System and method for liquid hydrocarbon desulfurization

Abstract

A method of desulfurizing a liquid hydrocarbon having the steps of: adding a liquid hydrocarbon to a vessel, the hydrocarbon having a sulfur content; adding a catalyst and an oxidizer to create a mixture; oxidizing at least some of the sulfur content of the liquid hydrocarbon to form oxidized sulfur in the liquid hydrocarbon; separating the liquid hydrocarbon from the mixture; and removing at least some of the oxidized sulfur from the liquid hydrocarbon. Such methods can be carried out by batch or continuously. Systems for undertaking such methods are likewise disclosed.

What is claimed is: 
     
         1 . A method of desulfurizing a liquid hydrocarbon comprising the steps of:
 (a) adding a liquid hydrocarbon to a first vessel, the hydrocarbon having a first sulfur content;   (b) adding a first catalyst and a first oxidizer to the first vessel create a first mixture;   (c) oxidizing at least some of the sulfur content of the liquid hydrocarbon to form oxidized sulfur in the liquid hydrocarbon within the first vessel;   (d) separating the liquid hydrocarbon and oxidized sulfur from within the first mixture;   (e) directing the liquid hydrocarbon and oxidized sulfur into a second vessel, the hydrocarbon having a second sulfur content that is lower than the first sulfur content;   (f) adding a second catalyst and a second oxidizer to the second vessel to create a second mixture;   (g) oxidizing at least some of the sulfur content of the liquid hydrocarbon to form additional oxidized sulfur in the liquid hydrocarbon within the second vessel;   (h) separating the liquid hydrocarbon and oxidized sulfur from within the second mixture; and   (i) removing the liquid hydrocarbon and oxidized sulfur from within the second vessel, the liquid hydrocarbon having a third sulfur content which is lower than the second sulfur content.   
     
     
         2 . The method of  claim 1  wherein the step of oxidizing at least some of the sulfur content within at least one of the first vessel and the second vessel further comprises at least one of the steps of:
 (a) agitating the first mixture within the first vessel; 
 (b) heating the first mixture within the first vessel; 
 (c) cooling the first mixture within the first vessel; and 
 (d) recirculating the first mixture within the first vessel. 
 
     
     
         3 . The method of  claim 2  wherein the step of agitating the first mixture further comprises the step of directing the first mixture through a shear device. 
     
     
         4 . The method of  claim 1  further comprising the steps of:
 (a) removing the second catalyst and the second oxidizer from the second mixture; 
 (b) adding the removed second catalyst and second oxidizer into the first vessel as the first catalyst and the first oxidizer. 
 
     
     
         5 . The method of  claim 1  further comprising the step of:
 (a) separating the oxidized sulfur from the liquid hydrocarbon and oxidized sulfur. 
 
     
     
         6 . The method of  claim 5  wherein the step of separating further comprises the step of:
 (a) passing the liquid hydrocarbon and oxidized sulfur through one of a solid absorbent and a liquid stripping section. 
 
     
     
         7 . The method of  claim 6  wherein the step of separating further comprises the step of:
 (a) filtering the liquid hydrocarbon and oxidized sulfur prior to the step of passing. 
 
     
     
         8 . The method of  claim 1  wherein the step of separating the liquid hydrocarbon and oxidized sulfur from within the first mixture removes more than 70% of the liquid hydrocarbon within the first mixture, and more preferably more than 90% of the liquid hydrocarbon within the first mixture, and the step of separating the liquid hydrocarbon and the oxidized sulfur from within the second mixture removes more than 70% of the liquid hydrocarbon within the second mixture, and more preferably more than 90% of the liquid hydrocarbon within the second mixture. 
     
     
         9 . The method of  claim 1  wherein at least a portion of the first catalyst and the second catalyst are reused, with only a portion thereof being replaced. 
     
     
         10 . The method of  claim 1  further comprising the steps of:
 (j) directing the liquid hydrocarbon and oxidized sulfur into a third vessel; 
 (k) adding a third catalyst and a third oxidizer to the third vessel to create a third mixture; 
 (l) oxidizing at least some of the sulfur content of the liquid hydrocarbon to form additional oxidized sulfur in the liquid hydrocarbon within the third vessel; and 
 (m) separating the liquid hydrocarbon and oxidized sulfur from within the third mixture; and 
 (n) removing the liquid hydrocarbon and oxidized sulfur from within the third vessel, the liquid hydrocarbon having a fourth sulfur content which is lower than the third sulfur content. 
 
     
     
         11 . The method of  claim 10  wherein the steps (j) through (n) are repeated until a final desired sulfur content is reached. 
     
