Preparation of titanosilicate zeolite ts-1

Abstract

A method is disclosed for preparing crystalline titanosilicate zeolite TS-1 from a reaction mixture containing only sufficient water to produce zeolite TS-1. In one embodiment, the reaction mixture is self-supporting and may be shaped if desired. In the method, the reaction mixture is heated at crystallization conditions and in the absence of an added external liquid phase, so that excess liquid need not be removed from the crystallized product.

1 . A method for preparing crystalline titanosilicate zeolite TS-1, said method comprising:
 a. preparing a reaction mixture comprising at least one active source of silica and at least one hydrolysable titanium compound in amounts sufficient to produce zeolite TS-1, at least one quaternary ammonium cation capable of forming crystals of TS-1 and sufficient water to produce zeolite TS-1; with said reaction mixture having a water/silica molar ratio during crystallization of no greater than about 3; and   b. heating said reaction mixture under crystallization conditions and in the absence of an added external liquid phase for sufficient time to form crystals of zeolite TS-1.   
     
     
         2 . The method of  claim 1 , wherein said reaction mixture during crystallization has a water/silica molar ratio between about 0.7 and about 2. 
     
     
         3 . The method of  claim 1 , wherein said reaction mixture has the following molar composition ranges:
 SiO 2 /TiO 2 =25-500   OH − /SiO 2 =0.04-0.30   H 2 O/SiO 2 =0.5-3   Q/SiO 2 =0.04-0.30   where Q is the quaternary ammonium cation.   
     
     
         4 . The method according to  claim 3 , wherein said reaction mixture has the following molar composition ranges:
 SiO 2 /TiO 2 =30-150   OH − /SiO 2 =0.06-0.15   H 2 O/SiO 2 =0.7-2   Q/SiO 2 =0.06-0.15.   
     
     
         5 . The method according to  claim 3 , wherein the quaternary ammonium cation is a tetraalkylammonium cation. 
     
     
         6 . The method according to  claim 5 , wherein the tetraalkylammonium cation is a tetrapropylammonium cation. 
     
     
         7 . A reaction mixture composition capable of forming crystals of titanosilicate zeolite TS-1, said composition comprising at least one active source of silica and at least one active source of titanium oxide in amounts sufficient to produce zeolite TS-1, at least one quaternary ammonium cation capable of forming crystals of TS-1 and sufficient water to produce TS-1, said composition being in the form of a self-supporting, shapeable mass. 
     
     
         8 . A shaped, binderless catalyst comprising essentially all titanosilicate TS-1 and TS-1 precursors. 
     
     
         9 . Crystalline titanosilicate zeolite TS-1 having a crystallite size of less than 0.2 micron. 
     
     
         10 . A process for oxidation of hydrocarbons comprising contacting said hydrocarbon with hydrogen peroxide in the presence of a catalytically effective amount of crystalline, titanosilicate zeolite TS-1 for a time and at a temperature effective to oxidize said hydrocarbon, wherein the catalyst is in the form of a binderless, shaped particle having a cross-sectional diameter between about 1/64 inch and about ½ inch and comprising essentially all TS-1 and TS-1 precursors. 
     
     
         11 . A process for epoxidation of an olefin comprising contacting said olefin with hydrogen peroxide in the presence of a catalytically effective amount of a crystalline, titanosilicate zeolite TS-1 for a time and at a temperature effective to epoxidize said olefin, wherein the catalyst is in the form of a binderless, shaped particle having a cross-sectional diameter between about 1/64 inch and about ½ inch, and comprising essentially all TS-1 and TS-1 precursors. 
     
     
         12 . A process for oxidizing cyclohexane comprising contacting said cyclohexane with hydrogen peroxide in the presence of a catalytically effective amount of a crystalline, titanosilicate zeolite TS-1 for a time and at a temperature effective to oxidize the cyclohexane, wherein the catalyst is in the form of a binderless, shaped particle having a cross-sectional diameter between about 1/64 inch and about ½ inch, and comprising essentially all TS-1 and TS-1 precursors. 
     
     
         13 . The process of  claim 12 , wherein the binderless, shaped particle is in the form of an extrudate, cylinder, sphere, granule, agglomerate, or pill. 
     
     
         14 . The process of  claim 12 , wherein the binderless, shaped particle is an extrudate. 
     
     
         15 . The process of  claim 11 , wherein the binderless, shaped particle is in the form of an extrudate, cylinder, sphere, granule, agglomerate, or pill. 
     
     
         16 . The process of  claim 11 , wherein the binderless, shaped particle is an extrudate. 
     
     
         17 . The process of  claim 10 , wherein the binderless, shaped particle is in the form of an extrudate, cylinder, sphere, granule, agglomerate, or pill. 
     
     
         18 . The process of  claim 10 , wherein the binderless, shaped particle is an extrudate.