Hydroprocessing catalyst and hydroprocessing catalyst of making the same

Abstract

The present invention is directed to a hydroprocessing catalyst containing at least one catalyst support, one or more metals, optionally one or more molecular sieves, optionally one or more promoters, wherein deposition of at least one of the metals is achieved in the presence of a modifying agent.

What is claimed is: 
     
         1 . A hydroprocessing catalyst, comprising:
 at least one molecular sieve which is a Y zeolite with a unit cell size of between 24.15 Å and 24.45 Å; and   at least one metal deposited on an amorphous silica-alumina catalyst support containing SiO 2  in an amount of 10 wt. % to 70 wt. % of the dry bulk weight of the carrier as determined by ICP elemental analysis, a BET surface area of between 450 m 2 /g and 550 m 2 /g, a total pore volume of between 0.75 mL/g and 1.05 mL/g, and a mean mesopore diameter of between 70 Å and 130 Å;   wherein deposition of the metal is achieved in the presence of a modifying agent and with the catalyst support after the deposition subjected to drying for a period of time ranging from 1 to 5 hours and at a temperature sufficient to remove impregnation solution solvent but below the decomposition temperature of the modifying agent.   
     
     
         2 . The hydroprocessing catalyst of  claim 1 , wherein the Y zeolite has a silica-to-alumina ratio of greater than 10, a micropore volume of from 0.15 mL/g to 0.27 mL/g, a BET surface area of from 700 m 2 /g to 825 m 2 /g, and a unit cell size of from 24.15 Å to 24.45 Å. 
     
     
         3 . The hydroprocessing catalyst of  claim 1 , wherein Y zeolite has a silica-to-alumina ratio of greater than 10, a micropore volume of from 0.15 mL/g to 0.27 mL/g, a BET surface area of from 700 m 2 /g to 825 m 2 /g, and a unit cell size of from 24.15 Å to 24.35 Å, and a low-acidity, highly dealuminated ultrastable Y zeolite having an Alpha value of less than about 5 and Brønsted acidity of from 1 to 40 micro-mole/g. 
     
     
         4 . The hydroprocessing catalyst of  claim 1 , wherein the modifying agent is selected from the group consisting of compounds represented by structures (1) through (4), and condensated forms thereof: 
       
         
           
           
               
               
           
         
       
       wherein:
 (1) R 1 , R 2  and R 3  are independently selected from the group consisting of hydrogen; hydroxyl; methyl; amine; and linear or branched, substituted or unsubstituted C 1 -C 3  alkyl groups, C 1 -C 3  alkenyl groups, C 1 -C 3  hydroxyalkyl groups, C 1 -C 3  alkoxyalkyl groups, C 1 -C 3  aminoalkyl groups, C 1 -C 3  oxoalkyl groups, C 1 -C 3  carboxyalkyl groups, C 1 -C 3  aminocarboxyalkyl groups and C 1 -C 3  hydroxycarboxyalkyl groups; 
 (2) R 4  through R 10  are independently selected from the group consisting of hydrogen; hydroxyl; and linear or branched, substituted or unsubstituted C 2 -C 3  carboxyalkyl groups; and 
 (3) R 11  is selected from the group consisting of linear or branched, saturated and unsaturated, substituted or unsubstituted C 1 -C 3  alkyl groups, C 1 -C 3  hydroxyalkyl groups, and C 1 -C 3  oxoalkyl groups. 
 
     
     
         5 . The hydroprocessing catalyst of  claim 1 , wherein the modifying agent selected from the group consisting of N,N′-bis(2-aminoethyl)-1,2-ethane-diamine, 2-amino-3-(1H-indol-3-yl)-propanoic acid, benzaldehyde, [[(carboxymethyl)imino]bis(ethylenenitrilo)]-tetra-acetic acid, 1,2-cyclohexanediamine, 2-hydroxybenzoic acid, thiocyanate, thiosulfate, thiourea, pyridine, and quinoline. 
     
     
         6 . The hydroprocessing catalyst of  claim 1 , wherein the at least one metal is selected from the group consisting of elements from Group 6 and Groups 8 through 10 of the Periodic Table. 
     
     
         7 . The hydroprocessing catalyst of  claim 6 , wherein the at least one metal is selected from the group consisting of nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iron (Fe), chromium (Cr), molybdenum (Mo), tungsten (W), and mixtures thereof. 
     
