US2022339614A1PendingUtilityA1

Hydrotreating catalyst with a titanium containing carrier and organic additive

57
Assignee: ALBEMARLE EUROPE SRLPriority: Jul 21, 2017Filed: Jun 29, 2022Published: Oct 27, 2022
Est. expiryJul 21, 2037(~11 yrs left)· nominal 20-yr term from priority
Inventors:Jana Juan AlcanizJacob Arie BergwerffKar Ming Au YeungWilhelmus Clemens Jozef Veerman
B01J 21/063B01J 37/0213B01J 37/0009B01J 23/883C10G 45/08B01J 37/0203B01J 37/031B01J 31/0204C10G 45/04B01J 27/19B01J 37/0244B01J 31/38B01J 23/85B01J 37/0207B01J 23/882B01J 23/888C10G 45/06B01J 37/20B01J 37/082B01J 21/06B01J 37/024B01J 37/0205B01J 31/0202B01J 31/04
57
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Claims

Abstract

Disclosed is a catalyst for use in hydrotreating hydrocarbon feedstocks and methods of making the same catalyst. Specifically, a catalyst is disclosed comprises at least one Group VIB metal component, at least one Group VIII metal component, an organic additive resulting in a C-content of the final catalysts of 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 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 (TiO 2 ) 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 Al 2 O 3 precursor to form a porous support material primarily comprising Al 2 O 3 or by impregnating a titanium source onto a porous support material primarily comprising Al 2 O 3 . Special preference is given to alumina and alumina containing up to and no more than 1 wt % of silica, preferably no more than 0.5 wt % based on the total weight of the support (dry base)

Claims

exact text as granted — not AI-modified
1 . A catalyst comprising
 at least one Group VIB metal component,   at least one Group VIII metal component,   at least one organic additive component, and   a titanium-containing carrier component,   
       wherein the titanium content is in the range of about 1 to about 60 wt. %, expressed as an oxide (TiO 2 ) and based on the total weight of the catalyst and wherein the silica content is less than 1.0 wt. % expressed as an oxide (SiO 2 ) and 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 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 silica content is less than 0.5 wt. % expressed as an oxide (SiO 2 ) and based on the total weight of the catalyst. 
     
     
         7 . The catalyst of  claim 1  wherein the organic component is an organic compound selected from the group consisting of organic compounds comprising at least two oxygen atoms and 2-10 carbon atoms and the compounds built up from these compounds. 
     
     
         8 . The catalyst of  claim 7  wherein the organic component is an organic compound selected from the group consisting of at least two oxygen-containing moieties, such as a carboxyl moiety and the compounds built up from these compounds. 
     
     
         9 . The catalyst of  claim 8  wherein the organic component is an organic compound selected from the group consisting of ethylene glycol, propylene glycol, triethylene glycol, propanediol, glycerin, trimethylol ethane, trimethylol propane, diethylene glycol. 
     
     
         10 . The catalyst of  claim 7  wherein the organic component is an organic compounds comprising at least two hydroxyl groups and a H:O ratio of 2:1, e.g., monosaccharides such as glucose, ribose, and compounds built up from these organic compounds. 
     
     
         11 . The catalyst of  claim 1  wherein the organic component is a sulfur-containing component. 
     
     
         12 . The catalyst of  claim 11  wherein the organic component is mercapto carboxylic acid. 
     
     
         13 . The catalyst of  claim 12  wherein the mercapto carboxylic acid is thioglycolic acid, thiolactic acid, thiopropionic acid, mercapto succinic acid or cysteine. 
     
     
         14 . The catalyst of  claim 1  further comprising a phosphorous component in the amount of about 1 to about 8 wt. % expressed as oxide based on the total weight of the catalyst. 
     
     
         15 . The catalyst of  claim 1  wherein the organic additive component is in amount of about 1 to about 30 wt. % C. 
     
     
         16 . The catalyst of  claim 15  wherein the organic additive component is in amount of about 1 to about 20 wt. % C. 
     
     
         17 . The catalyst of  claim 16  wherein the organic additive component is in amount of about 5 to about 15 wt. % C. 
     
     
         18 . 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 an 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 to about 60 wt. %, expressed as an oxide (TiO 2 ) based on the total weight of the catalyst and has less than 1.0 wt. % silica expressed as an oxide (SiO 2 ) and based on the total weight of the catalyst. 
     
     
         19 . 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 an 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 to about 60 wt. %, expressed as an oxide (TiO 2 ) based on the total weight of the catalyst and has less than 1.0 wt. % silica expressed as an oxide (SiO 2 ) and based on the total weight of the catalyst. 
     
     
         20 . The method of  claim 19  wherein the precipitation comprises the steps of (a) simultaneous dosing of sodium aluminate and aluminum sulfate to water at a fixed pH (b) re-slurrying the formed alumina filter cake in water (c) adding to this slurry TiOSO 4  or titanium sulfate at a fixed pH>7 controlled by an alkaline solution. 
     
     
         21 . The method of  claim 19  wherein the aluminum source and the titanium source are mixed in one stream and sodium aluminate are dosed either simultaneously or subsequently to water at a pH>7. 
     
     
         22 . 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 an 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 to about 60 wt. %, expressed as an oxide (TiO 2 ), based on the total weight of the catalyst and has less than 1.0 wt. % silica expressed as an oxide (SiO 2 ) based on the total weight of the catalyst. 
     
     
         23 . The method of  claims 18 ,  19  or  22  wherein the organic additive is an organic compound selected from the group consisting of organic compounds comprising at least two oxygen atoms and 2-10 carbon atoms, and the ethers, esters, acetals, acid chlorides, acid amides, oligomers or polymers thereof and the impregnation is performed in a single step with a solution comprising an organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source. 
     
     
         24 . The method of  claims 18 ,  19  or  22  wherein the organic additive is an organic compound selected from the group consisting of organic compounds comprising at least two oxygen atoms and 2-10 carbon atoms, and the ethers, esters, acetals, acid chlorides, acid amides, oligomers or polymers thereof and the impregnation is 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 an organic additive. 
     
     
         25 . The method of  claims 18 ,  19  or  22  further comprising the titanium source being selected from the group consisting of titanyl sulfate, titanium sulfate, titanium alkoxide, or Titanium(IV)bis(ammonium lactato)dihydroxide. 
     
     
         26 . 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.

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