PRODUCTION OF UPGRADED PETROLEUM BY SUPERCRITICAL WATER

• US 20160312129A1
• Filed: 12/18/2013
• Published: 10/27/2016
• Est. Priority Date: 12/18/2013
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: Garhoush, Mohammad S., Alshareef, Ali H., Choi, Ki-Hyouk, Lee, Joo-Hyeong
• Granted Patent: US 9,771,527 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01D 11/0407 the supercritical fluid acting as solvent for the solute
• CPC Class Codes: B01J 2208/00911 Sparger-type feeding elements
• CPC Class Codes: B01J 2219/185 vertical
• CPC Class Codes: B01J 3/008 Processes carried out under supercritical conditions
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/206 Asphaltenes
• CPC Class Codes: C10G 2300/308 Gravity, density, e.g. API
• CPC Class Codes: C10G 2300/4006 Temperature
• CPC Class Codes: C10G 47/02 characterised by the catalyst used
• CPC Class Codes: C10G 47/32 in the presence of hydrogen-generating compounds
• CPC Class Codes: C10G 49/18 in the presence of hydrogen-generating compounds, e.g. ammonia, water, hydrogen sulfide
• CPC Class Codes: C10G 55/00 Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
• CPC Class Codes: Y02P 20/54 using solvents, e.g. supercritical solvents or ionic liquids

Abstract

A method for upgrading a petroleum feedstock using a supercritical water petroleum upgrading system includes introducing the petroleum feedstock, water and an auxiliary feedstock. The method includes operating the system to combine the petroleum feedstock and the water to form a mixed petroleum feedstock and introducing separately and simultaneously into a lower portion of an upflowing supercritical water reactor. The auxiliary feedstock is introduced such that a portion of a fluid contained within the upflowing reactor located proximate to the bottom does not lack fluid momentum. An embodiment of the method includes operating the supercritical water petroleum upgrading system such that the upflowing reactor product fluid is introduced into an upper portion of a downflowing supercritical water reactor. The supercritical water petroleum upgrading system includes the upflowing supercritical water reactor and optionally a downflowing supercritical water reactor.

Claims

1. A method for upgrading a petroleum feedstock using a supercritical water petroleum upgrading system, the method comprising the steps of:

introducing the petroleum feedstock into the supercritical water petroleum upgrading system;

introducing a water into the supercritical water petroleum upgrading system;

introducing an auxiliary feedstock into the supercritical water petroleum upgrading system;

operating the supercritical water petroleum upgrading system such that the petroleum feedstock and the water combine to form a mixed petroleum feedstock;

operating the supercritical water petroleum upgrading system such that the mixed petroleum feedstock and the auxiliary feedstock are introduced separately and simultaneously into a lower portion of an upflowing supercritical water reactor, where the auxiliary feedstock is introduced into the upflowing reactor such that a portion of a fluid contained within the upflowing reactor located proximate to the bottom of the upflowing reactor does not lack fluid momentum;

operating the upflowing supercritical water reactor such that the fluid contained within the upflowing reactor is maintained at a temperature equal to or greater than about the critical temperature of water, at a pressure equal to or greater than about the critical pressure of water, and is moving in a generally upwards direction, such that supercritical water forms from the introduced water in the fluid contained within the upflowing reactor;

operating the upflowing supercritical water reactor such that the upgraded and desulfurized petroleum product forms as the reaction product between the introduced petroleum feedstock and the supercritical water in the fluid contained within the upflowing reactor;

operating the supercritical water petroleum upgrading system such that an upflowing reactor product fluid passes from an upper portion of the upflowing reactor, where the product fluid comprises the upgraded and desulfurized petroleum product, and where the amount of passing upflowing reactor product fluid is equivalent to the combined amount of the introduced mixed petroleum feedstock and the auxiliary feedstock; and

operating the supercritical water petroleum upgrading system such that a gas-phase hydrocarbon product, the upgraded and desulfurized petroleum product and an aqueous-phase product are separately selectively separated from the upflowing reactor product fluid.

2. The method of claim 1 where the petroleum feedstock and the water are introduced such that a volumetric flow ratio of introduced water to introduced petroleum feedstock is maintained in a range of from about 10:

1 to about 1;

10 at standard conditions.

