Desulfurization and novel process for same

Abstract

A composition comprising a metal oxide 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 method for the production of a composition comprising: 
 (a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a silica-containing material, and 4) a promoter so as to form a mixture thereof;    (b) adding alumina to said mixture to form an alumina-containing mixture;    (c) drying said alumina-containing mixture to form a dried mixture;    (d) calcining said dried mixture to form a calcined mixture;    (e) reducing said calcined mixture with a reducing agent under reducing conditions to produce a composition having a reduced valence promoter content therein, and    (f) recovering said composition.    
     
     
         2 . A method in accordance with  claim 1  wherein said calcined 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.  
     
     
         3 . A method in accordance with  claim 1  wherein said metal-containing compound comprises a metal selected from the group consisting of zinc manganese, silver, copper, cadmium, tin, lanthanum, scandium, cerium, tungsten, molybdenum, iron, mobium, tantalium, gallium, indium, and combinations of any two or more thereof.  
     
     
         4 . A method in accordance with  claim 1  wherein said promoter is selected from the group consisting of at least one metal, a metal oxide, a metal oxide precursor, a solid solution of more than one metal, an alloy of more than one metal, and combinations of any two or more thereof.  
     
     
         5 . A method in accordance with  claim 1  wherein said promoter 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.  
     
     
         6 . A method in accordance with  claim 3  wherein said promoter comprises nickel.  
     
     
         7 . A method in accordance with  claim 1  wherein said promoter comprises nickel nitrate.  
     
     
         8 . A method in accordance with  claim 1  wherein said promoter comprises nickel hydroxide.  
     
     
         9 . A method in accordance with  claim 1  wherein an attrition-resistance enhancing component is admixed with said liquid, said metal-containing compound, said silica-containing material, and said promoter so as to form said mixture of step (a).  
     
     
         10 . A method in accordance with  claim 9  wherein said attrition-resistance enhancing component is selected from the group consisting of bentonite, sodium bentonite, acid-washed bentonite, atapulgite, china clay, kaolinite, montmorillonite, illite, halloysite, hectorite, sepiolite, and combinations of any two or more thereof.  
     
     
         11 . A method in accordance with  claim 1  wherein said silica-containing material is in the form of crushed expanded perlite.  
     
     
         12 . A method in accordance with  claim 1  wherein said mixture from step (a) is in the form of one of a wet mix, dough, paste, or slurry.  
     
     
         13 . A method in accordance with  claim 6  wherein said mixture from step (a) is in the form of a slurry.  
     
     
         14 . A method in accordance with  claim 1  wherein said alumina-containing mixture from step (b) is particulated prior to said drying in step (c).  
     
     
         15 . A method in accordance with  claim 1  wherein said alumina-containing mixture from step (b) is particulated in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres prior to said drying in step (c).  
     
     
         16 . A method in accordance with  claim 1  wherein said alumina-containing mixture from step (b) is particulated by spray drying in step (c) so as to form said dried mixture.  
     
     
         17 . A method in accordance with  claim 1  wherein said alumina-containing mixture is dried in step (c) at a temperature in the range of from about 65.5° C. to about 550° C.  
     
     
         18 . A method in accordance with  claim 1  wherein said dried mixture is calcined in step (c) at a temperature in the range of from about 204.4° C. to about 815.5° C.  
     
     
         19 . A method in accordance with  claim 1  wherein said calcined mixture is reduced in step (d) 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.  
     
     
         20 . A method in accordance with  claim 1  wherein during said calcining of step (c) at least a portion of said alumina is converted to an aluminate.  
     
     
         21 . A composition produced by the method of  claim 1 .  
     
     
         22 . A composition produced by the method of  claim 9 .  
     
     
         23 . A composition produced by the method of  claim 16 .  
     
     
         24 . A method for the production of a composition comprising: 
 (a) admixing: 1) a liquid, 2) a first metal formate, 3) a silica-containing material, 4) alumina, and 5) a second metal formate so as to form a mixture thereof;    (b) drying said mixture so as to form a dried mixture;    (c) calcining said dried mixture so as to form a calcined mixture; and    (d) recovering said composition.    
     
     
         25 . A method in accordance with  claim 24  wherein said calcined incorporated mixture is reduced in step (f) such that said composition of step (g) will effect the removal of sulfur from a stream of hydrocarbons when such stream is contacted with same under desulfurization conditions.  
     
     
         26 . A method in accordance with  claim 24  wherein said liquid is ammonia.  
     
     
         27 . A method in accordance with  claim 24  wherein said first metal formate comprises a metal selected from the group consisting of zinc, manganese, silver, copper, cadmium, tin, lanthanum, scandium, cerium, tungsten, molybdenum, iron, niobium, tantalum, gallium, indium, and combinations of any two or more thereof.  
     
     
         28 . A method in accordance with  claim 24  wherein said first metal formate is zinc formate.  
     
     
         29 . A method in accordance with  claim 24  wherein said second metal formate 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.  
     
     
         30 . A method in accordance with  claim 24  wherein said second metal formate is nickel formate.  
     
     
         31 . A method in accordance with  claim 24  wherein said silica-containing material is present in the form of crushed expanded perlite.  
     
     
         32 . 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.  
     
     
         33 . A method in accordance with  claim 32  wherein said mixture from step (a) is in the form of a slurry.  
     
     
         34 . A method in accordance with  claim 24  wherein said mixture from step (a) is particulated prior to drying in step (b).  
     
     
         35 . A method in accordance with  claim 24  wherein said mixture from step (a) is particulated in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres.  
     
     
         36 . A method in accordance with  claim 24  wherein said mixture from step (a) is particulated by spray drying in step (b) so as to form said dried mixture.  
     
