Desulfurization and novel compositions for same

Abstract

A composition comprising a metal oxide, a silica-containing material, a gallium-containing material, an aluminum-containing material, and a promoter, wherein at least a portion of the promoter is present as a reduced-valence promoter and methods of preparing such composition are disclosed. The thus-obtained composition is employed in a desulfurization zone to remove sulfur from a hydrocarbon stream.

1 . A composition comprising: 
 (a) a metal oxide;    (b) a silica-containing material;    (c) a gallium-containing material;    (d) an aluminum-containing material selected from the group consisting of alumina, aluminate, and combinations thereof; and    (e) a promoter metal    wherein at least a portion of said promoter metal is present as a reduced valence promoter metal.    
   
   
       2 . A composition in accordance with  claim 1  wherein said promoter metal is present in an amount, which will effect the removal of sulfur from a hydrocarbon stream when contacted with said composition under desulfurization conditions.  
   
   
       3 . A composition in accordance with  claim 1  wherein said promoter metal comprises a metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium, and combinations of any two or more thereof.  
   
   
       4 . A composition in accordance with  claim 1  wherein said metal oxide is present in an amount in the range of from about 10 to about 90 weight percent.  
   
   
       5 . A composition in accordance with  claim 1  wherein said metal oxide is present in an amount in the range of from about 30 to about 80 weight percent.  
   
   
       6 . A composition in accordance with  claim 1  wherein said metal oxide is present in an amount in the range of from 40 to 70 weight percent.  
   
   
       7 . A composition in accordance with  claim 1  wherein said promoter metal is present in an amount in the range of from about 1 to about 60 weight percent.  
   
   
       8 . A composition in accordance with  claim 1  wherein said promoter metal is present in an amount in the range of from about 5 to about 40 weight percent.  
   
   
       9 . A composition in accordance with  claim 1  wherein said promoter metal is present in an amount in the range of from 8 to 20 weight percent.  
   
   
       10 . A composition in accordance with  claim 1  wherein said silica-containing material is present in an amount in the range of from about 10 to about 40 weight percent and said aluminum-containing material is present in an amount in the range of from about 1 to about 30 weight percent.  
   
   
       11 . A composition in accordance with  claim 1  wherein said silica-containing material is present in an amount in the range of from about 12 to about 35 weight percent and said aluminum-containing material is present in an amount in the range of from about 5 to about 25 weight percent.  
   
   
       12 . A composition in accordance with  claim 1  wherein said silica-containing material is present in an amount in the range of from 15 to 30 weight percent and said aluminum-containing material is present in an amount in the range of from 10 to 22 weight percent.  
   
   
       13 . A composition in accordance with  claim 1  wherein said gallium-containing material is present in an amount in the range of from about 0.05 to about 30 weight percent based on the total weight of said composition.  
   
   
       14 . A composition in accordance with  claim 1  wherein said gallium-containing material is present in an amount in the range of from about 1 to about 20 weight percent based on the total weight of said composition.  
   
   
       15 . A composition in accordance with  claim 1  wherein said gallium-containing material is present in an amount in the range of from 5 to 10 weight percent based on the total weight of said composition.  
   
   
       16 . A composition in accordance with  claim 1  wherein said metal oxide comprises a metal selected from the group consisting of zinc, manganese, silver, copper, cerium, scandium, lanthanum, iron, tin, cadmium, gallium, indium, niobium, tantalum, and combinations of any two or more thereof.  
   
   
       17 . A composition in accordance with  claim 16  wherein said metal is zinc.  
   
   
       18 . A composition in accordance with  claim 1  wherein said promoter metal comprises nickel.  
   
   
       19 . A composition in accordance with  claim 1  wherein said silica-containing material is present in the form of expanded perlite.  
   
   
       20 . A composition in accordance with  claim 19  wherein said expanded perlite is milled.  
   
   
       21 . A composition in accordance with  claim 1  wherein said composition is a particulate in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres.  
   
   
       22 . A composition in accordance with  claim 21  wherein said particulate is a microsphere.  
   