3. The method of claim 1 further comprising the step of operating the supercritical water petroleum upgrading system such that the petroleum feedstock combined into the mixed petroleum feedstock has a temperature no greater than about 150°

C. and a pressure equal to or greater than about the critical pressure of water.

4. The method of claim 1 further comprising the step of operating the supercritical water petroleum upgrading system such that a volumetric flow ratio of the auxiliary feedstock to the mixed petroleum feedstock at ambient temperature and at respective pressure conditions is in a range of from about 2:

1 to about 1;

1000 at standard conditions.

5. The method of claim 1 further comprising the step of operating the supercritical water petroleum upgrading system such that a temperature difference between the auxiliary feedstock and the mixed petroleum feedstock is maintained in a range of from about −

50°

C. to about 250°

C.

6. The method of claim 1 further comprising the step of operating the upflowing supercritical water reactor such that the temperature of the fluid within in the upflowing reactor is maintained in a range of from about 380°

C. to about 600°

C.

7. The method of claim 1 further comprising the step of operating the supercritical water petroleum upgrading system such that the temperature difference between the upflowing reactor product fluid and the mixed petroleum feedstock is maintained in a range of from about 50°

C. to about 300°

C. and the pressure of the upflowing reactor product fluid is maintained in a range of from about 3,200 psig to about 6,000 psig.

8. The method of claim 1 where the auxiliary fluid is introduced into the upflowing supercritical water reactor such that the auxiliary fluid has a greater upward fluid velocity than the average superficial velocity of fluid in the reactor.

9. The method of claim 1 where the auxiliary fluid is introduced into the upflowing supercritical water reactor such that the fluid in the lower portion of the upflowing reactor is maintained in a turbulent fluid flow regime.

10. The method of claim 1 where the auxiliary feedstock comprises supercritical water.

11. The method of claim 10 where the auxiliary feedstock further comprises aromatic hydrocarbons, where the aromatic hydrocarbons are present in a range of from about 1 weight percent (wt. %) to about 75 wt. % of the auxiliary feedstock.

12. The method of claim 11 where the aromatic hydrocarbons consist essentially of toluene.

13. The method of claim 11 where the auxiliary feedstock further comprises a catalytic material, where the catalytic material is present in a range of from about 100 ppm wt. % to about 1 wt. % of the auxiliary feedstock and consists of one to five active metals selected from the group consisting of iron, nickel, vanadium, molybdenum, chromium, manganese, cobalt, copper, zinc, tungsten, zirconium and titanium.

14. The method of claim 11 where the auxiliary feedstock further comprises a catalyst precursor, where the catalyst precursor is operable to convert into a catalytic material at the operating conditions of the upflowing supercritical water reactor, the catalyst precursor is present in a range of from about 100 ppm wt. % to about 1 wt. % of the auxiliary feedstock and consists of one to five active metals selected from the group consisting of iron, nickel, vanadium, molybdenum, chromium, manganese, cobalt, copper, zinc, tungsten, zirconium and titanium.

15. The method of claim 11 where the auxiliary feedstock also comprises paraffinic sulfur, where the paraffinic sulfur is present in a range of from 0.05 wt. % to about 1 wt. % of the auxiliary feedstock as calculated on a sulfur-only basis.

16. The method of claim 15 where the paraffinic sulfur is selected from the group consisting of thiol compounds having a carbon number in a range of from 1 to 8 and combinations thereof.

17. The method of claim 1 where the auxiliary feedstock comprises light hydrocarbons.

18. The method of claim 17 where the auxiliary feedstock also comprises paraffinic sulfur, where the paraffinic sulfur is present in a range of from 0.05 wt. % to about 1 wt. % of the auxiliary feedstock as calculated on a sulfur-only basis and is selected from the group consisting of thiol compounds having a carbon number in a range of from 1 to 8 and combinations thereof.

