SUPERCRITICAL WATER UPGRADING PROCESS TO PRODUCE PARAFFINIC STREAM FROM HEAVY OIL

• US 20170166821A1
• Filed: 12/09/2016
• Published: 06/15/2017
• 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, AlAbdullah, Mohammad A., Al-Shafei, Emad N., Punetha, Ashok K.
• Granted Patent: US 10,066,172 B2
• Time in Patent Office: Days
• CPC Class Codes: C10G 2300/107 Atmospheric residues having a boiling point of at least about 538 °C
• CPC Class Codes: C10G 2300/1074 Vacuum distillates
• CPC Class Codes: C10G 2300/1077 Vacuum residues
• CPC Class Codes: C10G 2400/00 Products obtained by processes covered by groups C10G9/00 - C10G69/14
• CPC Class Codes: C10G 2400/10 Lubricating oil
• CPC Class Codes: C10G 47/32 in the presence of hydrogen-generating compounds
• CPC Class Codes: C10G 49/007 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
• CPC Class Codes: C10G 51/023 only thermal cracking steps
• CPC Class Codes: C10G 65/10 including only cracking 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 9/36 with heated gases or vapours

Abstract

Embodiments of a process for producing paraffins from a petroleum-based composition comprising long chain aromatics comprise mixing a supercritical water stream with a pressurized, heated petroleum-based composition to create a combined feed stream, introducing the combined feed stream to a first reactor through an inlet port of the first reactor, where the first reactor operates at supercritical pressure and temperature, cracking at least a portion of the long chain aromatics in the first reactor to form a first reactor product, and then introducing the first reactor product to a second reactor through an upper inlet port of the second reactor operating at supercritical pressure and temperature, where the second reactor is a downflow reactor comprising an upper inlet port, a lower outlet port, and a middle outlet port are provided. The middle outlet product passing out of the middle outlet port comprises paraffins and short chain aromatics.

Claims

1. A process for producing paraffins from a petroleum-based composition comprising long chain aromatics, the process comprising:

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

where the supercritical water stream is at a pressure greater than a critical pressure of water and at a temperature greater than a critical temperature of water, and

where the pressurized, heated petroleum-based composition is at a pressure greater than the critical pressure of water and at a temperature greater than 75°

C.,

introducing the combined feed stream to a first reactor through an inlet port of the first reactor, where the first reactor operates at a first temperature greater than the critical temperature of water and a first pressure greater than the critical pressure of water;

cracking at least a portion of the long chain aromatics in the first reactor to form a first reactor product, where the first reactor product comprises water, paraffins, short chain aromatics, olefins, and unconverted long chain aromatics;

introducing the first reactor product to a second reactor through an upper inlet port of the second reactor, the second reactor operating at a second temperature less than the first temperature but greater than the critical temperature of water and a second pressure greater than the critical pressure of water,

where the second reactor is a downflow reactor comprising the upper inlet port, a lower outlet port, and a middle outlet port disposed between the upper inlet port and the lower outlet port;

where the second reactor has a volume less than or equal to a volume of the first reactor;

where a middle outlet product is passed out of the second reactor though the middle outlet port, the middle outlet product comprising paraffins and short chain aromatics; and

where a lower outlet product is passed out of the second reactor through the lower outlet port, the lower outlet product comprising multi-ring aromatics and oligomerized olefins;

cooling the middle outlet product to a temperature less than 200°

C.;

reducing the pressure of the cooled middle outlet product to create a cooled, depressurized middle stream with a pressure from 0.05 MPa to 2.2 MPa; and

at least partially separating the cooled, depressurized middle stream into a gas-phase stream and a liquid-phase stream, where the liquid-phase stream comprises water, short chain aromatics, and paraffins;

at least partially separating the liquid-phase stream into a water-containing stream and an oil-containing stream, where the oil-containing stream comprises paraffins and short chain aromatics; and

at least partially separating the paraffins and the short chain aromatics from the oil-containing stream.

2. The process of claim 1, further comprising separating the paraffins and the short chain aromatics in an extraction unit.

3. The process of claim 2, where the extraction unit is a solvent extraction unit.

4. The process of claim 2, further comprising a distillation column upstream of the extraction unit.

5. The process of claim 1, where the first reactor and the second reactor are absent an external supply of hydrogen gas and catalyst.

6. The process of claim 1, where a ratio of the volume of the first reactor to the volume of the second reactor is 0.1:

1 to 1;

1 at standard ambient temperature and pressure.

7. The process of claim 1, further comprising delivering the lower outlet product to a mechanical mixer.

8. The process of claim 1, where the multi-ring aromatics include asphaltenes.

9. The process of claim 1, further comprising injecting plug remover solution into the lower outlet port of the second reactor.

10. The process of claim 9, where the plug remover solution comprises toluene.

11. The process of claim 1, where the lower outlet port is not continuously opened.

12. The process of claim 1, where the middle outlet product includes less than 1 weight percent of olefins.

13. The process of claim 1, where the petroleum-based composition comprises atmospheric residue, vacuum gas oil, or vacuum residue.

14. The process of claim 1, where the supercritical water stream and the pressurized, heated petroleum-based composition each define flow rates, where a ratio of the flow rates of the supercritical water stream and the pressurized, heated petroleum-based composition is 5:

1 to 1;

1 at standard ambient temperature and pressure.

15. The process of claim 1, where the first reactor, the second reactor, or both include agitating or stirring devices.