Method of producing high-strength high surface area catalyst supports

Abstract

A catalyst support having both substantial high strength and high surface area can be produced by heating a shaped mixture of a porous oxide having a surface area of at least 20 m2/g and the precursor of an inorganic binder for the porous oxide. The binders are precursors of alumina, silica, or [titania,] zirconia and are capable of imparting substantial strength to the support at relatively low firing temperatures.

We claim: 
     
       1. A method of producing a monolithic catalyst support having substantial strength and high surface area comprising: (a) Mixing into a substantially homogeneous body (i) a porous oxide having a surface area of at least 20 m 2  /g selected from the group consisting of zeolite, silica, alumina, .Iadd.having a particle size of about 1-100 microns which when calcined provides gamma-alumina or other transition alumina, .Iaddend.spinel, .[.titania,.]. zirconia, and mixtures of these;   (ii) a precursor of a permanent binder for the porous oxide selected from the group consisting of alumina .[.precursors,.]. .Iadd.hydrate, aluminum propoxide, aluminum chlorohydrate, .Iaddend.silica precursors, .[.titania precursors,.]. zirconia .[.precursors,.]. .Iadd.hydrate, zirconium propoxide, .Iaddend.and mixtures of these, .[.said binder precursor having a crystallite size below 200 angstoms;.]. and   (iii) a temporary binder; and     (b) heating the body to a temperature of from 500°-1000° C. to result in substantial strength and substantial surface area and to substantially completely burn off said temporary binder.   
     
     
       2. The method of claim 1 in which the mixing step is performed using 70-97 parts by weight of the porous oxide, 3-30 parts by weight of the permanent binder precursor, and 1-20 parts by weight of a temporary binder. .[.3. The method of claim 2 in which the permanent binder precursor is a suspension of amorphous hydrated titanium oxide in the form of a suspension of titanium hydrate or a suspension of hydrolyzed titanium isopropoxide..]. .[.4. The method of claim 2 in which the porous oxide is titania; the permanent binder precursor is a suspension of hydrolyzed titanium isopropoxide, aluminum chlorohydrate, or a silicone resin; and 
     
     
        the temporary binder is methyl cellulose..]. 5. The method of claim 2 in which the permanent binder precursor is a suspension of amorphous hydrated zirconium oxide in the form of a suspension of zirconium hydrate or a 
     
     
        suspension of hydrolyzed zirconium n-propoxide. 6. The method of claim 2 in which the porous oxide is zirconia, the permanent binder precursor is a suspension of hydrolyzed zirconium n-propoxide, and the temporary binder 
     
     
        is methyl cellulose. 7. The method of claim 2 in which the porous oxide has a surface are of at least 100 m 2  /g and is selected from the 
     
     
        group consisting of alumina, silica, zeolite, and spinels. 8. The method of claim 7 in which the permanent binder precursor is a suspension of hydrated alumina, aluminum chlorhydrate, or a suspension of hydrolyzed 
     
     
        aluminum isopropoxide. 9. The method of claim 8 in which the porous oxide is alumina; the permanent binder precurser is a suspension of hydrated alumina, a suspension of hydrolyzed aluminum isopropoxide, or aluminum 
     
     
        chlorohydrate; and the temporary binder is methyl cellulose. 10. The method of claim 7 in which the porous oxide is a spinel, the permanent binder precursor is a suspension of hydrated alumina, a suspension of hydrolyzed aluminum isopropoxide, or aluminum chlorohydrdate; and the 
     
     
        temporary binder is methyl cellulose. 11. The method of claim 7 in which 
     
     
        the permanent binder precursor is a silicon resin. 12. The method of claim 7 in which the porous oxide is silica; the permanent binder precursor is a silicone resin, a suspension of a hydrated alumina, a suspension of hydrolyzed aluminum isopropoxide, or aluminum chlorohydrate; and the 
     
