Flexible benzene production via selective-higher-olefin oligomerization of ethylene

Patent metadata

Field	Value
Publication number	US-12435016-B2
Application number	US-202318225967-A
Country	US
Kind code	B2
Filing date	Jul 25, 2023
Priority date	Jul 28, 2022
Publication date	Oct 7, 2025
Grant date	Oct 7, 2025

Abstract

The present disclosure relates to the integration of systems and methods associated with steam cracking, oligomerization reactions, hydrogenation reactions, and aromatization reactions for the production of benzene via the hydrogenation of oligomers produced from ethylene. In some aspects, the disclosed systems and methods utilize one or more of an oligomerization process, a hydrotreating process, and an aromatization process for producing a benzene comprising effluent. In further aspects, the systems and methods disclosed herein utilize one or more selective oligomerization catalyst systems.

First claim

What is claimed is:

1. A method comprising:
contacting, in an oligomerization process, ethylene with a selective-higher-olefin catalyst to yield an oligomerization reactor effluent comprising C 6 hydrocarbons which include 1-hexene and C 8 hydrocarbons which include 1-octene;
recovering 1-hexene and 1-octene from the oligomerization reactor effluent;
contacting, in a hydrotreating process, 1-hexene, 1-octene, or both 1-hexene and 1-octene recovered from the oligomerization reactor effluent with a hydrogenation catalyst to yield an aromatization feed comprising hexane, octane, or both; and
contacting, in an aromatization process, the aromatization feed with an aromatization catalyst to yield an aromatization effluent comprising benzene.

2. The method of claim 1 , wherein the C 6 hydrocarbons are present in an amount of about 20 wt. % to about 99 wt. % based on a total weight of the oligomerization reactor effluent, and the C 8 hydrocarbons are present in an amount of about 0.1 wt. % to about 75 wt. % based on a total weight of the oligomerization reactor effluent.

3. The method of claim 1 , wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises:
fractionating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons comprising C 9+ hydrocarbons and spent catalyst, a second stream comprising octenes, and a third stream comprising hexenes,
wherein, of the first stream, the second stream, and the third stream, only a portion of the third stream is fed to the hydrotreating process.

4. The method of claim 1 , wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises:
fractionating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons comprising C 9+ hydrocarbons and spent catalyst, a second stream comprising octenes, and a third stream comprising hexenes,
wherein, of the first stream, the second stream, and the third stream, only a portion of the second stream and only a portion of the third stream are fed to the hydrotreating process.

5. The method of claim 1 , wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises:
fractionating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons comprising C 9+ hydrocarbons and spent catalyst and a second stream comprising hexenes and octenes,
wherein, of the first stream and the second stream, only a portion of the second stream is fed to the hydrotreating process.

6. The method of claim 1 , wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises:
fractionating the oligomerization reactor effluent into a first stream comprising spent catalyst and a second stream comprising hexenes, octenes, and heavy hydrocarbons comprising C 9+ hydrocarbons,
wherein, of the first stream and the second stream, only a portion of the second stream is fed to the hydrotreating process.

7. The method of claim 1 , wherein recovering 1-hexene and 1-octene from the oligomerization reactor effluent comprises:
separating the oligomerization reactor effluent into a first stream comprising heavy hydrocarbons comprising C 9+ hydrocarbons and spent catalyst, a second stream comprising octenes, and a third stream comprising hexenes;
fractionating the third stream to yield a 1-hexene stream and a C 6 feed stream; and
flowing the C 6 feed stream to the hydrotreating process.

8. The method of claim 1 , further comprising:
fractionating a refinery stream to recover a naphtha stream;
feeding the naphtha stream to the hydrotreating process; and
contacting, in the hydrotreating process, naphtha with the hydrogenation catalyst to yield one or more of n-hexane and n-octane in the aromatization feed.

9. The method of claim 1 , wherein the aromatization effluent further comprises toluene, ethylbenzene, xylene, 1-hexene, 1-octene, or a combination thereof, the method further comprising:
fractionating the aromatization effluent into a benzene stream, a toluene stream, a xylene stream, and a raffinate stream.

10. The method of claim 9 , wherein the aromatization process is further configured to produce a hydrogen effluent, the method further comprising:
flowing a portion of the benzene stream and a portion of the hydrogen effluent to a hydrogenation process to yield cyclohexane; and
feeding the cyclohexane to the oligomerization process.

11. The method of claim 1 , wherein the oligomerization reactor effluent further comprises cyclohexane and other hexanes, the method further comprising:
recovering cyclohexane and the other hexanes from the oligomerization reactor effluent;
flowing the other hexanes recovered from the oligomerization reactor effluent to the hydrotreating process; and
recycling cyclohexane recovered from the oligomerization reactor effluent to the oligomerization process.

12. The method of claim 1 , further comprising:
cracking ethane, propane, butane, pentane, naphtha, or mixtures thereof in a steam cracker to yield a cracker effluent comprising ethylene; and
flowing ethylene recovered from the cracker effluent to the oligomerization process.

13. The method of claim 12 , wherein the cracker effluent further comprises light hydrocarbons, the method further comprising:
using light hydrocarbons recovered from the cracker effluent as a cooling source for an oligomerization reactor in the oligomerization process, for a first fractionation process located downstream of the oligomerization process, for a second fractionation process located downstream of the aromatization process, or a combination thereof.

14. The method of claim 12 , further comprising:
recovering steam from the steam cracker; and
using steam as a heating source for the oligomerization process, for a first fractionation process located downstream of the oligomerization process, for a second fractionation process located downstream of the aromatization process, or a combination thereof.

15. The method of claim 12 , further comprising:
flowing a raffinate recovered from the aromatization process to the steam cracker; and
cracking the raffinate in the steam cracker.

16. The method of claim 1 , wherein the step of contacting ethylene and a selective-higher-olefin catalyst is performed in the presence of a diluent recovered from the aromatization effluent, wherein the diluent is a raffinate, benzene, toluene, xylene, branched alkanes, or combinations thereof.

17. The method of claim 1 , further comprising:
flowing a raffinate recovered from the aromatization process to a steam cracker; and
cracking the raffinate in the steam cracker.

18. The method of claim 1 , wherein the oligomerization reactor effluent further comprises C 9+ hydrocarbons, the method further comprising:
blending the C 9+ hydrocarbons, a raffinate stream obtained from the aromatization effluent, or both the C 9+ hydrocarbons and the raffinate stream into a motor fuel stream.

19. The method of claim 1 , further comprising:
flowing hydrogen obtained from the aromatization effluent to the oligomerization process, the hydrotreating process, or both the oligomerization process and the hydrotreating process.

20. A method comprising: contacting, in an oligomerization process, ethylene with a selective-higher-olefin catalyst to vield an oligomerization reactor effluent comprising C 6 hydrocarbons which include 1-hexene and C 8 hydrocarbons which include 1-octene;
contacting, in a hyd

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Bischof Steven M
• Hendrickson Gregory G
• Kilgore Uriah J
• Kreischer Bruce E
• Morrison Scott G
• Snell Ryan W
• Sydora Orson L

Classifications

• C07C7/09

  by fractional condensation · CPC title

• C07C5/327

  Formation of non-aromatic carbon-to-carbon double bonds only · CPC title

• C07C2529/62

  Noble metals · CPC title

• C07C9/15

  Straight-chain hydrocarbons · CPC title

• C07C5/03 Primary

  of non-aromatic carbon-to-carbon double bonds · CPC title