   
       23 . A method for the production of a composition comprising: 
 (a) a step selected from the group consisting of: 
 (1) incorporating a gallium-containing substance into or onto a first calcined mixture, said first calcined mixture comprising a liquid, a metal-containing compound, a silica-containing material, alumina, and a promoter metal, to form a first incorporated mixture; and  
 (2) incorporating a gallium-containing substance and a promoter metal simultaneously into or onto a second calcined mixture comprising a liquid, a metal-containing compound, silica-containing material, and alumina, to form a second incorporated mixture;  
   (b) drying said first incorporated mixture or said second incorporated mixture to form a dried incorporated mixture;    (c) calcining said dried incorporated mixture to form a calcined incorporated mixture;    (d) reducing said calcined incorporated mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein, and    (e) recovering said composition.    
   
   
       24 . A method in accordance with  claim 23  wherein said first calcined mixture is formed by: 
 (a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a silica-containing material, 4) alumina, and 5) a promoter metal to form a mixture thereof;    (b) drying said mixture to form a dried mixture; and    (c) calcining said dried mixture to form said first calcined mixture.    
   
   
       25 . A method in accordance with  claim 23  wherein said first calcined mixture is formed by: 
 (a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a silica-containing material, and 4) alumina to form a mixture thereof;    (b) drying said mixture to form a preliminary dried mixture;    (c) calcining said preliminary dried mixture to form a preliminary calcined mixture;    (d) incorporating a promoter metal into or onto said preliminary calcined mixture to form a promoted mixture;    (e) drying said promoted mixture to form a dried mixture; and    (f) calcining said dried mixture to form said first calcined mixture.    
   
   
       26 . A method in accordance with  claim 23  wherein said second calcined mixture is formed by: 
 (a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a silica-containing material, and 4) alumina to form a mixture thereof;    (b) drying said mixture to form a dried mixture;    (c) calcining said dried mixture to form said second calcined mixture.    
   
   
       27 . A method in accordance with  claim 24  wherein said mixture from step (a) is in the form of one of a wet mix, dough, paste, or slurry.  
   
   
       28 . A method in accordance with  claim 25  wherein said mixture from step (a) is in the form of one of a wet mix, dough, paste, or slurry.  
   
   
       29 . A method in accordance with  claim 26  wherein said mixture from step (a) is in the form of one of a wet mix, dough, paste, or slurry.  
   
   
       30 . A method in accordance with  claim 23  wherein said calcined incorporated mixture is reduced in step (d) such that said composition will effect the removal of sulfur from a stream of hydrocarbons when such stream is contacted with same under desulfurization conditions.  
   
   
       31 . A method in accordance with  claim 23  wherein said promoter metal comprises a metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium, and combinations of any two or more thereof.  
   
   
       32 . A method in accordance with  claim 23  wherein said metal-containing compound comprises a metal selected from the group consisting of zinc, manganese, silver, copper, cerium, scandium, lanthanum, iron, tin, cadmium, gallium, indium, niobium, tantalum, and combinations of any two or more thereof.  
   
   
       33 . A method in accordance with  claim 23  wherein said silica-containing material is in the form of expanded perlite.  
   
   
       34 . A method in accordance with  claim 23  wherein said mixture from step (a) is particulated.  
   
   
       35 . A method in accordance with  claim 23  wherein said mixture from step (a) is particulated in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres prior to said drying in step (b).  
   
   
       36 . A method in accordance with  claim 23  wherein said incorporated mixture from step (b) is particulated by spray drying in step (c) so as to form said dried incorporated mixture.  
   
   
       37 . A method in accordance with  claim 23  wherein said first or second incorporated mixture is dried in step (b) at a temperature in the range of from about 65.5° C. to about 550° C.  
   
   
       38 . A method in accordance with  claim 23  wherein said dried incorporated mixture is calcined in step (c) at a temperature in the range of from about 204.4° C. to about 815.5° C.  
   
   
       39 . A method in accordance with  claim 23  wherein said composition recovered in step (f) comprises: 
 (a) a metal oxide;    (b) said silica-containing material;    (c) an aluminum-containing material selected from the group consisting of alumina, aluminate, and combinations thereof;    (d) a gallium-containing material; and    (e) a promoter metal    wherein at least a portion of said promoter metal is present as a reduced valence promoter metal.    
   