     
        temporary binder is methyl cellulose. 13. The method of claim 12 in which 
     
     
        the permanent binder precursor is a silicone resin. 14. The method of claim 7 in which the porous oxide is a zeolite; the permanent binder precursor is a silicone resin, a suspension of a hydrated alumina, aluminum chlorohydrate, or a suspension of hydrolyzed aluminum 
     
     
        isopropoxide; and the temporary binder is methyl cellulose. 15. The method of claim .[.4,.]. 6, 9, 10, 12, or 14 which further comprises the step of 
     
     
        forming the mixed body of step (a) into the shape of a honeycomb. 16. A 
     
     
        catalyst support produced according to the method of claim 15. 17. A catalyst support of claim 16 having at least 20 square meters of surface area per gram of weight and a modulus of rupture of at least 500 pounds 
     
     
        per square inch. 18. A catalyst support produced according to the method 
     
     
        of claim 1 or 2. 19. A catalyst support of claim 18 which is in the shape of a honeycomb and which has at least 20 square meters of surface area per gram of weight and a modulus of rupture of at least 500 pounds per square 
     
     
        inch. 20. A monolithic catalyst support having a modulus of rupture of at least 500 psi, comprising 70-97 parts by weight of a high surface area porous oxide phase and 3-30 parts by weight of a permanent binder for the porous oxide phase dispersed throughout wherein (i) the porous oxide phase has a surface area of at least 20 m 2  /g and consists of alumina, silica, zeolite, spinel, zirconia, or mixtures of these; and   (ii) the binder results from heating in situ, at a temperature of 500°-1,000° C., a binder precursor consisting of alumina precursors, silica precursors, zirconia precursors, or mixtures of these,   
     
     
        said binder precursor having a crystallite size below 200 anstroms. 21. A catalyst support of claim 20 in which the porous oxide is a spinel and the 
     
     
        binder results from an alumina precursor. 22. A catalyst support of claim 20 in which the porous oxide is zirconia and the binder results from a 
     
     
        zirconia precursor. 23. A catalyst support of claim 20 in which the porous oxide is alumina having a surface area of at least 100 m 2  /g and in which the binder results from an alumina precursor or a silica precursor. 
     
     
         4. A catalyst support of claim 20 in which the porous oxide is silica having a surface area of at least 100 m 2  /g and in which the binder 
     
     
        results from a silica precursor or an alumina precursor. 25. A catalyst support of claim 20 in which the porous oxide is a zeolite having a surface area of at least 100 m 2  /g and in which the binder results 
     
     
        from a silica precursor or an alumina precursor. 26. A catalyst support of claim 20, 21, 22, 23, 24 or 25 which has a surface area of at least 20 m 2  /g and in which the binder has a crystallite size of no greater 
     
     
        than about 2,000 angstroms. 27. A monolithic catalyst support having a surface area of at least 20 m 2  /g and a modulus of rupture of at least 500 psi, comprising 70-97 parts by weight of a high surface area porous oxide phase and 3-30 parts by weight of a permanent binder for the porous oxide phase dispersed throughout wherein (i) the porous oxide phase consists of alumina, silica, zeolite, spinel, zirconia, or a mixture or these; and (ii) the binder is alumina, silica, zirconia, or a mixture of these, the binder having a crystalline size of no greater than about 2000 
     
     
        angstroms. 28. A catalyst support of claim 27 in which the porous oxide is 
     
     
        a spinel and in which the binder is alumina. 29. A catalyst support of claim 27 in which the porous oxide is zirconia and the binder is zirconia. 
     
     
        0. A catalyst support of claim 27 in which the porous oxide is alumina, having a surface area of at least 100 m 2  /g, and in which the binder 
     
     
        is alumina, silica, or a mixture of these. 31. A catalyst support of claim 27 in which the porous oxide is silica, having a surface area of at least 100 m 2  /g, and in which the binder is silica, alumina, or a mixture 
     
     
        of these. 32. A catalyst support of claim 28 in which the porous oxide is a zeolite having a surface area of at least 100 m 2  /g, and in which the binder is silica, alumina, or a mixture of these.