Preparation of molecular sieve ssz-13

Abstract

Disclosed is a method for preparing crystalline zeolite SSZ-13, said method comprising (a) preparing a reaction mixture comprising (1) at least one active source of an oxide of a tetravalent element or mixture of tetravalent elements, (2) optionally at least on active source of an oxide of a trivalent element or mixture of trivalent elements, (3) at least one active source of an alkali metal, (4) seed crystals of zeolite SSZ-13, (5) benzyl trimethylammonium cation in an amount sufficient to form crystals of zeolite SSZ-13, the benzyl trimethylammonium cation being used in the absence of a 1-adamantammonium cation, and (6) an amount of water that is not substantially in excess of the amount required to cause and maintain crystallization of the small pore zeolite; and (b) heating said reaction mixture at crystallization conditions for sufficient time to form crystallized material containing crystals of SSZ-13.

1 . A method for preparing crystalline zeolite SSZ-13, said method comprising:
 a. preparing a reaction mixture comprising (1) at least one active source of an oxide of a tetravalent element or mixture of tetravalent elements, (2) optionally at least one active source of an oxide of a trivalent element or mixture of trivalent elements, (3) at least one active source of an alkali metal, (4) seed crystals capable of forming SSZ-13, (5) benzyl trimethylammonium cation in an amount sufficient to form crystals of zeolite SSZ-13, the benzyl trimethylammonium cation being used in the absence of a 1-adamantammonium cation, and (6) an amount of water that is not substantially in excess of the amount required to cause and maintain crystallization of the SSZ-13; and   b. heating said reaction mixture at crystallization conditions for sufficient time to form crystallized material containing crystals of said SSZ-13.   
     
     
         2 . The method of  claim 1  wherein said reaction mixture during crystallization has a water to (1) molar ratio between about 1 and about 5. 
     
     
         3 . The method of  claim 1  or  claim 2 , wherein the heating said reaction mixture at crystallization conditions is done in the absence of an external liquid phase. 
     
     
         4 . The method of  claim 1  wherein the mole ratio of the oxides in the SSZ-13 formed from (1) and (2) is greater than 12. 
     
     
         5 . The method of  claim 3  wherein the mole ratio of oxides in the SSZ-13 formed from (1) and (2) is 200 or more. 
     
     
         6 . The method of  claim 4  wherein the pore size of the SSZ-13 is less than 5 Angstroms. 
     
     
         7 . The method according to  claim 1  wherein said reaction mixture has the following molar composition ranges: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   YO 2 /W 2 O 3   
                   20-∞  
                 
                     
                   M + /YO 2   
                   0.1-0.4 
                 
                     
                   R/YO 2   
                   0.001-0.4  
                 
                     
                   OH − /YO 2   
                   0.2-0.6 
                 
                     
                   H 2 O/YO 2   
                   1-5 
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
               
            
           
         
         where Y is silicon, germanium or both, W is aluminum, boron, gallium, iron, or a mixture thereof, M +  is an alkali metal ion and R is a benzyl trimethylammonium cation, the benzyl trimethylammonium cation being used in the absence of a 1-adamantammonium cation. 
       
     
     
         8 . A method for preparing shaped crystalline zeolite SSZ-13, said method comprising:
 a. preparing a reaction mixture comprising at least (1) at least one active source of an oxide of a tetravalent element or mixture of tetravalent elements, (2) optionally at least one active source of an oxide of a trivalent element or mixture of trivalent elements, (3) at least one active source of an alkali metal, (4) seed crystals of SSZ-13, (5) a benzyl trimethylammonium cation in an amount sufficient to form crystals of zeolite SSZ-13, the benzyl trimethylammonium cation being used in the absence of a 1-adamantammonium cation, and (6) an amount of water that is not substantially in excess of the amount required to cause and maintain crystallization of the SSZ-13;   b. forming said reaction mixture into shaped particles; and   c. heating said shaped particles at crystallization conditions for sufficient time to form crystals of said SSZ-13 within said shaped particles.   
     
     
         9 . The method of  claim 8  wherein said shaped particles during crystallization have a water to (1) mole ratio between about 1 and about 5. 
     
     
         10 . The method of  claim 8  or  9 , wherein the heating said reaction mixture at crystallization conditions is done in the absence of an external liquid phase. 
     
     
         11 . The method of  claim 8  wherein the mole ratio of the oxides in the SSZ-13 formed from (1) and (2) is greater than 12. 
     
     
         12 . The method of  claim 11  wherein the mole ratio of oxides in the SSZ-13 formed from (1) and (2) is 200 or more. 
     
     
         13 . The method of  claim 8  wherein the pore size of the small pore zeolite is less than 5 Angstroms. 
     
     
         14 . The method according to  claim 8  wherein said reaction mixture has the following molar composition ranges: 
       
         
           
                 
                 
                 
               
                     
                     
                 
                     
                   YO 2 /W 2 O 3   
                   20-∞  
                 
                     
                   M + /YO 2   
                   0.1-0.4 
                 
                     
                   R/YO 2   
                   0.001-0.4  
                 
                     
                   OH − /YO 2   
                   0.2-0.6 
                 
                     
                   H 2 O/YO 2   
                   1-5 
                 
                     
                     
                 
             
                
               
               
                
                
                
                
                
                
               
            
           
         
         where Y is silicon, germanium or both, W is aluminum, boron, gallium, iron, or a mixture thereof, M +  is an alkali metal ion and R is a benzyl trimethylammonium cation, the benzyl trimethylammonium cation being used in the absence of a 1-adamantammonium cation. 
       
     
     
         15 . A molecular sieve having a composition, as synthesized and in the anhydrous state, comprising (1) a tetravalent oxide or mixture of tetravalent oxides, (2) optionally, a trivalent oxide or mixtures of trivalent oxides, and (3) benzyl trimethylammonium cation, wherein the as-synthesized SSZ-13 does not contain a 1-adamantammonium cation. 
     
     
         16 . The molecular sieve of  claim 15 , wherein the tetravalent oxide or mixture of tetravalent oxides is selected from the group consisting of silicon oxide, germanium oxide, and mixtures thereof. 
     
     
         17 . The molecular sieve of  claim 15 , wherein the trivalent oxide or mixtures of trivalent oxides is selected from the group consisting of aluminum oxide, boron oxide, gallium oxide, iron oxide, and mixtures thereof. 
     
     
         18 . The molecular sieve of  claim 15 , wherein the composition is aluminum free. 
     
     
         19 . The molecular sieve of  claim 15 , wherein a mole ratio of oxides (1) and (2) in the composition is greater than 12. 
     
     
         20 . The molecular sieve of  claim 19 , wherein the mole ratio of oxides (1) and (2) is 200 or more.