Hydrocarbon oils desulfurization by supercritical water hydrogenation process

Abstract

A process for upgrading a hydrocarbon-based composition includes combining a heated water stream, a hydrogen stream, and a hydrocarbon-based composition in a mixing device to create a combined feed stream. The combined feed stream is introduced into a supercritical water hydrogenation reactor operating at a temperature greater than a critical temperature of water and a pressure greater than a critical pressure of water. The combined feed stream is at least partially converted to an upgraded product stream, and the upgraded product stream is introduced to a gas/oil/water separator where the upgraded product stream is separated to produce a gas fraction, a liquid oil fraction, and a water fraction. The liquid oil fraction is introduced to a mild hydrotreating unit to produce a hydrotreated product.

What is claimed is: 
     
         1 . A process for upgrading a hydrocarbon-based composition comprising:
 combining a heated water stream, a hydrogen stream, and a hydrocarbon-based composition in a mixing device to create a combined feed stream;   introducing the combined feed stream into a supercritical water hydrogenation reactor operating at a temperature greater than a critical temperature of water and a pressure greater than a critical pressure of water;   at least partially converting the combined feed stream to an upgraded product stream;   passing the upgraded product stream to a gas/oil/water separator;   separating the upgraded product stream to produce a gas fraction, a liquid oil fraction, and a water fraction; and   introducing the liquid oil fraction to a mild hydrotreating unit to produce a hydrotreated product.   
     
     
         2 . The process of  claim 1 , further comprising passing the upgraded product stream to a cooling device prior to introducing the upgraded product stream to the gas/oil/water separator. 
     
     
         3 . The process of  claim 1 , further comprising passing the upgraded product stream to a depressurizer prior to introducing the upgraded product stream to the gas/oil/water separator. 
     
     
         4 . The process of  claim 3 , wherein the upgraded product stream is depressurized to less than 1 MPa in the depressurizer. 
     
     
         5 . The process of  claim 1 , wherein the pressurized, heated hydrocarbon-based composition has a temperature from 100° C. to 370° C. 
     
     
         6 . The process of  claim 1 , wherein the supercritical water hydrogenation reactor has a temperature of greater than 375° C. and less than 600° C. and a pressure greater than 22.1 MPa and less than 75 MPa. 
     
     
         7 . The process of  claim 1 , wherein the supercritical water hydrogenation reactor has a temperature of greater than 390° C. and less than 470° C. and a pressure greater than 24 MPa and less than 30 MPa. 
     
     
         8 . The process of  claim 1 , wherein the supercritical water hydrogenation reactor has a residence time of from 1 to 30 minutes. 
     
     
         9 . The process of  claim 1 , wherein the supercritical water hydrogenation reactor has a residence time of from 2 to 15 minutes. 
     
     
         10 . The process of  claim 1 , wherein
 the hydrocarbon-based composition has a T 5  true boiling point from 351° C. to 500° C., and   the hydrotreated product has a T 5  true boiling point from 25° C. to 250° C.   
     
     
         11 . The process of  claim 1 , wherein
 the hydrocarbon-based composition has a T 90  true boiling point from 601° C. to 750° C., and   the hydrotreated product has a T 90  true boiling point from 200° C. to 500° C.   
     
     
         12 . The process of  claim 1 , wherein
 the hydrocarbon-based composition has an API gravity from 5° to 11°, and   the hydrotreated product has an API gravity from 25° to 30°.   
     
     
         13 . The process of  claim 1 , wherein
 the hydrocarbon-based composition has from 2.1 wt. % to 5 wt. % total sulfur content by weight of the hydrocarbon-based composition, and   the hydrotreated product has from 0.1 wt. % to 1.0 wt. % total sulfur content by weight of the hydrotreated product.   
     
     
         14 . The process of  claim 1 , wherein
 the hydrocarbon-based composition has from 0.51 wt. % to 2.00 wt. % total nitrogen content by weight of the hydrocarbon-based composition, and   the hydrotreated product has from 0.01 wt. % to 0.10 wt. % total nitrogen content by weight of the hydrotreated product.   
     
     
         15 . The process of  claim 1 , wherein
 the hydrocarbon-based composition has from 0.51 wt. % to 2.00 wt. % asphaltenes by weight of the hydrocarbon-based composition, and   the hydrotreated product has from 0.01 wt. % to 0.20 wt. % asphaltenes by weight of the hydrotreated product.   
     
     
         16 . The process of  claim 1 , wherein
 the hydrocarbon-based composition has from 10 ppm to 100 ppm metals, and   the hydrotreated product has 0.01 ppm to 0.50 ppm metals.   
     
     
         17 . The process of  claim 1 , wherein
 the hydrocarbon-based composition has a viscosity at 50° C. from 101 cSt to 700 cSt, and   the hydrotreated product has a viscosity at 50° C. from 5 cSt to 20 cSt.   
     
     
         18 . The process of  claim 1 , wherein the hydrotreated product comprises:
 a T 5  true boiling point from 25° C. to 250° C.;   a T 90  true boiling point from 200° C. to 500° C.;   an API gravity from 25° to 30°;   from 0.1 wt. % to 1.0 wt. % total sulfur content by weight of the hydrotreated product;   from 0.01 wt. % to 0.10 wt. % total nitrogen content by weight of the hydrotreated product;   from 0.01 wt. % to 0.20 wt. % asphaltenes by weight of the hydrotreated product;   0.01 ppm to 0.50 ppm metals; and   a viscosity at 50° C. from 5 cSt to 20 cSt.