     
         37 . A method in accordance with  claim 24  wherein said mixture and said incorporated mixture are each dried in steps (b) and (e), respectively, at a temperature in the range of from about 65.5° C. to about 550° C.  
     
     
         38 . A method in accordance with  claim 24  wherein said dried incorporated mixture is calcined in step (e) at a temperature in the range of from about 204.4° C. to about 815.5° C.  
     
     
         39 . A method in accordance with  claim 24  wherein the reduction of said calcined incorporated mixture in step (g) is carried out at a temperature in the range of from about 37.4° 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.  
     
     
         40 . A method in accordance with  claim 24  wherein during said calcining in step (c) at least a portion of said alumina is converted to an aluminate.  
     
     
         41 . A composition produced by the process of  claim 24 .  
     
     
         42 . A composition produced by the process of  claim 26 .  
     
     
         43 . A process for the removal of sulfur from a hydrocarbon stream comprising: 
 (a) contacting said hydrocarbon stream with a composition produced by the process of  claim 1  in a desulfurization zone under conditions such that there is formed a at least partially desulfurized hydrocarbon stream and a sulfurized composition;    (b) separating said at least partially desulfurized hydrocarbon stream from said sulfurized composition thereby forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition;    (c) regenerating at least a portion of said separated sulfurized composition in a regeneration zone so as to remove at least a portion of the sulfur contained therein and/or thereon thereby forming a regenerated composition;    (d) reducing said regenerated composition in a reduction zone so as to provide a reduced composition having a reduced valence promoter content therein which will effect the removal of sulfur from sulfur-containing hydrocarbons when contacted with same; and thereafter    (e) returning at least a portion of said reduced composition to said desulfurization zone.    
     
     
         44 . A process in accordance with  claim 43  wherein said hydrocarbon stream comprises a fuel selected from the group consisting of cracked-gasoline, diesel fuel, and combinations thereof.  
     
     
         45 . A process in accordance with  claim 43  wherein said desulfurization in step (a) is carried out at a temperature in the range of from about 37.8° C. to about 537.8° C. and a pressure in the range of from about 15 to about 1500 psia for a time sufficient to effect the removal of sulfur from said stream.  
     
     
         46 . A process in accordance with  claim 43  wherein said regeneration in step (c) is carried out at a temperature in the range of from about 37.8° C. to about 815.5° C. and a pressure in the range of from about 10 to about 1500 psia for a time sufficient to effect the removal of at least a portion of the sulfur from said separated sulfurized composition.  
     
     
         47 . A process in accordance with  claim 43  wherein air is employed in step (c) as a regeneration agent in said regeneration zone.  
     
     
         48 . A process in accordance with  claim 43  wherein said regenerated composition from step (c) is subjected to reduction with hydrogen in step (d) in said reduction zone which is maintained 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 period of time sufficient to effect a reduction of the valence of the promoter content of said regenerated composition.  
     
     
         49 . A process in accordance with  claim 43  wherein said separated sulfurized composition from step (b) is stripped prior to introduction into said regeneration zone in step (c).  
     
     
         50 . A process in accordance with  claim 43  wherein said regenerated composition from step (c) is stripped prior to introduction to said reduction zone in step (d).  
     
     
         51 . The cracked-gasoline product of the process of  claim 44 .  
     
     
         52 . The diesel fuel product of the process of  claim 44 .  
     
     
         53 . A process for the removal of sulfur from a hydrocarbon stream comprising: 
 (a) contacting said hydrocarbon stream with a composition produced by the process of  claim 24  in a desulfurization zone under conditions such that there is formed a desulfurized hydrocarbon stream and a sulfurized composition;    (b) separating said desulfurized hydrocarbon stream from said sulfurized composition thereby forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition;    (c) regenerating at least a portion of said separated sulfurized composition in a regeneration zone so as to remove at least a portion of the sulfur contained therein and/or thereon thereby forming a regenerated composition;    (d) reducing said regenerated composition in an activation zone so as to provide a reduced composition having a reduced valence promoter content therein which will effect the removal of sulfur from a hydrocarbon stream when contacted with same; and thereafter    (e) returning at least a portion of said reduced composition to said desulfurization zone.    
     
     
         54 . A process in accordance with  claim 53  wherein said hydrocarbon stream comprises a fuel selected from the group consisting of cracked-gasoline, diesel fuel, and combinations thereof.  
     
     
         55 . A process in accordance with  claim 53  wherein said desulfurization in step (a) is carried out at a temperature in the range of from about 37.8° C. to about 537.8° C. and a pressure in the range of from about 15 to about 1500 psia for a time sufficient to effect the removal of sulfur from said stream.  
     
     
         56 . A process in accordance with  claim 53  wherein said regeneration in step (c) is carried out at a temperature in the range of from about 37.8° C. to about 815.5° C. and a pressure in the range of from about 10 to about 1500 psia for a time sufficient to effect the removal of at least a portion of the sulfur from said separated sulfurized composition.  
     
     
         57 . A process in accordance with  claim 53  wherein air is employed in step (c) as a regeneration agent in said regeneration zone.  
     
     
         58 . A process in accordance with  claim 53  wherein said regenerated composition from step (c) is subjected to reduction with hydrogen in step (d) in said reduction zone which is maintained 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 period of time sufficient to effect a reduction of the valence of the promoter content of said regenerated composition.  
     
     
         59 . A process in accordance with  claim 53  wherein said separated sulfurized composition from step (b) is stripped prior to introduction into said regeneration zone in step (c).  
     
     
         60 . A process in accordance with  claim 53  wherein said regenerated composition from step (c) is stripped prior to introduction to said reduction zone in step (d).  
     
     
         61 . The cracked-gasoline product of the process of  claim 54 .  
     
     
         62 . The diesel fuel product of the process of  claim 54.