Processes and systems for producing desulfurized alpha olefins

Patent metadata

Field	Value
Publication number	US-12378483-B2
Application number	US-202318149458-A
Country	US
Kind code	B2
Filing date	Jan 3, 2023
Priority date	Jan 3, 2023
Publication date	Aug 5, 2025
Grant date	Aug 5, 2025

Abstract

A process for producing desulfurized alpha olefins may include reacting a conjugated diene compound and a hydrocarbon oil stream including alpha olefins in a Diels-Alder reactor at a temperature of 100° C. to 250° C. to form an effluent stream including adducts of the conjugated diene compound and the alpha olefins, subjecting the effluent stream to a hydrodesulfurization catalyst and a hydrogen stream in a hydrodesulfurization reactor to produce a hydrodesulfurized effluent stream including the adducts, a saturated C 5+ hydrocarbon stream, and a gaseous stream, separating the adducts, the saturated C 5+ hydrocarbon stream, and the gaseous stream, and cracking the adducts in a first thermal cracking reactor operating at a temperature greater than 250° C. to produce a decomposed adducts stream including an alpha olefin stream and a recovered conjugated diene compound stream, wherein the gaseous stream includes hydrogen, sulfides, C 1 -C 4 saturated hydrocarbons, or combinations thereof.

First claim

What is claimed is:

1. A process for producing desulfurized alpha olefins, the process comprising:
reacting a conjugated diene compound and a hydrocarbon oil stream comprising alpha olefins in a Diels-Alder reactor at a temperature of 100° C. to 250° C. to form an effluent stream comprising adducts of the conjugated diene compound and the alpha olefins;
subjecting the effluent stream to a hydrodesulfurization catalyst and a hydrogen stream in a hydrodesulfurization reactor to produce a hydrodesulfurized effluent stream comprising the adducts of the conjugated diene compound and the alpha olefins, a saturated C 5+ hydrocarbon stream, and a gaseous stream, wherein the gaseous stream comprises hydrogen, sulfides, C 1 -C 4 saturated hydrocarbons, or combinations thereof;
separating the adducts of the conjugated diene compound and the alpha olefins, the saturated C 5+ hydrocarbon stream, and the gaseous stream; and
cracking the adducts of the conjugated diene compound and the alpha olefins in a first thermal cracking reactor operating at a temperature greater than 250° C. to produce a decomposed adducts stream comprising an alpha olefin stream and a recovered conjugated diene compound stream.

2. The process of claim 1 , wherein a molar ratio of the conjugated diene compound to alpha olefins entering the Dies-Alder reactor is from 0.1:1 to 5:1 conjugated diene compound to alpha olefins.

3. The process of claim 1 , wherein the conjugated diene compound comprises substituted anthracene, unsubstituted anthracene, cyclohexadiene, cyclopentadiene, or combinations thereof.

4. The process of claim 1 , wherein:
the hydrocarbon oil stream has a sulfur content of from 20 ppm to 50,000 ppm; and
the alpha olefin stream has a sulfur content of less than 20 ppm.

5. The process of claim 1 , wherein the hydrocarbon oil stream comprises a crude oil with an API gravity of from 25° to 50°.

6. The process of claim 1 , wherein separating the adducts of the conjugated diene compound and the alpha olefins, the saturated C 5+ hydrocarbon stream, and the gaseous stream further comprises:
venting the gaseous stream from the adducts of the conjugated diene compound and the alpha olefins and the saturated C 5+ hydrocarbon stream; and
separating the adducts of the conjugated diene compound and the alpha olefins from the saturated C 5+ hydrocarbon stream in a first distillation tower operating at a cut point of from 50° C. to 250° C.

7. The process of claim 1 , wherein separating the adducts of the conjugated diene compound and the alpha olefins, the saturated C 5+ hydrocarbon stream, and the gaseous stream further comprises;
separating the adducts of the conjugated diene compound and the alpha olefins from the gaseous stream and the saturated C 5+ hydrocarbon stream in a first distillation tower operating at a cut point of from 50° C. to 250° C.

8. The process of claim 1 , further comprising separating the alpha olefin stream from the recovered conjugated diene compound stream in a second distillation tower at a cut point of from 300° C. to 400° C.

