Selective Hydrogenation Catalyst and Methods of Making and Using Same

Abstract

A composition comprising an extruded inorganic support comprising an oxide of a metal or metalloid, and at least one catalytically active metal, wherein the extruded inorganic support has pores, a total pore volume, and a pore size distribution, wherein the pore size distribution displays at least two peaks of pore diameters, each peak having a maximum, wherein a first peak has a first maximum of pore diameters of equal to or greater than about 120 nm and a second peak has a second maximum of pore diameters of less than about 120 nm, and wherein greater than or equal to about 5% of a total pore volume of the extruded inorganic support is contained within the first peak of pore diameters.

What is claimed is: 
     
         1 . A composition comprising:
 an inorganic support comprising an oxide of a metal or metalloid;   a halide; and   at least one catalytically active metal,   wherein the inorganic support has pores, a total pore volume, and a pore size distribution; wherein the pore size distribution displays at least two peaks of pore diameters, each peak having a maximum; wherein a first peak has a first maximum of pore diameters of from greater than 1,000 nm to about 6,000 nm; wherein a second peak has a second maximum of pore diameters of less than about 120 nm; and wherein greater than or equal to about 15% of the total pore volume of the inorganic support is contained within the first peak of pore diameters; and wherein the inorganic support is a sphere.   
     
     
         2 . The composition of  claim 1 , wherein the inorganic support is an extruded inorganic support. 
     
     
         3 . The composition of  claim 1 , wherein the inorganic support is an agglomerated inorganic support. 
     
     
         4 . The composition of  claim 1 , wherein the oxide of a metal or metalloid consists essentially of silica, titania, alumina, or aluminate. 
     
     
         5 . The composition of  claim 1 , wherein the oxide of a metal or metalloid consists essentially of a spinel. 
     
     
         6 . The composition of  claim 1 , having a total pore volume of from about 0.1 cc/g to about 0.6 cc/g as determined by differential mercury intrusion. 
     
     
         7 . The composition of  claim 1 , wherein the first peak is non-Gaussian and has a peak width at half height that is greater than the peak width at half height of the second peak. 
     
     
         8 . The composition of  claim 1 , further comprising a Group 10 metal and a Group 1B metal. 
     
     
         9 . The composition of  claim 1 , wherein the Group 10 metal comprises palladium and the Group 1B metal comprises silver. 
     
     
         10 . The composition of  claim 1 , wherein the halide is chloride. 
     
     
         11 . The composition of  claim 1 , wherein the at least one catalytically active metal comprises palladium and silver; the halide comprises chloride; and the oxide of a metal or metalloid comprises α-alumina. 
     
     
         12 . The composition of  claim 1 , wherein the at least one catalytically active metal comprises palladium and the palladium is present in the composition in an amount of from about 0.005 wt. % to about 2 wt. % based on the total weight of the composition. 
     
     
         13 . The composition of  claim 12  wherein greater than about 90 wt. % of the palladium is concentrated near the periphery of the composition. 
     
     
         14 . The composition of  claim 1 , wherein the inorganic support has a surface area of from about 3 m 2 /g to about 27 m 2 /g. 
     
     
         15 . The composition of  claim 1  wherein the inorganic support is an oil drop shaped inorganic support. 
     
     
         16 . A composition comprising:
 a support formed from a high surface area alumina having a spherical shape; and   at least one catalytically active metal,   wherein the support has pores, a total pore volume, and a pore size distribution; wherein the pore size distribution displays at least two peaks of pore diameters, each peak having a maximum; wherein a first peak has a first maximum of pore diameters of equal to or greater than 1,000 nm to about 6,000 nm; wherein a second peak has a second maximum of pore diameters of less than about 120 nm; and wherein greater than or equal to about 15% of the total pore volume of the support is contained within the first peak of pore diameters.   
     
     
         17 . The composition of  claim 16  wherein the support is agglomerated. 
     
     
         18 . The composition of  claim 16  wherein the support is an oil drop shaped support. 
     
     
         19 . The composition of  claim 16  wherein the support is an extrudate. 
     
     
         20 . The composition of  claim 16  having a surface area of from about 1 m 2 /g to about 35 m 2 /g. 
     
     
         21 . The composition of  claim 16  having a total pore volume of from about 0.1 cc/g to about 0.9 cc/g as determined by differential mercury intrusion. 
     
     
         22 . The composition of  claim 16  wherein the distance between the first maximum of the first peak and the second maximum of the second peak is at least about 400 nm. 
     
     
         23 . The composition of  claim 16  wherein the first peak is non-Gaussian and has a peak width at half height that is greater than the peak width at half height of the second peak. 
     
     
         24 . The composition of  claim 16  further comprising a halide, a Group 10 metal, and a Group 1B metal. 
     
     
         25 . A method of preparing a hydrogenation catalyst comprising:
 shaping a mixture comprising a high surface area alumina, a pore former, and water to form a shaped support, wherein the shaped support comprises a sphere;   drying the shaped support to form a dried support;   calcining the dried support to from a calcined support;   contacting the calcined support with a chlorine-containing compound to form a chlorided support;   reducing the amount of chloride in the chlorided support to form a cleaned support; and   contacting the cleaned support with a Group 10 metal and a Group 1B metal to form a hydrogenation catalyst,   wherein a pore size distribution for the hydrogenation catalyst displays at least two peaks of pore diameters, each peak having a maximum, wherein a first peak has a first maximum of pore diameters that is equal to or greater than 1,000 to about 6,000 nm, wherein a second peak has a second maximum of pore diameters that is less than about 120 nm, and wherein greater than or equal to about 15% of a total pore volume of the hydrogenation catalyst is contained within the first peak of pore diameters.   
     
     
         26 . The method of  claim 25 , wherein the hydrogenation catalyst has a total pore volume of from about 0.1 cc/g to about 0.6 cc/g as determined by differential mercury intrusion. 
     
     
         27 . The method of  claim 25 , wherein the hydrogenation catalyst has a surface area of from about 3 m 2 /g to about 27 m 2 /g. 
     
     
         28 . A spherical particle shape support formed from a high surface area alumina, wherein a pore size distribution for the spherical particle shape support displays at least two peaks of pore diameters, each peak having a maximum; wherein a first peak has a first maximum of pore diameters of equal to or greater than 1,000 nm to about 6,000 nm, wherein a second peak has a second maximum of pore diameters of less than about 120 nm; wherein greater than or equal to about 15% of a total pore volume of the spherical particle shape support is contained within the first peak of pore diameters; and wherein the spherical particle shape support is a sphere or an extrudate. 
     
     
         29 . A method for selectively hydrogenating a highly unsaturated hydrocarbon to a less unsaturated hydrocarbon in an olefin rich hydrocarbon stream comprising introducing into a reactor a hydrocarbon fluid stream comprising a highly unsaturated hydrocarbon in the presence of hydrogen and a catalyst composition under conditions effective to convert the highly unsaturated hydrocarbon to a less unsaturated hydrocarbon,
 wherein at least 50% of the catalyst composition comprises the hydrogenation catalyst produced according to  claim 25 .