Supported Hydrotreating Catalysts Having Enhanced Activity

Abstract

This invention provides supported catalysts comprising a carrier, phosphorus, at least one Group VI metal, at least one Group VIII metal, and a polymer. In the catalyst, the molar ratio of phosphorus to Group VI metal is about 1:1.5 to less than about 1:12, the molar ratio of the Group VI metal to the Group VIII metal is about 1:1 to about 5:1, and the polymer has a carbon backbone and comprises functional groups having at least one heteroatom. Also provided are a process for preparing such supported catalysts, as well as methods for hydrotreating, hydrodenitrogenation, and/or hydrodesulfurization, using supported catalysts.

That which is claimed is: 
     
         1 . A supported catalyst comprising a carrier, phosphorus, at least one Group VIB metal, at least one Group VIII metal, and a polymer, where
 the molar ratio of phosphorus to Group VIB metal is about 1:1.5 to less than about 1:12,   the molar ratio of the Group VIB metal to the Group VIII metal is about 1:1 to about 5:1, and   the polymer has a carbon backbone, comprises functional groups having at least one heteroatom,   
       wherein the polymer is formed by polymerizing a monomer in contact with the carrier, 
       wherein the monomer and carrier are brought together, and wherein the polymer loading is about 1.5 wt % or more, relative to the total weight of the other components in the catalyst. 
     
     
         2 . A catalyst as in  claim 1  wherein said carrier is silica, alumina, silica-alumina, alumina with silica-alumina dispersed therein, alumina-coated silica, or silica-coated alumina, and/or wherein the functional groups of the polymer are carboxylic acid groups. 
     
     
         3 . A catalyst as in  claim 1  wherein the molar ratio of phosphorus to Group VIB metal is about 1:2.5 to less than about 1:12. 
     
     
         4 . A catalyst as in  claim 1  wherein the polymer is polymaleic acid, polyfumaric acid, or polyacrylic acid. 
     
     
         5 . A catalyst as in  claim 1  wherein said Group VIB metal is molybdenum and/or tungsten, and/or wherein said Group VIII metal is nickel and/or cobalt. 
     
     
         6 . A catalyst as in  claim 1  wherein the carrier is about 40 wt % to about 80 wt % of the catalyst, relative to the total weight of the carrier, the Group VI metal or metals and the Group VIII metal or metals, and phosphorus, where the Group VI metal or metals and the Group VIII metal or metals and phosphorus are expressed as their oxides. 
     
     
         7 . A method for hydrotreating, hydrodenitrogenation, and/or hydrodesulfurization, which method comprises contacting a hydrocarbon feed and a catalyst of  claim 1 . 
     
     
         8 . A catalyst as in  claim 1  wherein at least the phosphorus, Group VIB metal, and Group VIII metal are introduced to the carrier in a single impregnation step, and/or wherein the carrier has been calcined and/or extruded prior to contact with the other catalyst components. 
     
     
         9 . A supported catalyst formed by a process comprising
 I) bringing together components in any of the following combinations:
 a-i) a carrier, one or more monomer species, a polar solvent, and optionally an initiator, 
 b-i) a carrier, one or more monomer species, at least one phosphorus compound, at least one Group VIB metal compound, and at least one Group VIII metal compound, and optionally an initiator, or 
 c-i) a carrier and an impregnation solution, forming an impregnated carrier, followed by mixing the impregnated carrier with one or more monomer species and optionally an initiator, 
 to form a monomer-containing mixture, where said monomer species is soluble in the polar solvent and has carbon-carbon unsaturation and at least one functional group comprising at least one heteroatom; and 
   II) polymerizing at least a portion of said monomer species in the monomer-containing mixture to form a polymerized product;   III) when I) does not include at least one phosphorus compound, at least one Group VIB metal compound, and at least one Group VIII metal compound,
 contacting an impregnation solution and the monomer-containing mixture during the polymerizing in II); 
   
       to form the supported catalyst, where the molar ratio of phosphorus to Group VIB metal is about 1:1.5 to less than about 1:12, where the molar ratio of the Group VIB metal to the Group VIII metal is about 1:1 to about 5:1, where said impregnation solution comprises a polar solvent, phosphorus, at least one Group VIB metal, and at least one Group VIII metal, where a polymer is formed during the polymerizing and the polymer has a carbon backbone, and comprises functional groups having at least one heteroatom, and the polymer loading is about 1.5 wt % or more, relative to the total weight of the other components in the catalyst. 
     
     
         10 . A supported catalyst as in  claim 9  wherein said Group VIB metal is molybdenum and/or tungsten, and/or wherein said Group VIII compound is nickel and/or cobalt. 
     
     
         11 . A supported catalyst as in  claim 9  wherein the catalyst has an average particle size of about 0.5 mm to about 5 mm. 
     
     
         12 . A supported catalyst as in  claim 9  wherein the carrier is about 40 wt % to about 80 wt % of the catalyst, relative to the total weight of the carrier, hydrogenation metals, and phosphorus, where the hydrogenation metals and phosphorus are expressed as their oxides. 
     
     
         13 . A method for hydrotreating, hydrodenitrogenation, and/or hydrodesulfurization, which method comprises contacting a hydrocarbon feed and a catalyst of  claim 9 .