   
       40 . A method in accordance with  claim 39  wherein said metal oxide is present in an amount in the range of from about 10 to about 90 weight percent.  
   
   
       41 . A method in accordance with  claim 39  wherein said metal oxide is present in an amount in the range of from about 30 to about 80 weight percent.  
   
   
       42 . A method in accordance with  claim 39  wherein said metal oxide is present in an amount in the range of from 40 to 70 weight percent.  
   
   
       43 . A method in accordance with  claim 39  wherein said promoter metal is present in an amount in the range of from about 1 to about 60 weight percent.  
   
   
       44 . A method in accordance with  claim 39  wherein said promoter metal is present in an amount in the range of from about 5 to about 40 weight percent.  
   
   
       45 . A method in accordance with  claim 39  wherein said promoter metal is present in an amount in the range of from 8 to 20 weight percent.  
   
   
       46 . A method in accordance with  claim 39  wherein said silica-containing material is present in an amount in the range of from about 10 to about 40 weight percent and said aluminum-containing material is present in an amount in the range of from about 1 to about 30 weight percent.  
   
   
       47 . A method in accordance with  claim 39  wherein said silica-containing material is present in an amount in the range of from about 12 to about 35 weight percent and said aluminum-containing material is present in an amount in the range of from about 5 to about 25 weight percent.  
   
   
       48 . A method in accordance with  claim 39  wherein said silica-containing material is present in an amount in the range of from 15 to 30 weight percent and said aluminum-containing material is present in an amount in the range of from 10 to 22 weight percent.  
   
   
       49 . A method in accordance with  claim 39  wherein said gallium-containing material is present in an amount in the range of from about 0.05 to about 30 weight percent based on the total weight of said composition.  
   
   
       50 . A method in accordance with  claim 39  wherein said gallium-containing material is present in an amount in the range of from about 1 to about 20 weight percent based on the total weight of said composition.  
   
   
       51 . A method in accordance with  claim 39  wherein said gallium-containing material is present in an amount in the range of from 5 to 10 weight percent based on the total weight of said composition.  
   
   
       52 . A method in accordance with  claim 39  wherein said metal oxide comprises a metal selected from the group consisting of zinc, manganese, silver, copper, cerium, scandium, lanthanum, iron, tin, cadmium, gallium, indium, niobium, tantalum, and combinations of any two or more thereof.  
   
   
       53 . A method in accordance with  claim 52  wherein said metal is zinc.  
   
   
       54 . A method in accordance with  claim 39  wherein said promoter metal comprises a metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium, and combinations of any two or more thereof.  
   
   
       55 . A method in accordance with  claim 39  wherein said promoter metal is comprised of nickel.  
   
   
       56 . A method in accordance with  claim 23  wherein said calcined incorporated mixture is reduced in step (g) at a temperature in the range of from about 37.8° C. to about 815.5° C. and at a pressure in the range of from about 15 to about 1500 psia and for a time sufficient to permit the formation of a reduced valence promoter metal.  
   
   
       57 . A method in accordance with  claim 23  wherein during said calcining of step (c) at least a portion of said alumina is converted to aluminate.  
   
   
       58 . A composition prepared by the method of  claim 23 .  
   
   
       59 . A composition prepared by the method of  claim 24 .  
   
   
       60 . A composition prepared by the method of  claim 25 .  
   
   
       61 . A composition prepared by the method of  claim 26 .  
   
   
       62 . A composition prepared by the method of  claim 39   
   
   
       63 . A composition prepared by the method of  claim 40 .  
   
   
       64 . A composition prepared by the method of  claim 43 .  
   
   
       65 . A composition prepared by the method of  claim 46 .  
   
   
       66 . A composition prepared by the method of  claim 49 .  
   
   
       67 . (canceled)  
   
   
       68 . (canceled)  
   
   
       69 . (canceled)  
   
   
       70 . (canceled)  
   
   
       71 . (canceled)  
   
   
       72 . (canceled)  
   
   
       73 . (canceled)  
   
   
       74 . (canceled)  
   
   
       75 . The cracked-gasoline product of the process of  claim 68 .  
   
   
       76 . The diesel fuel product of the process of  claim 68.