     
         12 . The method of  claim 11  wherein the steps (j) through (n) are repeated at least once. 
     
     
         13 . The method of  claim 1  wherein the method is operated continuously, so as to continuously desulfurize liquid hydrocarbon. 
     
     
         14 . The method of  claim 13  wherein the liquid hydrocarbon and oxidizer travels sequentially from the first vessel to the second vessel, while at least a portion of the catalyst travels in an opposite direction within the system. 
     
     
         15 . The method of  claim 10  wherein the first catalyst, the second catalyst or the third catalyst comprise a strong catalyst. 
     
     
         16 . The method of  claim 15  wherein the strong catalyst is selected from the group consisting of: acetic acid, trifluoroacetic acid, sulfuric acid, nitric acid, hydrofluoric acid, hydrochloric acids. 
     
     
         17 . The method of  claim 10  wherein the first oxidizer, the second oxidizer or the third oxidizer comprise hydrogen peroxide or co compounds that can produce hydrogen peroxide in aqueous environments, super oxides or organic peroxides. 
     
     
         18 . The method of  claim 10  wherein the first catalyst, the second catalyst or the third catalyst comprise (NH 4 ) 7-x  H x PW 11 O 39  where x=0−3. 
     
     
         19 . The method of  claim 10  wherein the first catalyst, second catalyst or the third catalyst comprises between 0.1 and 3 moles per mole of sulfur, and more preferably between 0.5 and 1 moles per mole sulfur. 
     
     
         20 . The method of  claim 10  wherein the first oxidizer, the second oxidizer or the third oxidizer comprises between 0.1 and 3 moles per mole of sulfur, and more preferably between 0.5 and 1 moles per mole sulfur. 
     
     
         21 . A method of continuously desulfurizing a liquid hydrocarbon comprising the steps of:
 (a) continuously adding a liquid hydrocarbon to a first vessel, the hydrocarbon having an initial sulfur content;   (b) continuously adding a first catalyst and a first oxidizer to the first vessel create a first mixture;   (c) continuously oxidizing at least some of the sulfur content of the liquid hydrocarbon to form oxidized sulfur in the liquid hydrocarbon within the first vessel;   (d) continuously separating a portion the liquid hydrocarbon and oxidized sulfur from within the first mixture, the hydrocarbon having an initial lowered sulfur content that is lower than the initial sulfur content;   (e) continuously directing the liquid hydrocarbon and oxidized sulfur into at least one subsequent vessel, the hydrocarbon having a subsequent sulfur content;   (f) continuously adding a subsequent catalyst and a subsequent oxidizer to the second vessel to create a subsequent mixture;   (g) continuously oxidizing at least some of the sulfur content of the liquid hydrocarbon to form additional oxidized sulfur in the liquid hydrocarbon within the subsequent vessel;   (h) continuously separating a portion the liquid hydrocarbon and oxidized sulfur from within the subsequent mixture; and   (i) continuously removing the liquid hydrocarbon and oxidized sulfur from within the subsequent vessel, the liquid hydrocarbon having a completed subsequent sulfur content which is lower than the subsequent sulfur content.   
     
     
         22 . A system for desulfurizing a liquid hydrocarbon comprising:
 a first vessel having an infeed in fluid communication with the first vessel, a lower exit and an upper exit, the upper exit spaced apart from the lower exit, each spaced apart from the infeed, and, an agitator associated with the first vessel, the agitator configured to agitate the contents of the first vessel;   a second vessel having an infeed in fluid communication with the first vessel, a lower exit and an upper exit, the upper exit spaced apart from the lower exit, each spaced apart from the infeed, and, an agitator associated with the second vessel, the agitator configured to agitate the contents of the second vessel; and   the upper exit of the first vessel in fluid communication with the infeed of the second vessel, the infeed of the first vessel coupled to a supply of a hydrocarbon, a catalyst and an oxidizer, the infeed of the second vessel further coupled to a supply of a catalyst and an oxidizer.   
     
     
         23 . A system for desulfurizing a liquid hydrocarbon comprising:
 a first vessel having an infeed in fluid communication with the first vessel, an exit spaced apart from the infeed, and, an agitator associated with the first vessel, the agitator configured to agitate the contents of the first vessel;   a second vessel having an infeed in fluid communication with the first vessel, an exit spaced apart from the infeed, and, an agitator associated with the second vessel, the agitator configured to agitate the contents of the second vessel; and   a first separator associated with the exit of the first vessel, the separator configured with at least two outlets, at least one outlet in fluid communication with the infeed of the second vessel;   a second separator associated with the exit of the second vessel, the second separator configured with at least two outlets.