Two-stage hpc process

Abstract

The present invention pertains to a method for hydroprocessing a heavy hydrocarbon oil, comprising bringing a heavy hydrocarbon oil in a first stage into contact with hydroprocessing catalyst I in the presence of hydrogen, after which the effluent of the first stage is contacted in whole or in part with hydroprocessing catalyst II in the presence of hydrogen. The method of the invention combines efficient contaminant removal with high residue conversion and low sediment formation. The invention also comprises a combination of catalysts for use in the above method.

1 . A method for hydroprocessing a heavy hydrocarbon oil, comprising bringing a heavy hydrocarbon oil in a first stage into contact with hydroprocessing catalyst I in the presence of hydrogen, after which the effluent of the first stage is contacted in whole or in part with hydroprocessing catalyst II in the presence of hydrogen, wherein catalyst I comprises 7 to 20 wt. % of a Group VIB metal component, calculated as trioxide on the weight of the catalyst, and 0.5 to 6 wt. % of a Group VIII metal component, calculated as oxide on the weight of the catalyst, on a porous inorganic carrier, said catalyst having a specific surface area of at least 100 m 2 /g, a total pore volume of at least 0.55 ml/g, at least 50% of the total pore volume in pores with a diameter of at least 20 nm (200 Å) and at least 65% of the total pore volume in pores with a diameter of 10-120 nm (100-1200 Å), and catalyst II comprises 7 to 20 wt. % of a Group VIB metal component, calculated as trioxide on the weight of the catalyst, and 0.5 to 6 wt. % of a Group VIII metal component, calculated as oxide on the weight of the catalyst, on a porous inorganic carrier, said catalyst having a specific surface area of at least 100 m 2 /g, a total pore volume of at least 0.55 ml/g, 30-80% of the pore volume in pores with a diameter of 10-20 nm (100-200 Å), and at least 5% of the pore volume in pores with a diameter of at least 100 nm (1000 Å) with catalyst I having a larger percentage of its pore volume in pores with a diameter of at least 20 nm (200 Å) than catalyst II.  
     
     
         2 . The method of  claim 1  wherein catalyst I has less than 25% of its pore volume in pores with a diameter of less than 10 nm (100 Å).  
     
     
         3 . The method of  claim 1  wherein the carrier of catalyst I consists essentially of alumina.  
     
     
         4 . The method of  claim 1  wherein catalyst II has less than 50% of its pore volume in pores with a diameter of at least 20 nm (200 Å).  
     
     
         5 . The method of  claim 1  wherein the carrier of catalyst II consists essentially of alumina and at least 3.5 wt. % of silica.  
     
     
         6 . The method of  claim 1  wherein catalyst II comprises 0.1-2 wt. % of a Group IA metal component.  
     
     
         7 . The method of  claim 1  wherein the heavy hydrocarbon feed is a feed of which at least 50 wt. % boils above 538° C. (1000° F.) and which comprises at least 2 wt. % of sulfur and at least 5 wt. % of Conradson carbon.  
     
     
         8 . The method of  claim 1  wherein at least one of the stages is carried out in an ebullating bed.  
     
     
         9 . A combination of catalysts comprising a 
 catalyst I that comprises 7 to 20 wt. % of a Group VIB metal component, calculated as trioxide on the weight of the catalyst, and 0.5 to 6 wt. % of a Group VIII metal component, calculated as oxide on the weight of the catalyst, on a porous inorganic carrier, said catalyst having a specific surface area of at least 100 m 2 /g, a total pore volume of at least 0.55 ml/g, at least 50% of the total pore volume in pores with a diameter of at least 20 nm (200 Å) and at least 65% of the total pore volume in pores with a diameter of 10-120 nm (100-1200 Å), and a    catalyst II that comprises 7 to 20 wt. % of a Group VIB metal component, calculated as trioxide on the weight of the catalyst, and 0.5 to    6 wt. % of a Group VIII metal component, calculated as oxide on the weight of the catalyst, on a porous inorganic carrier, said catalyst having a specific surface area of at least 100 m 2 /g, a total pore volume of at least 0.55 ml/g, 30-80% of the pore volume in pores with a diameter of 10-20 nm (100-200 Å), and at least 5% of the pore volume in pores with a diameter above 100 nm (1000 Å), with catalyst I having a larger percentage of its pore volume in pores with a diameter of at least 20 nm (200 Å) than catalyst II.    
     
     
         10 . The catalyst combination of  claim 9  wherein catalyst I has less than 25% of its pore volume in pores with a diameter of less than 10 nm (100 Å).  
     
     
         11 . The catalyst combination of  claim 9  wherein the carrier of catalyst I consists essentially of alumina.  
     
     
         12 . The catalyst combination of  claim 9  wherein catalyst II has less than 50% of its pore volume in pores with a diameter above 200 Å.  
     
     
         13 . The catalyst combination of  claim 9  wherein the carrier of catalyst II consists essentially of alumina and at least 3.5 wt. % of silica.  
     
     
         14 . The catalyst combination of  claim 9  wherein catalyst II comprises 0.1-2 wt. % of a Group IA metal component.