Removal of olefins from hydrothermally upgraded heavy oil

Abstract

A method for sulfur removal and upgrading comprising the steps of mixing a heated oil feed and a supercritical water feed in a feed mixer, allowing conversion reactions to occur in the supercritical water reactor, reducing the temperature in the cooling device to produce a cooled fluid, reducing the pressure in the depressurizing device to produce a discharged fluid, separating the discharged fluid in the gas-liquid separator to produce a liquid phase product, increasing the pressure to produce pressurized liquid product, the pressure of pressurized liquid product is greater than the critical pressure of water, processing the pressurized liquid product in the hydration reactor to produce a hydrated oil stream, separating the hydrated oil stream to produce an extracted upgraded oil and an oxygenate concentrated stream, the oxygenate concentrated stream comprises the oxygenates, and processing the extracted upgraded oil in the hydrotreater to produce a desulfurized upgraded oil.

That which is claimed is: 
     
         1 . A method of sulfur removal and upgrading a feed oil, the method comprising the steps of:
 introducing the feed oil and a water feed to a supercritical water unit, wherein a ratio of the volumetric flow rate of the feed oil to the water feed is such that there is a greater amount of water than oil by volume as measured at standard temperature and pressure (SATP);   operating the supercritical water unit to produce a gas phase product, a water product, and an upgraded feed oil;   introducing the upgraded feed oil to an olefin converter, wherein the olefin converter operates at a temperature less than 250 deg C. and a pressure of less than 10 MPa such that olefins are in the vapor phase;   processing the upgraded feed oil in the olefin converter to produce a reduced olefin stream, wherein the amount of olefins in the reduced olefin stream is reduced relative to the amount of olefins in the upgraded feed oil;   introducing the reduced olefin stream to a hydrotreater unit, wherein the hydrotreater unit comprises a hydrotreating catalyst, wherein the hydrotreaters unit is at a temperature between 250 deg C. and 450 deg C. and a pressure between 0.5 MPa and 25 MPa; and   processing the reduced olefin stream in the hydrotreater to produce a desulfurized upgraded oil.   
     
     
         2 . The method of  claim 1 , wherein the step of operating the supercritical water unit to produce the gas phase product, the water product, and the upgraded feed oil comprises the steps of:
 increasing a pressure of the feed oil in an oil feed pump to produce a pressurized oil feed;   increasing a temperature of the pressurized oil feed in an oil feed heater to produce a heated oil feed;   increasing a pressure of the water feed in a water pump to produce a pressurized water stream;   increasing a temperature of the pressurized water stream in a water heater to produce supercritical water feed;   mixing a heated oil feed and a supercritical water feed in a feed mixer to produce a mixed stream;   introducing the mixed stream to a supercritical water reactor;   allowing conversion reactions to occur in the supercritical water reactor to produce a reactor effluent;   introducing the reactor effluent to a cooling device;   reducing the temperature of the reactor effluent in the cooling device to produce a cooled fluid;   introducing the cooled fluid to a depressurizing device;   reducing the pressure of the cooled fluid in the depressurizing device to produce a discharged fluid;   introducing the discharged fluid to a gas-liquid separator;   separating the discharged fluid in the gas-liquid separator to produce a gas phase product and a liquid phase product;   introducing the liquid phase product to an oil-water separator; and   separating the liquid phase product in the oil-water separator to produce a water product and an upgraded feed oil.   
     
     
         3 . The method of  claim 1 , wherein the olefin converter can be selected from the group consisting of a catalytic hydrogenation unit and a catalytic alkylation unit. 
     
     
         4 . The method of  claim 1 , wherein the olefin converter comprises an olefin catalyst, wherein the olefin catalyst is selected from the group consisting of a hydrogenation catalyst and an alkylation catalyst. 
     
     
         5 . The method of  claim 1 , further comprising the step of introducing hydrogen gas to the olefin converter. 
     
     
         6 . The method of  claim 1 , wherein the olefin converter is in the absence of water. 
     
     
         7 . The method of  claim 1 , wherein the hydrotreating catalyst comprises a metal sulfide, the metal sulfide selected from the group consisting of cobalt-molybdenum sulfides, nickel-molybdenum sulfides, nickel tungsten sulfides, and combinations of the same. 
     
     
         8 . The method of  claim 1 , wherein the liquid hourly space velocity in the hydrotreater unit is between 0.1 per hour and 5 per hour. 
     
     
         9 . The method of  claim 1 , wherein the feed oil is selected from the group comprising petroleum, coal liquid, and biomaterials.