Process for effecting ultra-deep HDS of hydrocarbon feedstocks

Abstract

The present invention pertains to a process for reducing the sulfur content of a hydrocarbon feedstock to a value of less than about 200 ppm, comprising optionally subjecting a catalyst comprising a Group VIB metal component, a Group VIII metal component, and an S-containing organic additive to a sulfidation step and/or activation step, and contacting a feedstock with a 95% boiling point of about 450° C. or less with the optionally sulfided and/or activated catalyst under conditions of elevated temperature and pressure to form a product with a sulfur content of less than about 200 ppm, preferably less than about 50 ppm.

1 . A process for reducing the sulfur content of a hydrocarbon feedstock having an initial boiling point of not less than about 100° C. and a 95% boiling point of about 450° C. or less and a sulfur content not greater than about 2 wt. % to a sulfur content of less than about 200 ppm, comprising contacting said feedstock with a catalyst comprising a Group VIB metal component, a Group VIII metal component, and an S-containing organic additive at a temperature from about 200 to about 450° C., a hydrogen partial pressure from about 5 to about 200 bar, a liquid hourly space velocity from about 0.1 to about 10 vol./vol.h and an H 2 /oil ratio from about 50 to about 2000 NI/I.  
     
     
         2 . The process of  claim 1 , wherein the sulfur content of the product is less than about 50 ppm.  
     
     
         3 . The process of  claim 1 , wherein the S-containing organic additive is a mercaptocarboxylic acid represented by the general formula HS—R1—COOR, wherein R1 stands for a divalent hydrocarbon group with 1 to about 10 carbon atoms and R stands for a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a linear or branched alkyl group having 1 to about 10 carbon atoms.  
     
     
         4 . The process of  claim 1 , wherein the sulfur content of the feedstock is between about 150 ppm and about 2 wt. %.  
     
     
         5 . The process of  claim 4 , wherein the sulfur content of the feedstock is between about 0.1 wt. % and about 2 wt. %.  
     
     
         6 . The process of  claim 4 , wherein the sulfur content of the feedstock is between about 150 ppm and about 500 ppm.  
     
     
         7 . The process of  claim 1 , wherein said feedstock is contacted with said catalyst at a temperature from about 280 to about 430° C.  
     
     
         8 . The process of  claim 1 , wherein said hydrogen partial pressure is from about 10 to about 100 bar.  
     
     
         9 . The process of  claim 1 , wherein said hydrogen partial pressure is from about 15 to about 60 bar.  
     
     
         10 . The process of  claim 1 , wherein said liquid hourly space velocity is from about 0.5 to about 4 vol./vol.h.  
     
     
         11 . The process of  claim 1 , wherein said H 2 /oil ratio is from about 80 to about 1000 NI/I.  
     
     
         12 . A process for reducing the sulfur content of a hydrocarbon feedstock having an initial boiling point of not less than about 100° C. and a 95% boiling point of about 450° C. or less and a sulfur content not greater than about 2 wt. % to a sulfur content of less than about 200 ppm, comprising contacting said feedstock with a catalyst at a temperature from about 200 to about 450° C., a hydrogen partial pressure from about 5 to about 200 bar, a liquid hourly space velocity from about 0.1 to about 10 vol./vol.h and an H 2 /oil ratio from about 50 to about 2000 NI/l, said catalyst comprising a Group VIB metal component, a Group VIII metal component, and an S-containing organic additive, said catalyst being subjected to a sulfidation step and/or activation step before contact with said feedstock.  
     
     
         13 . The process of  claim 12 , wherein the sulfur content of the product is less than about 50 ppm.  
     
     
         14 . The process of  claim 12 , wherein the S-containing organic additive is a mercaptocarboxylic acid represented by the general formula HS—R1—COOR, wherein R1 stands for a divalent hydrocarbon group with 1 to about 10 carbon atoms and R stands for a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or a linear or branched alkyl group having 1 to about 10 carbon atoms.  
     
