Process to upgrade whole crude oil by hot pressurized water and recovery fluid

• US 7,740,065 B2
• Filed: 11/24/2008
• Issued: 06/22/2010
• Est. Priority Date: 11/28/2007
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: Choi, Ki-Hyouk
• Primary Examiner(s): Bates; Zakiya W.
• Application Number:
  US12/277,275
• Publication Number:
  US 20090139715A1
• Time in Patent Office: 575 Days
• Field of Search: None
• US Class Current: 166/267
• CPC Class Codes: B01J 3/008 Processes carried out under supercritical conditions
• CPC Class Codes: C10G 2300/1033 Oil well production fluids
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/205 Metal content
• CPC Class Codes: C10G 2300/206 Asphaltenes
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 2300/805 Water
• CPC Class Codes: C10G 31/08 by treating with water
• CPC Class Codes: C10G 45/26 Steam or water
• CPC Class Codes: C10G 47/32 in the presence of hydrogen-generating compounds
• CPC Class Codes: C10G 75/00 Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general C10G7/10, C10G9/16 take precedence
• CPC Class Codes: C10G 9/00 Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
• CPC Class Codes: E21B 43/16 Enhanced recovery methods for obtaining hydrocarbons

Abstract

A process for upgrading whole crude oil utilizing a recovery fluid, depressurizing an extracted whole crude oil/recovery fluid mixture in a step-wise fashion, and subsequently contacting at least a portion of the whole crude oil with supercritical water fluid to produce high value crude oil having low sulfur, low nitrogen, and low metallic impurities for use as hydrocarbon feedstock.

Claims

1. A process for upgrading whole crude oil, the process comprising the steps of:

injecting into an injection well a pressurized recovery fluid at a pressure exceeding the recovery fluid'"'"'s minimum miscibility pressure such that the recovery fluid is operable to sweep an underground formation to enhance recovery of whole crude oil from a production well, the recovery fluid being intimately mixed with the whole crude oil upon recovery from the production well to create a high pressure stream, wherein the whole crude oil comprises a light fraction and a heavy fraction;

depressurizing the high pressure stream under conditions to maintain miscibility of a small portion of the recovery fluid within the heavy fraction, and separating the heavy fraction from the high pressure stream to form a light crude oil stream and a heavy fraction stream, the light crude oil stream containing a significant portion of the recovery fluid;

separating the recovery fluid from the light crude oil stream to form a light fraction stream;

reforming the heavy fraction stream into a reformed heavy fraction by contacting the heavy fraction stream with a water feed stream under supercritical conditions, wherein the reformed heavy fraction has reduced amounts of heavy fraction, asphaltene, sulfur, nitrogen or metal containing substances as compared to the whole crude oil.

2. The process of claim 1, further comprising combining the light fraction stream with the reformed heavy fraction to create upgraded whole crude oil, wherein the upgraded whole crude oil contains has reduced amounts of heavy fraction asphaltene, sulfur, nitrogen or metal containing substances as compared to the whole crude oil.

3. The process of claim 1 wherein the recovery fluid is selected from the group consisting of gas, liquid, steam, chemicals, and combinations thereof.

4. The process of claim 1 wherein the recovery fluid is a gas selected from the group consisting of carbon dioxide, nitrogen, natural gas, and combinations thereof.

5. The process of claim 1 wherein the recovery fluid is carbon dioxide.

6. The process of claim 1 wherein the step of separating the recovery fluid from the light crude oil stream comprises a flash evaporator.

7. The process of claim. 1, wherein the step of reforming the heavy fraction stream further comprises:

combining the heavy fraction with the water feed stream to create a mixture, wherein the mixture is created in the absence of externally supplied hydrogen;

modifying the temperature of the mixture such that the temperature of the mixture in a reaction zone is at or above the critical temperature of water, such that at least a portion of hydrocarbons in the mixture undergo cracking to create a hot adapted mixture;

cooling and depressurizing the hot adapted mixture to create a pressure-reduced adapted mixture;

separating the pressure-reduced adapted mixture into a gas portion and a liquid portion; and

separating the liquid portion into a recovered water stream and the reformed heavy fraction.

8. The process of claim 7, wherein the mixture is created in the absence of an externally supplied catalyst.

9. The process of claim 7, wherein the reaction zone comprises a main reactor having an interior portion , the main reactor comprising a vertically oriented reactor, such that the pre-heated mixture flows downwardly through the vertically oriented reactor.

10. The continuous process of claim 7, wherein the hot adapted mixture is depressurized by a pressure regulating device, the pressure regulating device comprises at least one back pressure regulator.

11. The continuous process of claim 10, wherein the pressure regulating device is comprised of two or more back pressure regulators configured in a parallel fashion.

