Processes for upgrading alkanes and alkyl aromatic hydrocarbons

Patent metadata

Field	Value
Publication number	US-11859136-B2
Application number	US-202217744830-A
Country	US
Kind code	B2
Filing date	May 16, 2022
Priority date	Mar 6, 2020
Publication date	Jan 2, 2024
Grant date	Jan 2, 2024

Abstract

Processes for upgrading a hydrocarbon. The process can include (I) contacting a hydrocarbon-containing feed with a catalyst that can include a Group 8-10 element or a compound thereof disposed on a support to effect conversion of the hydrocarbon-containing feed to produce a coked catalyst and an effluent. The process can also include (II) contacting the coked catalyst with an oxidant to effect combustion the coke to produce a regenerated catalyst. The process can also include (IIa) contacting the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst. The process can also include (III) contacting an additional quantity of the hydrocarbon-containing feed with the regenerated and reduced catalyst. A cycle time from the contacting the hydrocarbon-containing feed with the catalyst in step (I) to the contacting the additional hydrocarbon-containing feed with the regenerated and reduced catalyst in step (III) can be ≤1 hours.

First claim

What is claimed is:

1. A process for upgrading a hydrocarbon, comprising:
(I) contacting a hydrocarbon-containing feed with a catalyst comprising a Group 8-10 element disposed on a support to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce a coked catalyst and an effluent comprising one or more upgraded hydrocarbons and molecular hydrogen, wherein:
the hydrocarbon-containing feed comprises one or more of C 2 -C 16 linear or branched alkanes, or one or more of C 4 -C 16 cyclic alkalies, or one or more C 8 -C 16 alkyl aromatics, or a mixture thereof;
the hydrocarbon-containing teed and the catalyst are contacted at a temperature in a range from 300° C. to 900° C. under a hydrocarbon partial pressure of at least 20 kPa-absolute, wherein the hydrocarbon partial pressure is the total partial pressure of any C 2 -C 16 alkanes, any C 4 -C 16 cyclic alkanes, and any C 8 -C 16 alkyl aromatics in the hydrocarbon- containing feed;
the hydrocarbon-containing feed and the catalyst are contacted in a presence of steam at an amount from 0.1 vol % to 50 vol %, based on a total volume of any C 2 -C 16 alkanes, any C 4 -C 16 cyclic alkanes, and any C 8 -C 16 alkyl aromatics in the hydrocarbon-containing feed;
the catalyst comprises from 0.001 wt % to 6 wt % of the Group 8-10 element based. on the weight of the support; and
the one or more upgraded hydrocarbons comprise at least one of a dehydrogenated hydrocarbon, a dehydroaromatized hydrocarbon, and a dehydrocyclized hydrocarbon;
(II) contacting at least a portion of the coked catalyst with an oxidant to effect combustion of at least a portion of the coke to produce a regenerated catalyst lean in coke and a combustion gas, wherein at least a portion of the Group 8-10 element in the regenerated catalyst is at a higher oxidized state as compared to the Group 8-10 element in the catalyst contacted with the hydrocarbon-containing feed;
(IIa) contacting at least a portion of the regenerated catalyst with a reducing gas to produce a regenerated and reduced catalyst, wherein at a least a portion of the Group 8-10 element in the regenerated and reduced catalyst is reduced to a lower oxidation state as compared to the Group 8 - 10 element in the regenerated catalyst; and
(III) contacting an additional quantity of the hydrocarbon-containing feed with at least a portion of the regenerated and reduced catalyst to produce a re-coked catalyst and additional effluent, wherein a cycle time from the contacting the hydrocarbon-containing feed with the catalyst in step (I) to the contacting the additional quantity of the hydrocarbon-containing feed with the regenerated and reduced catalyst in step (III) is ≤1 hour.

2. The process of claim 1 , wherein the support comprises a mixed Mg/Al metal oxide, and wherein in step (I), the hydrocarbon-containing feed and. the catalyst are contacted in the presence of steam at an amount from 0.1 vol % to 30 vol %, based on a total volume of any C 2 -C 16 alkanes, any C 4 -C 16 cyclic alkanes, and any C 8 -C 16 alkyl aromatics in the hydrocarbon-containing feed.

