Supercritical reactor systems and processes for petroleum upgrading

• US 9,920,258 B2
• Filed: 12/13/2016
• Issued: 03/20/2018
• Est. Priority Date: 12/15/2015
• 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, Alabdulhadi, Abdullah T., Al-Abdullah, Mohammad A.
• Primary Examiner(s): ROBINSON, RENEE E
• Application Number:
  US15/377,351
• Publication Number:
  US 20170166822A1
• Time in Patent Office: 462 Days
• CPC Class Codes: B01J 3/008 Processes carried out under supercritical conditions
• CPC Class Codes: B01J 3/02 Feed or outlet devices therefor
• CPC Class Codes: C10G 11/10 with stationary catalyst bed
• CPC Class Codes: C10G 2300/70 Catalyst aspects
• CPC Class Codes: C10G 2300/703 Activation
• CPC Class Codes: C10G 2300/805 Water
• CPC Class Codes: C10G 2300/807 Steam
• CPC Class Codes: C10G 31/08 by treating with water
• CPC Class Codes: C10G 49/18 in the presence of hydrogen-generating compounds, e.g. ammonia, water, hydrogen sulfide
• CPC Class Codes: C10G 51/026 only catalytic cracking steps
• CPC Class Codes: C10G 65/02 plural serial stages only
• CPC Class Codes: C10G 65/10 including only cracking steps
• CPC Class Codes: C10G 65/12 including cracking steps and other hydrotreatment steps
• 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 75/04 by addition of antifouling agents
• CPC Class Codes: Y02P 20/54 using solvents, e.g. supercritical solvents or ionic liquids

Abstract

Supercritical upgrading reactors and reactor systems for upgrading a petroleum-based compositions comprising one or more catalyst layers and, in some embodiments, one or more purging fluid inlets, where one or more catalyst layers at least partially sift and convert heavy hydrocarbon fractions to light hydrocarbon fractions to produce an upgraded supercritical reactor product. In some embodiments, upgrading reactor systems comprise one or more supercritical upgrading reactors and one or more supercritical standby reactors alternating functions such that a supercritical upgrading reactor is converted to a supercritical standby reactor and the supercritical standby reactor is converted to a supercritical upgrading reactor, where the supercritical upgrading reactor upgrades a combined feed stream while a supercritical standby reactor delivers a cleaning fluid into the supercritical standby reactor.

Claims

1. A process for upgrading a petroleum-based composition comprising:

combining a supercritical water stream with a pressurized, heated petroleum-based composition in a mixing device to create a combined feed stream;

introducing the combined feed stream into an upgrading reactor system comprising at least one downflow supercritical upgrading reactor operating at a temperature greater than a critical temperature of water and a pressure greater than a critical pressure of water,

where the downflow supercritical upgrading reactor comprises a first catalyst layer and a second catalyst layer, the second catalyst layer disposed vertically below the first catalyst layer in the downflow supercritical upgrading reactor,

where the first catalyst layer comprises a heterogeneous porous metal containing catalyst having a first void volume ratio and the second catalyst layer comprises a heterogeneous porous metal containing catalyst having a second void volume ratio,

where the second void volume ratio differs from the first void volume ratio, and

where the downflow supercritical upgrading reactor includes one or more purging fluid inlets disposed on one or more side locations of the downflow supercritical upgrading reactor proximate the first catalyst layer, the second catalyst layer, or both;

passing the combined feed stream through the first catalyst layer and the second catalyst layer, where light hydrocarbons in the combined feed stream at least partially flow through the first catalyst layer and the second catalyst layer while heavy hydrocarbons in the combined feed stream are at least partially sifted in voids of the first catalyst layer, voids of the second catalyst layer, or both;

at least partially converting the sifted heavy hydrocarbons to light hydrocarbons in the first catalyst layer or the second catalyst layer in the presence of the supercritical water;

injecting purging fluid through the purging inlets to contact the first catalyst layer, the second catalyst layer, or both to reduce plugging; and

passing upgraded product comprising light hydrocarbons and the converted light hydrocarbons out of the downflow supercritical upgrading reactor.

