metal comprises at least one metal selected from the group consisting of iron, zinc, zirconium, chromium, nickel, cobalt, magnesium, phosphorous, gallium and mixtures thereof.  
     
     
         22 . A composition according to  claim 20 , wherein the metal comprises at least one metal selected from the group consisting of iron, zinc and mixtures thereof.  
     
     
         23 . A composition according to  claim 20 , which is prepared from a gel mixture having the following molar ratios: 
 SiO 2 /Al 2 O 3  from 5 to 80,    SiO 2 /DO x  from 10 to 1500,    SiO 2 /(Al 2 O 3 +DO x ) from 5 to 70,    Na 2 O/SiO 2  from 0.22 to 2.20,    OH/SiO 2  from 0.01 to 2.00,    H 2 O/SiO 2  from 14 to 40,    where D is the metal.    
     
     
         24 . A composition according to  claim 20 , wherein the composition has mole ratios of oxides according to an equation selected from the following:  
       
         
           
                 
                 
               
                     
                     
                 
                     
                     
                 
                     
                   1. - a(M 2 / n O) : b(Al 2 O 3 ) : c(E 2 O 3 ) : d(SiO 2 ) : e(H 2 O) 
                 
                     
                   2. - a(M 2 / n O) : b(Al 2 O 3 ) : c(FO 2 ) : d(SiO 2 ) : e(H 2 O) 
                 
                     
                   3. - a(M 2 / n O) : b(Al 2 O 3 ) : c(GO) : d(SiO 2 ) : e(H 2 O) 
                 
                     
                   4. - a(M 2 / n O) : b(Al 2 O 3 ) : c(H 2 O 5 ) : d(SiO 2 ) : e(H 2 O) 
                 
                     
                     
                 
                     
                     
                 
             
                
                
               
               
                
                
                
                
                
                
               
            
           
         
       
       where M is at least one ion-exchangeable cation having a valence of n; E is an element with valence 3+; F is an element with valence 4+; G is an element with valence 2+; H is an element with valence 5+; a is from >0 to 6; b is equal to 1, c is from >0 to 10; d is from 10 to 80; d/c is from 10 to 1500; e is from 0 to 100; a/(b+c) is from >0 to 5; and d/(b+c) is from 10 to 70.