3. The process of claim 1 , wherein the support comprises a mixed Mg/Al metal oxide, and wherein in step (I) the hydrocarbon-containing feed and the catalyst are contacted in the presence of steam at an amount from 1 vol % to 15 vol %, based on a total volume of any C 2 -C 16 alkanes, any C 4 -C 16 cyclic alkanes, and any C 8 -C 16 alkyl aromatics in the hydrocarbon-containing feed.

4. The process of claim 1 , wherein the hydrocarbon-containing feed comprises propane, wherein the upgraded hydrocarbon comprises propylene, and wherein contacting the hydrocarbon-containing feed with the catalyst in step (I) has a propylene yield of at least 57% at a propylene selectivity of ≥75%.

5. The process of claim 1 , wherein the hydrocarbon-containing feed comprises ≥85 vol % of propane, based on a total volume of the hydrocarbon-containing feed, wherein the hydrocarbon-containing feed and catalyst are contacted under a propane partial pressure of at least 100 kPa-absolute, and wherein contacting the hydrocarbon-containing feed with the catalyst in step (I) has a propylene yield of at least 57% at a propylene selectivity of ≥85%.

6. The process of claim 1 , wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a temperature in a range from >700° C. to 900° C.

7. The process of claim 1 , wherein in step (I), at least one of the following is met:
(i) the hydrocarbon-containing feed and the catalyst are contacted at a temperature in a range from 600° C. to 900° C.; and
(ii) the hydrocarbon-containing feed and the catalyst are contacted under a hydrocarbon partial pressure in a range from 20 kPa-absolute to 10,000 kPa-absolute.

8. The process of claim 1 , wherein in step (II), the coked catalyst and the oxidant are contacted at a temperature in a range from >700° C. to 1,100° C.

9. The process of claim 1 , wherein the catalyst further comprises up to 10 wt % of a promoter based on the weight of the support, and wherein the promoter comprises one or more of the following elements: Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, a combination thereof, or a mixture thereof.

10. The process of claim 9 , wherein:
the Group 8-10 element comprises Pt,
the support comprises at least 11 wt % of a Group 2 element based on the weight of the support, and.
the Group 2 element comprises Mg.

11. The process of claim 1 , wherein the catalyst further comprises up to 5 wt % of an alkali metal element based on the weight of the support, and wherein the alkali metal element comprises one or more of the following: Li, Na, K, Rb, Cs, a combination thereof, or a mixture thereof.

12. The process of claim 1 , wherein the support is produced by calcining hydrotalcite.

13. The process of claim 1 , wherein the support comprises a mixed Mg/Al metal oxide.

14. The process of claim 1 , wherein the cycle time is ≤30 minutes.

15. The process of claim 1 , wherein the catalyst is in a fixed bed when contacted with the hydrocarbon-containing feed.

16. The process of claim 1 , wherein:
the catalyst comprises 0.025 wt % of the Group 8-10 element,
the Group 8-10 element comprises Pt, and
the support comprises a mixed Mg/Al metal oxide.

17. The process of claim 1 ; wherein in step (II), the coked catalyst and the oxidant are contacted at a temperature in a range from ≥750° C. to 1,100° C.

18. The process of claim 1 , wherein in step (II), the coked catalyst and the oxidant are contacted at a temperature in a range from ≥800° C. to 1,100° C.

19. The process of claim 1 , wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a temperature in a range from ≥720° C. to 900° C.

20. The process of claim 1 , wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a temperature in a range from ≥750° C. to 900° C.

21. The process of claim 1 , wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted for a time period of <1 minute.

22. The process of claim 1 , wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a temperature >700° C. for a time period of <1 minute.

23. The process of claim 1 , wherein:
the support comprises a mixed Mg/Al metal oxide;
in step (I), the hydrocarbon-containing feed and the catalyst are contacted in the presence of

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Bao Xiaoying

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• C10G29/04 Primary

  Metals, or metals deposited on a carrier · CPC title

• B01J21/04

  Alumina · CPC title

• B01J21/10

  Magnesium; Oxides or hydroxides thereof · CPC title

• B01J23/10

  of rare earths · CPC title