2. The process of claim 1, where the second void volume ratio is less than the first void volume ratio.

3. The process of claim 2, where the purging fluid inlets are vertically disposed between the first catalyst layer and the second catalyst layer.

4. The process of claim 1, where the purging fluid inlets are vertically disposed above the first catalyst layer.

5. The process of claim 1, where the purging fluid inlets comprise one or more angled linear pipes, the angle being relative to a horizontal plane defined by the first catalyst layer.

6. A process for upgrading a petroleum-based composition comprising:

combining a supercritical water stream with a pressurized, heated petroleum-based composition in a mixing device to create a combined feed stream,

introducing the combined feed stream into an upgrading reactor system comprising at least one supercritical upgrading reactor operating at a temperature greater than a critical temperature of water and a pressure greater than a critical pressure of water,

where the supercritical upgrading reactor comprises a first catalyst layer and a second catalyst layer, the second catalyst layer disposed vertically below the first catalyst layer in the supercritical upgrading reactor

where the first catalyst layer comprises a heterogeneous porous metal containing catalyst having a first void volume ratio and the second catalyst layer comprises a heterogeneous porous metal containing catalyst having a second void volume ratio, and

where the second void volume ratio is less than the first void volume ratio,

passing the combined feed stream through the first catalyst layer and the second catalyst layer, where light hydrocarbons in the combined feed stream at least partially flow through the first catalyst layer and the second catalyst layer while heavy hydrocarbons in the combined feed stream are at least partially sifted in voids of the first catalyst layer, voids of the second catalyst layer, or both;

at least partially converting the sifted heavy hydrocarbons to light hydrocarbons in the first catalyst layer or the second catalyst layer in the presence of the supercritical water;

passing upgraded product comprising light hydrocarbons and the converted light hydrocarbons out of the supercritical upgrading reactor.

7. The process of claim 6, further comprising activating the first catalyst layer, the second catalyst layer, or both by heating at a temperature of at least 400°

C.

8. The process of claim 6, further comprising conditioning the first catalyst layer, the second catalyst layer, or both with supercritical water at the temperature and pressure of the upgrading reactor system prior to introduction of the combined feed stream.

9. The process of claim 6, where the first catalyst layer and the second catalyst layer are in contact with one another.

10. The process of claim 6, where the first catalyst layer and the second catalyst layer are spaced apart a distance.

11. The process of claim 6, where a ratio of the first void volume ratio to the second void volume ratio is from 1 to 10.

12. The process of claim 6, where the first catalyst layer, the second catalyst layer, or both comprises one or more structures selected from the group consisting of metallic honeycomb, sintered metal disk, and metallic woven cloth.

13. The process of claim 6, where the downflow supercritical upgrading reactor includes one or more purging fluid inlet disposed on one or more side locations of the downflow supercritical upgrading reactor proximate the catalyst layer.

14. The process of claim 13, where the purging fluid inlets comprise one or more linear pipes extending horizontally within the downflow supercritical upgrading reactor.

15. The process of claim 13, where the one or more purging fluid inlets comprise one or more linear pipes positioned at an angle, the angle being relative to a horizontal plane defined by the first catalyst layer.

16. The process of claim 13, where the one or more purging fluid inlets comprise one or more non-linear pipes, the non-linear pipes including at least one bend oriented at an angle θ

relative to a plane defined by a straight section of the non-linear pipe or a curvature relative to a straight section of the non-linear pipe.

17. The process of claim 13, where the one or more purging fluid inlets comprises an annular ring having one or more openings, multiple pipes spaced apart or interconnected with one or more openings, or both.

18. The process of claim 13, where the purging fluid also comprises aromatic hydrocarbons selected from the group consisting of benzene, toluene, xylene, and combinations thereof.

19. The process of claim 13, further comprising one or more pressure sensors upstream and downstream of the downflow supercritical upgrading reactor.

20. The process of claim 19, where the pressure sensors trigger one of the purging fluid inlets to deliver purging fluid when the pressure of the downflow supercritical upgrading reactor deviates from 1%-10% of operating pressure.