Two stage catalytic process for mixed pyrolysis oil upgrading to BTEX

Patent metadata

Field	Value
Publication number	US-12227706-B2
Application number	US-202218046034-A
Country	US
Kind code	B2
Filing date	Oct 12, 2022
Priority date	Oct 12, 2022
Publication date	Feb 18, 2025
Grant date	Feb 18, 2025

Abstract

In accordance with one or more embodiments of the present disclosure, a multi-stage process for upgrading a mixed pyrolysis oil comprising polyaromatic compounds to benzene, toluene, ethylbenzene, and xylenes (BTEX) includes combining light pyrolysis oil with heavy pyrolysis oil to form the mixed pyrolysis oil; upgrading the mixed pyrolysis oil in a slurry-phase reactor zone to produce intermediate products, wherein the slurry-phase reactor zone comprises a mixed metal oxide catalyst; and hydrocracking the intermediate products in a fixed-bed reactor zone to produce the BTEX, wherein the fixed-bed reactor zone comprises a mesoporous zeolite-supported metal catalyst.

First claim

What is claimed is:

1. A multi-stage process for upgrading a mixed pyrolysis oil comprising polyaromatic compounds to benzene, toluene, ethylbenzene, and xylenes (BTEX), the method comprising:
combining light pyrolysis oil, wherein the light pyrolysis oil comprises paraffins, BTEX, mono-aromatics, naphthalenes, indenes, mono-naphthenes, and dicyclopentadiene, with heavy pyrolysis oil to form the mixed pyrolysis oil;
upgrading the mixed pyrolysis oil in a slurry-phase reactor zone to produce intermediate products, wherein the slurry-phase reactor zone comprises a mixed metal oxide catalyst; and
hydrocracking the intermediate products in a fixed-bed reactor zone to produce the BTEX, wherein the fixed-bed reactor zone comprises a mesoporous zeolite-supported metal catalyst.

2. The multi-stage process of claim 1 , wherein the mixed metal oxide catalyst comprises two or more of Fe 2 O 3 , ZrO 2 , CeO 2 , Al 2 O 3 , TiO 2 , MoO 3 , Co 2 O 3 , and NiO.

3. The multi-stage process of claim 1 , wherein the mixed metal oxide catalyst comprises:
from 70 wt. % to 90 wt. % Fe 2 O 3 ;
from 5 wt. % to 60 wt. % ZrO 2 ;
from 1 wt. % to 4 wt. % CeO 2 ; and
from 5 wt. % to 10 wt. % Al 2 O 3 ,

where wt. % is calculated based on the total amount of oxides.

4. The multi-stage process of claim 1 , wherein the metal of the mesoporous zeolite-supported metal catalyst comprises molybdenum.

5. The multi-stage process of claim 4 , wherein the metal of the mesoporous zeolite-supported metal catalyst further comprises nickel, cobalt, or a combination thereof.

6. The multi-stage process of claim 4 , wherein the mesoporous zeolite-supported metal catalyst comprises from 2 wt. % to 20 wt. % molybdenum, and from 0.1 wt. % to 5 wt. % of nickel, cobalt, or a combination thereof.

7. The multi-stage process of claim 6 , wherein the mesoporous zeolite-supported metal catalyst comprises:
from 5 wt. % to 15 wt. % molybdenum; and
from 0.5 wt. % to 3 wt. % nickel.

8. The multi-stage process of claim 4 , wherein the zeolite support comprises a zeolite selected from the group consisting of zeolite Beta, ZSM-5, Mordenite, Zeolite Y, and combinations thereof.

9. The multi-stage process of claim 8 , wherein the zeolite support comprises a zeolite selected from the group consisting of zeolite Beta, Zeolite Y, and combinations thereof.

10. The multi-stage process of claim 9 , wherein the zeolite support has a silica to alumina ratio of from 10 to 50.

11. The multi-stage process of claim 9 , wherein the zeolite support comprises zeolite Beta.

12. The multi-stage process of claim 11 , wherein the zeolite support has a silica to alumina ratio of from 20 to 45.

13. The multi-stage process of claim 1 , wherein 25% to 45% of the mixed pyrolysis oil is converted to BTEX.

14. The multi-stage process of claim 1 , wherein the mixed pyrolysis oil comprises:
from 5 wt. % to 40 wt. % light pyrolysis oil; and
from 60 wt. % to 95 wt. % heavy pyrolysis oil.

15. The multi-stage process of claim 1 , wherein the mixed pyrolysis oil comprises dicyclopentadiene.

16. The multi-stage process of claim 15 , wherein the multi-stage process consumes from 80% to 100% of the dicyclopentadiene in the mixed pyrolysis oil.

17. The multi-stage process of claim 1 , wherein the light pyrolysis oil comprises from from 1 wt. % to 20 wt. % BTEX.

18. The multi-stage process of claim 1 , wherein the light pyrolysis oil comprises from 1 wt. % to 30 wt. % paraffins, from 1 wt. % to 20 wt. % BTEX, from 10 wt. % to 90 wt. % mono-aromatics, from 1 wt. % to 15 wt. % naphthalenes, from 1 wt. % to 30 wt. % indenes, from 1 wt. % to 15 wt. % mono-naphthenes, and from 1 wt. % to 60 wt. % dicyclopentadiene.

19. The multi-stage process of claim 1 , wherein the heavy pyrolysis oil comprises mono-aromatics, di-aromatics, tri-aromatics, tetra-aromatics, penta-aromatics, hexa-aromatics, and hepta and greater aromatics.

Assignees

• Saudi Arabian Oil Co
• Sabic Global Technologies Bv

Inventors

• Sun Miao
• Shaikh Sohel K
• Supronowicz Wojciech Andrzej
• Subramani Chandrasekar
• Albaher Eman Z

Classifications

• C10G2400/30

  Aromatics · CPC title

• B01J29/045

  containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium · CPC title

• B01J23/83

  with rare earths or actinides · CPC title

• B01J21/04

  Alumina · CPC title

• C10G47/20

  the catalyst containing other metals or compounds thereof · CPC title