     
         8 . The hydroprocessing catalyst of  claim 6 , wherein the at least one metal is at least one metal selected from Group 6 of the Periodic Table and at least one metal selected from Groups 8 through 10 of the periodic table. 
     
     
         9 . A method for making a hydroprocessing catalyst comprising at least one metal deposited on an amorphous silica-alumina catalyst support containing SiO 2  in an amount of 10 wt. % to 70 wt. % of the dry bulk weight of the carrier as determined by ICP elemental analysis, the hydroprocessing catalyst made by a method comprising the steps of:
 (a) forming an extrudable mass comprising the amorphous silica-alumina catalyst support,   (b) extruding then calcining the mass to form a calcined extrudate,   (c) exposing the calcined extrudate to an impregnation solution comprising the at least one metal and a modifying agent to form an impregnated extrudate, and   (d) drying the impregnated extrudate for a period of time ranging from 1 to 5 hours and at a temperature sufficient to remove impregnation solution solvent but below the decomposition temperature of the modifying agent.   
     
     
         10 . The method of  claim 10 , wherein the amorphous silica-alumina catalyst support has a BET surface area of between 450 m 2 /g and 550 m 2 /g, a total pore volume of between 0.75 mL/g and 1.05 mL/g, and a mean mesopore diameter of between 70 Å and 130 Å 
     
     
         11 . The hydroprocessing catalyst of  claim 10 , further comprising the step of calcining the dried impregnated extrudate at a temperature high enough to remove the modifying agent and impregnation solution solvent and to convert the at least one metal to a metal oxide. 
     
     
         12 . The hydroprocessing catalyst of  claim 10 , wherein the extrudable mass further comprises at least one molecular sieve. 
     
     
         13 . The hydroprocessing catalyst of  claim 12 , wherein the molecular sieve is a Y zeolite with a unit cell size of between 24.15 Å and 24.45 Å. 
     
     
         14 . The hydroprocessing catalyst of  claim 12 , wherein the at least one molecular sieve is a Y zeolite having a silica-to-alumina ratio of greater than 10, a micropore volume of from 0.15 mL/g to 0.27 mL/g, a BET surface area of from 700 m 2 /g to 825 m 2 /g, and a unit cell size of from 24.15 Å to 24.45 Å. 
     
     
         14 . The hydroprocessing catalyst of  claim 10 , wherein the extrudable mass further comprises a Y zeolite having a silica-to-alumina ratio of greater than 10, a micropore volume of from 0.15 mL/g to 0.27 mL/g, a BET surface area of from 700 m 2 /g to 825 m 2 /g, and a unit cell size of from 24.15 Å to 24.35 Å, and a low-acidity, highly dealuminated ultrastable Y zeolite having an Alpha value of less than about 5 and Brønsted acidity of from 1 to 40 micro-mole/g. 
     
     
         15 . The hydroprocessing catalyst of  claim 10 , wherein the modifying agent is selected from the group consisting of compounds represented by structures (1) through (4), an condensated forms thereof: 
       
         
           
           
               
               
           
         
       
       wherein:
 (1) R 1 , R 2  and R 3  are independently selected from the group consisting of hydrogen; hydroxyl; methyl; amine; and linear or branched, substituted or unsubstituted C 1 -C 3  alkyl groups, C 1 -C 3  alkenyl groups, C 1 -C 3  hydroxyalkyl groups, C 1 -C 3  alkoxyalkyl groups, C 1 -C 3  aminoalkyl groups, C 1 -C 3  oxoalkyl groups, C 1 -C 3  carboxyalkyl groups, C 1 -C 3  aminocarboxyalkyl groups and C 1 -C 3  hydroxycarboxyalkyl groups; 
 (2) R 4  through R 10  are independently selected from the group consisting of hydrogen; hydroxyl; and linear or branched, substituted or unsubstituted C 2 -C 3  carboxyalkyl groups; and 
 (3) R 11  is selected from the group consisting of linear or branched, saturated and unsaturated, substituted or unsubstituted C 1 -C 3  alkyl groups, C 1 -C 3  hydroxyalkyl groups, and C 1 -C 3  oxoalkyl groups.