Process for the desulfurization of hydrocarbonacecus oil

Abstract

A process for the desulfurization of hydrocarbonaceous oil wherein the hydrocarbonaceous oil is contacted with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone to reduce the sulfur level to a relatively low level then contacting the resulting hydrocarbonaceous stream from the hydrodesulfurization zone with an oxidizing agent to convert the residual, low level of sulfur compounds into sulfur-oxidated compounds. The resulting hydrocarbonaceous oil stream containing the sulfur-oxidated compounds is separated after decomposing any residual oxidizing agent by contacting the stream with an adsorbent material to adsorb the sulfur-oxidated compounds to produce a hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds. The spent adsorbent is regenerated and subsequently returned to adsorbent service.

1 . A process for the desulfurization of a hydrocarbonaceous oil which process comprises: 
 (a) contacting the hydrocarbonaceous oil with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone at hydrodesulfurization conditions to produce hydrogen sulfide and a resulting first hydrocarbonaceous oil stream having a reduced concentration of sulfur;    (b) contacting the first hydrocarbonaceous oil stream having a reduced concentration of sulfur with an aqueous oxidizing solution in an oxidation zone to produce a second hydrocarbonaceous oil stream comprising sulfur-oxidated compounds;    (c) contacting the second hydrocarbonaceous stream comprising sulfur-oxidated compounds from step (b) with a selective adsorbent having a greater selectivity for the sulfur-oxidated compounds than for sulfur-free hydrocarbonaceous oil to produce an adsorbent containing at least a portion of the sulfur-oxidated compounds and a third hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds;    (d) separating the adsorbent containing at least a portion of the sulfur-oxidated compounds produced in step (c) to provide an adsorbent rich in sulfur-oxidated compounds; and    (e) recovering the third hydrocarbonaceous oil stream.    
     
     
         2 . The process of  claim 1  wherein the hydrocarbonaceous oil boils in the range from about 149° C. (300° F.) to about 538° C. (1000° F.).  
     
     
         3 . The process of  claim 1  wherein the hydrodesulfurization reaction zone is operated at conditions which include a pressure from about 800 kPa (100 psig) to about 12.5 MPa (1800 psig), a maximum catalyst temperature from about 204° C. (400° F.) to about 400° C. (750° F.) and a hydrogen to feed ratio from about 33.7 nm 3 /m 3  (200 SCFB) to about 1685 nm 3 /m 3  (10,000 SCFB).  
     
     
         4 . The process of  claim 1  wherein the hydrodesulfurization catalyst comprises a Group VIB metal component, a Group VIII metal component and alumina.  
     
     
         5 . The process of  claim 1  wherein the hydrocarbonaceous oil stream having a reduced concentration of sulfur and produced in step (a) has a sulfur level from about 100 ppm to about 1000 ppm.  
     
     
         6 . The process of  claim 1  wherein the sulfur-oxidated compounds are selected from the group consisting of sulfoxide and sulfones.  
     
     
         7 . The process of  claim 6  wherein the oxidizing agent is selected from the group consisting of a gas, a liquid and a solid.  
     
     
         8 . The process of  claim 1  wherein the oxidizing agent is selected from the group consisting of oxygen, ozone, nitrogen oxide, hydrogen peroxide, organic hydroperoxide, carboxylic peracids and metal superoxides.  
     
     
         9 . The process of  claim 1  wherein the oxidation zone contains an oxidation catalyst.  
     
     
         10 . The process of  claim 1  wherein at least a portion of any residual oxidizing solution from the step (b) is decomposed.  
     
     
         11 . The process of  claim 10  wherein the decomposition is conducted in the presence of a catalyst.  
     
     
         12 . The process of  claim 1  wherein the aqueous oxidizing solution comprises hydrogen peroxide and a carboxylic acid.  
     
     
         13 . The process of  claim 12  wherein the oxidation zone is operated at conditions including a molar feed ratio of hydrogen peroxide to sulfur ranging from about 1 to about 10 and a molar ratio of carboxylic acid to hydrogen peroxide from about 0.1 to about 10.  
     
     
         14 . The process of  claim 1  wherein the oxidation zone is operated at conditions including a pressure from about atmospheric to about 800 kPa (100 psig) and a temperature from about 38° C. (100° F.) to about 149° C. (300° F.).  
     
     
         15 . The process of  claim 1  wherein the selective adsorbent is selected from the group consisting of silica, alumina, silicalite, ZSM-5, zeolite L, X and Y-type zeolites, dealuminated Y-type zeolite, zeolite beta, zeolite omega, and SAPO-34.  
     