     
         15 . The process of  claim 12 , wherein the sulfur content of the feedstock is between about 150 ppm and about 2 wt. %.  
     
     
         16 . The process of  claim 15 , wherein the sulfur content of the feedstock is between about 0.1 wt. % and about 2 wt. %.  
     
     
         17 . The process of  claim 15 , wherein the sulfur content of the feedstock is between about 150 ppm and about 500 ppm.  
     
     
         18 . The process of  claim 12 , wherein said feedstock is contacted with said catalyst at a temperature from about 280 to about 430° C.  
     
     
         19 . The process of  claim 12 , wherein said hydrogen partial pressure is from about 10 to about 100 bar.  
     
     
         20 . The process of  claim 12 , wherein said hydrogen partial pressure is from about 15 to about 60 bar.  
     
     
         21 . The process of  claim 12 , wherein said liquid hourly space velocity is from about 0.5 to about 4 vol./vol.h.  
     
     
         22 . The process of  claim 12 , wherein said H 2 /oil ratio is from about 80 to about 1000 NI/I.  
     
     
         23 . A two-step process for converting a starting feedstock having an initial boiling point of not less than about 100° C. and a 95% boiling point of about 450° C. or less and having a sulfur content of above about 0.1 wt. % and not greater than about 2 wt. % into a product having a sulfur content of about 200 ppm or less, wherein the process comprises contacting said feedstock with a first catalyst followed by contact with a second catalyst, both catalysts comprising a Group VIB metal component and a Group VIII metal component, with at least said second catalyst additionally comprising an S-containing organic additive, the conditions for said contact with both catalysts being the same or different and comprising a temperature from about 200 to about 450° C., a hydrogen partial pressure from about 5 to about 200 bar, a liquid hourly space velocity from about 0.1 to about 10 vol./vol.h and an H 2 /oil ratio from about 50 to about 2000 NI/I, the effluent from contact with said first catalyst having a sulfur content of less than about 0.1 wt. %, and the product after contact with the second catalyst having a sulfur content of less than about 200 ppm.  
     
     
         24 . The process of  claim 23 , wherein the effluent following contact with said first catalyst is contacted with said second catalyst after fractionation or intermediate phase separation.  
     
     
         25 . The process of  claim 23  wherein the first catalyst comprises molybdenum as Group VIB metal component and cobalt and/or nickel as Group VIII metal component, while the second catalyst comprises molybdenum as Group VIB metal component and nickel as Group VIII metal component.  
     
     
         26 . A two-step process for converting a starting feedstock having an initial boiling point of not less than about 100° C. and a 95% boiling point of about 450° C. or less and having a sulfur content of above about 0.1 wt. % and not greater than about 2 wt. % into a product having a sulfur content of about 200 ppm or less, wherein the process comprises contacting said feedstock with a first catalyst followed by contact with a second catalyst, the conditions for said contact with both catalysts being the same or different and comprising a temperature from about 200 to about 450° C., a hydrogen partial pressure from about 5 to about 200 bar, a liquid hourly space velocity from about 0.1 to about 10 vol./vol.h and an H 2 /oil ratio from about 50 to about 2000 NI/I, the effluent from contact with said first catalyst having a sulfur content of less than about 0.1 wt. %, and the product after contact with the second catalyst having a sulfur content of less than about 200 ppm, both of said catalysts comprising a Group VIB metal component and a Group VIII metal component, with at least said second catalyst additionally comprising an S-containing organic additive, said first catalyst and/or said second catalyst being subjected to a sulfidation step and/or activation step before contact, respectively, with said feedstock or contact with the effluent from contact with said first catalyst.  
     
     
         27 . The process of  claim 26 , wherein the effluent following contact with said first catalyst is contacted with said second catalyst after fractionation or intermediate phase separation.  
     
     
         28 . The process of  claim 26  wherein the first catalyst comprises molybdenum as Group VIB metal component and cobalt and/or nickel as Group VIII metal component, while the second catalyst comprises molybdenum as Group VIB metal component and nickel as Group VIII metal component.