9. The process of claim 1 , wherein the hydrodesulfurization catalyst comprises:
a first metal selected from the group consisting of iron, ruthenium, osmium, cobalt, rhenium, iridium, nickel, palladium and platinum;
a second metal selected from the group consisting of iron, ruthenium, osmium, cobalt, rhenium, iridium, nickel, palladium and platinum; and
a support selected from activated carbon, activated carbon fiber, carbon black, activated carbon fabric, activated carbon honeycomb, silicon dioxide, titanium dioxide, aluminum oxide, and zirconium dioxide.

10. The process of claim 9 , wherein:
the hydrodesulfurization catalyst is selected from CoMo, NiMo, and NiCoMo; and
the support is selected from aluminum oxide, silica oxide, and activated carbon.

11. The process of claim 10 , wherein:
the molybdenum content is from 2 wt. % to 10 wt. % measured by weight of the hydrodesulfurization catalyst; and
the cobalt content, the nickel content, or both, is from 0.2 wt. % to 25 wt. % measured by weight of the hydrodesulfurization catalyst.

12. The process of claim 1 , further comprising passing the recovered conjugated diene compound stream to the Diels-Alder reactor to be re-used as the conjugated diene compound.

13. The process of claim 1 , further comprising passing the alpha olefin stream from the first thermal cracking reactor to the Diels-Alder reactor as additional alpha olefins in the hydrocarbon oil stream.

14. The process of claim 1 , further comprising introducing a crude oil to a supercritical water reactor in the presence of supercritical water, at a temperature of from 500° C. to 600° C., to form the hydrocarbon oil stream.

15. The process of claim 1 , further comprising:
introducing a crude oil to a crude oil refining process comprising one or more of supercritical water upgrading, pyrolysis, hydrocracking, hydrotreating, non-catalytic steam cracking, steam catalytic cracking, or fluid catalytic cracking to form an upgraded crude oil; and
separating the upgraded crude oil at a cut point of from 340° C. to 400° C. to form a heavy upgraded crude oil and the hydrocarbon oil stream, wherein:
the hydrocarbon oil stream comprises one or more of paraffins, linear alpha olefins, branched alpha olefins, internal olefins, aromatics, sulfur compounds, and nitrogen compounds,
the hydrocarbon oil stream comprises at least 5 wt. % linear alpha olefins by weight of the hydrocarbon oil stream,
the hydrocarbon oil stream comprises at least 100 ppm sulfur compounds, and
the conjugated diene compound is selected from substituted and unsubstituted anthracene.

16. The process of claim 1 , wherein the Diels-Alder reactor, the first thermal cracking reactor, the hydrodesulfurization reactor, or combinations thereof are a tubular-type reactor or continuous stirred-tank reactor.

17. A system for producing desulfurized alpha olefins, the system comprising:
a Diels-Alder reactor configured to form an effluent stream from a hydrocarbon oil stream and a conjugated diene compound, the effluent stream comprising adducts of the conjugated diene compound and alpha olefins from the hydrocarbon oil stream;
a hydrodesulfurization reactor comprising a hydrodesulfurization catalyst fluidly connected and downstream of the Diels Alder reactor;
a first distillation tower fluidly connected and downstream of the hydrodesulfurization reactor;
a first thermal cracking reactor fluidly connected and downstream of the first distillation tower; and
a second distillation tower fluidly connected and downstream of the first thermal cracking reactor.

18. The system of claim 17 , wherein:
the conjugated diene compound comprises substituted anthracene, unsubstituted anthracene, cyclohexadiene, cyclopentadiene, or combinations thereof;
the hydrodesulfurization catalyst is selected from CoMo, NiMo, and NiCoMo; and
the support is selected from aluminum oxide, silica oxide, and activated carbon.

19. The system of claim 17 , further comprising a supercritical water reactor fluidly connected and upstream of the Diels-Alder reactor, wherein the supercritical water reactor is configured to operate at a temperature of from 500° C. to 600° C.

20. The system of claim 17 , wherein:
the system further comprises a venting port interposed between the hydrodesulfurization reactor and the first distillation tower, and fluidly connected to both;
the first distillation tower is configured to operate at a cut point of fro

Assignees

• Saudi Arabian Oil Co

Inventors

• Choi Ki-Hyouk

Classifications

• C07C13/68

  with a bridged ring system · CPC title

• C07C2/50

  Diels-Alder conversion · CPC title

• C10G9/00

  Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils · CPC title

• C10G45/10

  containing platinum group metals or compounds thereof · CPC title

• C10G45/08 Primary

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title