19. The method of claim 1 further comprising the steps of:

operating the supercritical water petroleum upgrading system such that the upflowing reactor product fluid is introduced into an upper portion of a downflowing supercritical water reactor;

operating the downflowing supercritical water reactor such that a fluid contained in the downflowing reactor is maintained at a temperature and a pressure equal to or greater than the critical temperature and the critical pressure of water, respectively, and is moving in a generally downward direction; and

operating the supercritical water petroleum upgrading system such that a downflowing reactor product fluid passes from a lower portion of the downflowing supercritical water reactor,

where the amount of passing downflowing reactor product fluid is equivalent to the amount of introduced upflowing reactor product fluid;

where the step of operating the supercritical water petroleum upgrading system is such that the gas-phase hydrocarbon product, the upgraded and desulfurized petroleum product and the aqueous-phase product are produced through the separate selective separation of the downflowing reactor product fluid instead of the upflowing reactor product fluid; and

where the supercritical water petroleum upgrading system also includes the downflowing supercritical water reactor, where the downflowing reactor is fluidly coupled downstream of the upflowing supercritical water reactor and is operable to receive the upflowing reactor product fluid into the upper portion of the downflowing reactor.

20. The method of claim 19 further comprising the step of operating the downflowing supercritical water reactor such that the temperature of the fluid contained in the downflowing reactor is maintained at a temperature in a range of from about 0°

C. to about 100°

C. greater than the temperature of the fluid contained in the upflowing reactor.

21. The method of claim 1 further comprising the step of operating the supercritical water petroleum upgrading system such that the yield between the introduced petroleum feedstock and the upgraded and desulfurized petroleum product is equal to or greater than about 92 percent by weight.

22. The method of claim 1 further comprising the step of operating the supercritical water petroleum upgrading system such that the difference in API gravity between the upgraded and desulfurized petroleum product and the introduced petroleum feedstock is equal to or greater than about 8 degrees.

23. The method of claim 1 further comprising the step of operating the supercritical water petroleum upgrading system such that such that the upgraded and desulfurized petroleum product has less than about 3 wt. % insoluble material.

24. A supercritical water petroleum upgrading system comprising an upflowing supercritical water reactor,

where the upflowing supercritical water reactor has a lower portion, an upper portion, and an interior defined by an enclosing shell,

where the upflowing supercritical water reactor is operable to maintain a fluid contained within the interior at supercritical water conditions,

where the upflowing supercritical water reactor is operable to distribute both the mixed petroleum feedstock and the auxiliary feedstock separately into the interior of the upflowing reactor proximate to the lower portion of the upflowing reactor to facilitate upward movement of the fluid in the interior,

where the upflowing supercritical water reactor is operable to distribute the auxiliary feedstock into the lower portion of the upflowing reactor such that fluid located proximate to the lower portion of the upflowing reactor does not lack fluid momentum,

where the lower portion includes an auxiliary feedstock port and a mixed petroleum feedstock port that are separately operable to provide fluid communication between the interior and the exterior along the lower portion of the upflowing reactor, and

where the upper portion includes an outlet port that is operable to provide fluid communication between the interior and the exterior along the upper portion of the upflowing reactor.

25. The supercritical water petroleum upgrading system of claim 24 further comprising an internal fluid distribution device, where the internal fluid distribution device fluidly couples to the auxiliary feedstock port and is operable to distribute the auxiliary feedstock into the lower portion of the upflowing reactor such that fluid located proximate to the lower portion of the upflowing reactor does not lack fluid momentum.

26. The supercritical water petroleum upgrading system of claim 24 where the upflowing supercritical water reactor is operable to distribute the auxiliary feedstock into the lower portion of the upflowing reactor such that fluid located in the lower portion of the upflowing reactor is maintained in a turbulent fluid flow regime.

27. The supercritical water petroleum upgrading system of claim 24 further comprising a downflowing supercritical water reactor,

where the downflowing supercritical water reactor has a lower portion, an upper portion, and an interior defined by an enclosing shell,

where the downflowing supercritical water reactor is operable to maintain a fluid contained within the interior at supercritical water conditions,

where the upper portion includes an inlet port that is operable to provide fluid communication between the interior and the exterior along the upper portion of the downflowing reactor,

where the lower portion includes an outlet port that is operable to provide fluid communication between the interior and the exterior along the lower portion of the downflowing reactor, and

where the downflowing reactor is downstream of the upflowing reactor and the upper portion of the downflowing reactor is fluidly coupled the upper portion of the upflowing reactor.