Oxidative desulfurization of fuel oil

Abstract

A method for purifying a sulfur-containing fuel oil comprising (a) contacting the fuel oil with a supported exogenous binary catalyst and oxygen at a temperature in a range of from about 25° C. to about 150° C., and at a pressure in a range of from about 1 atmosphere to about 150 atmospheres to provide a first oxidized mixture; and (b) separating at least one oxidized sulfur compound from the first oxidized mixture to a provide a purified fuel oil. In one embodiment, the sulfur-containing fuel oil is deasphalted prior to contacting with the supported exogenous binary catalyst and oxygen.

1 . A method for purifying a sulfur-containing fuel oil, the method comprising:
 (a) contacting the fuel oil with a supported exogenous binary catalyst and oxygen at a temperature in a range of from about 25° C. to about 150° C., and at a pressure in a range of from about 1 atmosphere to about 150 atmospheres to provide a first oxidized mixture; and   (b) separating at least one oxidized sulfur compound from the first oxidized mixture to a provide a purified fuel oil.   
     
     
         2 . The method according to  claim 1 , wherein the sulfur-containing fuel oil comprises less than 5 weight percent sulfur. 
     
     
         3 . The method according to  claim 1 , wherein the sulfur-containing fuel oil comprises less than 3 weight percent sulfur. 
     
     
         4 . The method according to  claim 1 , wherein the supported exogenous binary catalyst comprises a metal oxide solid support selected from the group consisting of alumina, silica, magnesia, titania, ceria, and combinations of at least two of the foregoing. 
     
     
         5 . The method according to  claim 4 , wherein the metal oxide solid support is alumina. 
     
     
         6 . The method according to  claim 1 , wherein the exogenous binary catalyst comprises a first component selected from the group consisting of oxides and salts vanadium, manganese and copper, and combinations thereof, and a second component selected from the group consisting of oxides and salts of cerium, iron, titanium, manganese, cobalt, nickel, copper and combinations thereof. 
     
     
         7 . The method according to  claim 6 , wherein the first component comprises an oxide or a salt of vanadium. 
     
     
         8 . The method according to  claim 6 , wherein the first component comprises an oxide or a salt of manganese. 
     
     
         9 . The method according to  claim 6 , wherein the second component comprises an oxide or a salt of cobalt. 
     
     
         10 . The method according to  claim 6 , wherein the second component comprises an oxide or a salt of copper. 
     
     
         11 . The method according to  claim 1 , wherein the oxygen is provided as a mixture with an inert gas. 
     
     
         12 . The method according to  claim 1 , wherein the oxygen is provided as air. 
     
     
         13 . The method according to  claim 1 , wherein the sulfur-containing fuel oil is deasphalted prior to contacting the sulfur-containing fuel oil with the binary catalyst, hydrogen peroxide and the water-soluble acid by contacting the sulfur-containing fuel with an inert diluent. 
     
     
         14 . The method according to  claim 13 , wherein the inert diluent is selected from the group consisting of liquid saturated hydrocarbons, liquid cyclic hydrocarbons, and mixtures of at least two of the foregoing inert diluents. 
     
     
         15 . The method according to  claim 13 , wherein the inert diluent is selected from the group consisting of propane, butane, petroleum ether, cyclohexane, decalin and mixtures thereof. 
     
     
         16 . The method according to  claim 1 , wherein the separating is carried out using solid-liquid extraction. 
     
     
         17 . The method according to  claim 1 , wherein the separating is carried out using liquid-liquid extraction. 
     
     
         18 . The method according to  claim 1 , wherein the sulfur-containing fuel oil comprises benzothiophene, dibenzothiophene, alkyl substituted benzothiophenes, and alkyl substituted dibenzothiophenes. 
     
     
         19 . The method according to  claim 1 , further comprising a step of recovering the binary catalyst. 
     
     
         20 . A method for purifying a sulfur-containing fuel oil, the method comprising:
 (a) contacting the sulfur-containing fuel oil with a hydrocarbon diluent, an alumina supported exogenous binary catalyst, and oxygen at a temperature in a range of from about 50° C. to about 120° C., and at a pressure in a range of from about 1 atmosphere to about 150 atmospheres to provide a first oxidized mixture;   (b) separating at least one oxidized sulfur compound from the first oxidized mixture; and   (c) recovering the diluent to provide a purified fuel oil.   
     
     
         21 . The method according to  claim 20 , wherein the exogenous binary catalyst comprises a first component selected from the group consisting of oxides and salts vanadium, manganese and copper, and combinations thereof, and a second component selected from the group consisting of oxides and salts of cerium, iron, titanium, manganese, cobalt, nickel, copper and combinations thereof. 
     
     
         22 . The method according to  claim 20 , further comprising a step of recovering the binary catalyst. 
     
     
         23 . A method for purifying a sulfur-containing fuel oil, the method comprising:
 (a) contacting a sulfur-containing fuel oil comprising benzothiophene, dibenzothiophene, alkyl substituted benzothiophenes, and alkyl substituted dibenzothiophenes with petroleum-ether, a supported exogenous binary catalyst, and oxygen at a temperature in a range of from about 50° C. to about 120° C., and at a pressure in a range of from about 1 atmosphere to about 150 atmospheres to provide a first oxidized mixture comprising sulfoxides and sulfones of benzothiophene, dibenzothiophene, alkyl substituted benzothiophenes, and alkyl substituted dibenzothiophenes;   (b) separating at least one oxidized sulfur compound from the first oxidized mixture; and   (c) recovering petroleum-ether to provide a purified fuel oil.   
     
     
         24 . The method according to  claim 23 , wherein the exogenous binary catalyst comprises a first component selected from the group consisting of oxides and salts vanadium, manganese and copper, and combinations thereof, and a second component selected from the group consisting of oxides and salts of cerium, iron, titanium, manganese, cobalt, nickel, copper and combinations thereof. 
     
     
         25 . The method according to  claim 23 , further comprising a step of recovering the binary catalyst.