12. The process of claim 1, wherein the step of reforming the heavy fraction stream further comprises:

increasing the pressure of the water feed stream and the heavy fraction stream to a target pressure, the target pressure exceeding the critical pressure of water;

mixing the heavy fraction stream with the water feed stream at a slightly elevated temperature to form a mixture, the temperature being selected in a range such that mixture at the slightly elevated temperature is readily capable of being pumped;

pumping the mixture to a heating zone at a pressure exceeding the critical pressure of water;

heating the mixture in the heating zone to a temperature in the range of about 150°

C. to 350°

C. to form a pre-heated mixture;

feeding the pre-heated mixture into a reaction zone;

increasing the temperature within the reaction zone to a target temperature that is at or above the critical temperature water, such that a portion of hydrocarbons of the pre-heated mixture undergo cracking, forming a hot adapted-mixture, the reaction zone being essentially free of an externally-provided catalyst and essentially free of an externally-provided hydrogen source;

cooling and depressurizing the hot adapted-mixture to form a pressure reduced adapted-mixture;

separating the pressure reduced adapted-mixture into a gas portion and a liquid portion using at least one separator; and

separating the liquid portion into the reformed heavy fraction and a recovered water stream using at least one oil-water separator.

13. The process of claim 12, further comprising:

oxidizing the recovered water stream under supercritical conditions to form a treated water stream; and

recycling the treated water stream by combining the treated water stream with the water feed stream.

14. The process of claim 1, wherein the step of reforming the heavy fraction stream further comprises:

increasing the pressure of the water feed stream and the heavy fraction stream to a target pressure exceeding the critical pressure of water;

heating the water feed stream to an elevated temperature to form a heated water stream, such that the heated water stream is in a supercritical state;

mixing the heavy fraction stream with the heated water stream in a mixing zone to form a pre-heated mixture, wherein the mixing zone is at a location near a reaction zone, such that the pre-heated mixture remains in a supercritical state;

feeding the pre-heated mixture into the reaction zone;

increasing the temperature within the reaction zone to a target temperature that is at or above the critical temperature water, such that at least some of the hydrocarbons of the pre-heated mixture undergo cracking, forming a hot adapted-mixture, the reaction zone being essentially free of an externally-provided catalyst and essentially free of an externally-provided hydrogen source;

cooling and depressurizing the hot adapted-mixture to form a pressure reduced adapted-mixture;

separating the pressure reduced adapted-mixture into a gas portion and a liquid portion using at least one liquid-gas separator; and

separating the liquid portion into the reformed heavy fraction and a recovered water stream using at least one oil-water separator.

15. The process of claim 14, further comprising:

oxidizing the recovered water stream under supercritical conditions to form a treated water stream; and

recycling the treated water stream by combining the treated water stream with the water feed stream.

16. An apparatus for upgrading whole crude oil, the apparatus comprising:

an injection well in fluid communication with an underground formation, the injection well operable to receive a pressurized recovery fluid and introduce the pressurized recovery fluid into the underground formation wherein the pressurized recovery fluid intimately mixes with whole crude oil within the underground formation forming a high pressure stream, the high pressure stream comprising the recovery fluid and whole crude oil, wherein the whole crude oil comprises a light fraction and a heavy fraction;

a production well in fluid communication with the underground formation, the production well operable to produce the high pressure stream from the underground formation;

a fractionating device in fluid communication with the production well, wherein the fractionating device is operable to depressurize the high pressure stream in a step-wise manner such that the heavy fraction is separated from the high pressure stream to form a light crude oil stream and a heavy fraction stream, wherein a small portion of the recovery fluid maintains miscibility within the heavy fraction, and wherein the light crude oil stream contains a significant portion of the recovery fluid; and

a hydrothermal reforming facility operable to reform the heavy fraction stream into a reformed heavy fraction by contacting the heavy fraction stream with a water feed stream under supercritical conditions, wherein the reformed heavy fraction has reduced amounts of heavy fraction, asphaltene, sulfur, nitrogen or metal containing substances as compared to the whole crude oil.

17. The apparatus of claim 16, wherein the hydrothermal reforming facility comprises:

a mixing zone operable to receive the heavy fraction with the water feed at a slightly elevated temperature to create a heavy oil/water mixture;

a pre-heating zone that is fluidly connected with the mixing zone, the pre-heating zone operable to heat the heavy oil/water mixture to a temperature up to about 350°

C.;

a high pressure pumping means, the high pressure pumping means operable to increase pressure of the heavy oil/water mixture to at least the critical pressure of water; and

a reaction zone that is fluidly connected with the pre-heating zone;

the reaction zone comprising an interior portion of a main reactor, the main reactor being operable to withstand a temperature that is at least as high as the critical temperature of water;

the main reactor being operable to withstand pressure in excess of the critical pressure of water, the reaction zone being essentially free of an externally-provided catalyst and essentially free of an externally-provided hydrogen source.

18. The apparatus of claim 17, wherein the mixing zone further comprises an ultra sonic wave generator that is operable to subject the heavy oil/water mixture to cavitations and further induce mixing of the heavy oil/water mixture by creating a submicromulsion.

19. The apparatus of claim 17, further comprising:

a pressure regulating device;

a liquid-gas separator fluidly connected to the pressure regulating device, the liquid-gas separator operable to create a liquid stream and a gas stream; and

a water-oil separator fluidly connected to the liquid-gas separator via the liquid stream, the water-oil separator operable to create a recovered water stream and an upgraded hydrocarbon stream.

20. The apparatus of claim 19, wherein the recovered water stream can be recycled and combined with the water feed, and the apparatus further comprising an oxidation reactor fluidly connected with the recovered water stream, the oxidation reactor operable to clean the recovered water stream via oxidation.