Integrated desulfurization and denitrification process including mild hydrotreating and oxidation of aromatic-rich hydrotreated products

Abstract

Reduction of sulfur-containing and nitrogen-containing compounds from hydrocarbon feeds is achieved by first contacting the entire feed with a hydrotreating catalyst in a hydrotreating reaction zone operating under mild conditions to convert the labile organosulfur and organonitrogen compounds. An extraction zone downstream of the hydrotreating reaction zone separates an aromatic-rich fraction that contains a substantial amount of the remaining refractory organosulfur and organonitrogen compounds. The aromatic-lean fraction is substantially free of organosulfur and organonitrogen compounds, since the non-aromatic organosulfur and organonitrogen compounds were the labile organosulfur and organonitrogen compounds which were initially removed by mild hydrotreating. The aromatic-rich fraction is oxidized to convert the refractory organosulfur and organonitrogen compounds to oxidized sulfur-containing and nitrogen-containing hydrocarbon compounds. These oxidized organosulfur and organonitrogen compounds are subsequently removed.

1 . A method of processing a hydrocarbon feed to remove undesired aromatic and non-aromatic organosulfur compounds comprising:
 subjecting the hydrocarbon feed to a hydrotreating process to thereby lower the content of labile organosulfur compounds and produce a hydrotreated effluent;   conveying the hydrotreated effluent and an effective quantity of extraction solvent to an extraction zone to produce
 an extract containing a major proportion of the aromatic content of the hydrotreated effluent and a portion of the extraction solvent and 
 a raffinate containing a major proportion of the non-aromatic content of the hydrotreated effluent and a portion of the extraction solvent; 
   separating at least a substantial portion of the extraction solvent from the extract and retaining an aromatic-rich fraction;   contacting the aromatic-rich fraction with an oxidizing agent and an oxidizing catalyst to convert aromatic organosulfur compounds to oxides.   
     
     
         2 . The method of  claim 1 , wherein the hydrocarbon feed further includes undesired aromatic and non-aromatic organonitrogen compounds, the step of subjecting the hydrocarbon feed to a hydrotreating process also lowers the content of labile organonitrogen compounds, and the step of contacting the aromatic-rich fraction with the oxidizing agent and the oxidizing catalyst also convert aromatic organonitrogen compounds to oxides. 
     
     
         3 . The method of  claim 1 , wherein the hydrotreating process is operated at mild operating conditions. 
     
     
         4 . The method of  claim 3 , wherein the hydrotreating process operates with a hydrogen partial pressure of about 10 bars to about 40 bars. 
     
     
         5 . The method of  claim 3 , wherein the hydrotreating process operates with a hydrogen partial pressure of about 10 bars to about 30 bars. 
     
     
         6 . The method of  claim 3 , wherein the hydrotreating process operates with a hydrogen partial pressure of about 20 bars. 
     
     
         7 . The method of  claim 3 , wherein the hydrotreating process operates with an operating temperature of about 300° C. to about 400° C. 
     
     
         8 . The method of  claim 3 , wherein the hydrotreating process operates with an operating temperature of about 300° C. to about 360° C. 
     
     
         9 . The method of  claim 3 , wherein hydrotreating process operates with an operating temperature of about 300° C. to about 340° C. 
     
     
         10 . The method of  claim 3 , wherein the hydrogen feed rate in the hydrotreating process step is from about 100 liters of hydrogen per liter of oil to about 500 liters of hydrogen per liter of oil. 
     
     
         11 . The method of  claim 3 , wherein the hydrogen feed rate in the hydrotreating process step is from about 100 liters of hydrogen per liter of oil to about 300 liters of hydrogen per liter of oil. 
     
     
         12 . The method of  claim 3 , wherein the hydrogen feed rate in the hydrotreating process step is from about 100 liters of hydrogen per liter of oil to about 200 liters of hydrogen per liter of oil. 
     
     
         13 . The method of  claim 1 , wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, organic peroxides such as ter-butyl hydroperoxide, peroxo acids, oxides of nitrogen, oxygen, ozone, and air. 
     
     
         14 . The method of  claim 1 , wherein the oxidizing catalyst is selected from the group consisting of homogeneous catalysts and heterogeneous catalysts. 
     
     
         15 . The method of  claim 14 , wherein the oxidizing catalyst includes a metal from Group IVB to Group VIIIB of the Periodic Table. 
     
     
         16 . The method of  claim 1 , further comprising separating the oxidizing agent and oxidizing catalyst from the oxidized aromatic-rich fraction. 
     
     
         17 . The method of  claim 16 , wherein the oxidizing agent is separated by solvent extraction. 
     
     
         18 . The method of  claim 1 , further comprising recovering a hydrotreated hydrocarbon product. 
     
     
         19 . The method of  claim 1 , further comprising recovering a hydrocarbon product subjected to oxidative desulfurization. 
     
     
         20 . The method of  claim 1 , further comprising combining the aromatic-lean raffinate and the aromatic-rich fraction that has been subjected to oxidation to provide a reduced-organosulfur content hydrocarbon product. 
     
     
         21 . The method of  claim 1 , wherein the extraction solvent is selected from the group consisting of furfural, N-methyl-2-pyrrolidone, dimethylformamide and dimethylsulfoxide. 
     
     
         22 . The method of  claim 1 , wherein the extraction solvent is provided in a solvent to oil ratio of 20:1. 
     
     
         23 . The method of  claim 1 , wherein the extraction solvent is provided in a solvent to oil ratio of 4:1. 
     
     
         24 . The method of  claim 1 , wherein the extraction solvent is provided in a solvent to oil ratio of 1:1. 
     
     
         25 . The method of  claim 1 , wherein the extraction zone operates at a temperature of about 20° C. to about 120° C. 
     
     
         26 . The method of  claim 1 , wherein the extraction zone operates at a temperature of about 40° C. to about 80° C. 
     
     
         27 . The method of  claim 1 , wherein the extraction zone operates at a pressure of about 1 bar to about 10 bars. 
     
     
         28 . The method of  claim 1 , wherein the extraction zone operates at a pressure of about 1 bar to about 3 bars. 
     
     
         29 . An apparatus for processing a hydrocarbon feed containing undesired organosulfur compounds comprising:
 a hydrotreating zone having an inlet in fluid communication with the hydrocarbon feed and an outlet for discharging hydrotreated effluent;   an extraction zone operable to extract aromatic organosulfur compounds from the hydrotreated effluent, the aromatic zone extraction including
 an inlet for receiving the hydrotreated effluent and an inlet for receiving extraction solvent, 
 a raffinate outlet for discharging a raffinate containing a major proportion of the non-aromatic content of the hydrotreated effluent and a portion of the extraction solvent, and 
 an extract outlet for discharging an extract containing a major proportion of the aromatic content of the hydrotreated effluent and a portion of the extraction solvent; 
   an oxidation zone containing an oxidation catalyst and an oxidizing agent, the oxidative desulfurization zone having an inlet in fluid communication with the extract outlet and an outlet for discharging oxidized effluent.