     
         16 . The process of  claim 1  wherein the contacting in step (c) is selected from the group of consisting of fixed bed, ebullated bed, fluidized bed, or counter current solid-liquid contacting.  
     
     
         17 . A process for the desulfurization of a hydrocarbonaceous oil which process comprises: 
 a) contacting the hydrocarbonaceous oil with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone at hydrodesulfurization conditions to produce hydrogen sulfide and a resulting first hydrocarbonaceous oil stream having a reduced concentration of sulfur;    b) contacting the first hydrocarbonaceous oil stream having a reduced concentration of sulfur with an aqueous oxidizing solution in an oxidation zone to produce a second hydrocarbonaceous stream oil stream comprising sulfur-oxidated compounds;    c) contacting the second hydrocarbonaceous stream comprising sulfur-oxidated compounds from step (b) with a selective adsorbent having a greater selectivity for the sulfur oxidated compounds than for sulfur-free hydrocarbonaceous oil to produce an adsorbent containing at least a portion of the sulfur-oxidated compounds and a third hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds;    d) separating the adsorbent containing at least a portion of the sulfur-oxidated compounds produced in step (c) to provide an adsorbent rich in sulfur-oxidated compounds;    e) regenerating at least a portion of the adsorbent from step (d) and recycling to step (c) to provide at least a portion of the selective adsorbent, and;    f) recovering the third hydrocarbonaceous oil stream.    
     
     
         18 . The process of  claim 17  wherein at least a portion of any residual oxidizing solution from the step (b) is decomposed.  
     
     
         19 . The process of  claim 17  wherein the hydrodesulfurization reaction zone is operated at conditions which include a pressure from about 800 kPa (100 psig) to about 12.5 MPa (1800 psig), a maximum temperature from about 204° C. (400° F.) to about 400° C. (750° F.) and a hydrogen to feed ratio from about 33.7 nm 3 /m 3  (200 SCFB) to about 1685 nm  3 /m 3  (10,000 SCFB).  
     
     
         20 . The process of  claim 17  wherein the aqueous oxidizing solution comprises hydrogen peroxide and a carboxylic acid.  
     
     
         21 . The process of  claim 20  wherein the oxidation zone is operated at conditions including a molar feed ratio of hydrogen peroxide to sulfur ranging from about 1 to about 10 and a molar ratio of carboxylic acid to hydrogen peroxide from about 0.1 to about 10.  
     
     
         22 . The process of  claim 17  wherein the process of  claim 1  wherein the selective adsorbent is selected from the group consisting of silica, alumina, silicalite, ZSM-5, zeolite L, X and Y-type zeolites, dealuminated Y-type zeolite, zeolite beta, zeolite omega, and SAPO-34.  
     
     
         23 . A process for the desulfurization of a hydrocarbonaceous oil which process comprises: 
 a) contacting the hydrocarbonaceous oil boiling in the range from about 149° C. (300° F.) to about 538° C. (1000° F.) with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone at hydrodesulfurization conditions which include a pressure from about 800 kPa (100 psig) to about 12.5 MPa (1800 psig), a maximum temperature from about 204° C. (400° F.) to about 400° C. (750° F.) and a hydrogen to feed ratio from about 33.7 nm 3 /m 3  (200 SCFB) to about 1685 nm 3 /m 3  (10,000 SCFB) to produce hydrogen sulfide and a resulting first hydrocarbonaceous oil stream having a reduced concentration of sulfur;    b) contacting the first hydrocarbonaceous oil stream having a reduced concentration of sulfur with an aqueous oxidizing solution comprising acetic acid and hydrogen peroxide in an oxidation zone to produce a second hydrocarbonaceous oil stream comprising sulfur-oxidated compounds;    c) decomposing at least a portion of any residual oxidizing solution from the sulfur oxidation effluent;    d) contacting an effluent stream from step (c) comprising sulfur-oxidated compounds with a selective adsorbent selected from the group consisting of silica, alumina, silicalite, ZSM-5, zeolite L, X and Y-type zeolites, dealuminated Y-type zeolite, zeolite beta, zeolite omega and SAPO-34, and having a greater selectivity for the sulfur oxidated compounds than for sulfur-free hydrocarbonaceous oil to produce an adsorbent containing at least a portion of the sulfur-oxidated compounds and a third hydrocarbonaceous oil stream having a reduced concentration of sulfur-oxidated compounds;    e) separating the adsorbent containing at least a portion of the sulfur-oxidated compounds produced in step (d) to provide an adsorbent rich in sulfur-oxidated compounds;    f) regenerating at least a portion of the adsorbent from step (e) and recycling to step (d) to provide at least a portion of the selective adsorbent, and;    g) recovering the third hydrocarbonaceous oil stream.