Hydrotreating catalyst with a titanium containing carrier and sulfur containing organic additive

Abstract

Generally, it is disclosed a catalyst for use in a hydrotreating hydrocarbon feedstocks and the method of making such catalyst. It is generically provided that the catalyst comprises at least one Group VIB metal component, at least one Group VIII metal component, about 1 to about 30 wt % C, and preferably about 1 to about 20 wt % C, and more preferably about 5 to about 15 wt % C of one or more sulfur containing organic additive and a titanium-containing carrier component, wherein the amount of the titanium component is in the range of about 3 to about 60 wt %, expressed as an oxide (TiO2) and based on the total weight of the catalyst. The titanium-containing carrier is formed by co-extruding or precipitating a titanium source with a Al2O3 precursor to form a porous support material comprising Al2O3 or by impregnating a titanium source onto a porous support material comprising Al2O3.

1 . A catalyst comprising
 at least one Group VIB metal component,   at least one Group VIII metal component,   at least one sulfur containing organic additive component, and   a titanium-containing carrier component,   wherein the amount of titanium content is in the range of about 1 to about 60 wt %, expressed as an oxide (TiO 2 ), based on the total weight of the catalyst.   
     
     
         2 . The catalyst of  claim 1  wherein the Group VIB metal component is in an amount of about 15 to about 30 wt % expressed as an oxide based on the total weight of the catalyst. 
     
     
         3 . The catalyst of  claim 1  wherein the Group VIII metal component is in an amount of about 2 to about 8 wt % expressed as an oxide based on the total weight of the catalyst. 
     
     
         4 . The catalyst according to  claim 1  wherein the Group VIB metal component comprises molybdenum and/or tungsten. 
     
     
         5 . The catalyst according to  claim 1  wherein the Group VIII metal component comprises nickel and/or cobalt. 
     
     
         6 . The catalyst of  claim 1  wherein the at least one sulfur containing organic component comprises a mercapto carboxylic acid. 
     
     
         7 . The catalyst of  claim 6  wherein the mercapto carboxylic acid is thioglycolic acid, thiolactic acid, thiopropionic acid, mercapto succinic acid or cysteine. 
     
     
         8 . The catalyst of  claim 1  further comprising a phosphorous component in the amount of about 1 to about 8% expressed as oxide based on the total weight of the catalyst. 
     
     
         9 . The catalyst of  claim 1  wherein the at least one sulfur containing organic additive component is in amount of about 1 to about 30 wt % C. 
     
     
         10 . The catalyst of  claim 9  wherein the at least one sulfur containing organic additive component is in amount of about 1 to about 20 wt % C. 
     
     
         11 . The catalyst of  claim 10  wherein the at least one sulfur containing organic additive component is in amount of about 5 to about 15 wt % C. 
     
     
         12 . A method of producing a catalyst, the method comprising
 co-extruding a titanium source with a porous material comprising Al 2 O 3  to form a titanium-containing carrier extrudate,   drying and calcining the extrudate, and   impregnating the calcined extrudate with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source,   the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO 2 ), based on the total weight of the catalyst.   
     
     
         13 . A method of producing a catalyst, the method comprising
 precipitating a titanium source with an aluminum source,   extruding the precipitate to form a titanium-containing carrier extrudate,   drying and calcining the extrudate, and   impregnating the calcined extrudate with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source,   the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO 2 ), based on the total weight of the catalyst.   
     
     
         14 . The method of  claim 13  wherein the precipitation comprises the steps of (a) simultaneous dosing of sodium aluminate and aluminum sulfate to water at a fixed pH (b) the formed alumina filter cake is re-slurried in water (c) to this slurry TiOSO 4  or titanium sulfate is added at a fixed pH>7 controlled by an alkaline solution. 
     
     
         15 . The method of  claim 13  wherein the aluminum source and the titanium source are mixed in one stream and sodium aluminate is dosed either simultaneously or subsequently to water at a pH>7. 
     
     
         16 . A method of producing a catalyst, the method comprising
 impregnating a porous material comprising Al 2 O 3  with a titanium source to form a titanium-containing carrier,   drying and calcining the carrier, and   impregnating the calcined carrier with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source,   the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO 2 ), based on the total weight of the catalyst.   
     
     
         17 . The method of  claim 12 ,  13  or  16  further comprising the impregnation with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source being performed in a single step with a solution comprising a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source. 
     
     
         18 . The method of  claim 12 ,  13  or  16  further comprising the impregnation with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source being performed in more than one step, wherein the carrier is impregnated with a solution comprising at least one Group VIB metal source and/or at least one Group VIII metal source, followed by a step of impregnating the carrier with a solution comprising a sulfur containing organic additive. 
     
     
         19 . The method of  claim 12 ,  13  or  16  wherein the titanium source is selected from the group consisting of titanyl sulfate, titanium sulfate, titanium alkoxide or Titanium(IV)bis(ammonium lactato)dihydroxide. 
     
     
         20 . A method which comprises contacting a hydrocarbon feed with a catalyst according to any of the preceding claims, under hydrotreating conditions so as to hydrotreat the hydrocarbon feed.