Processes for upgrading alkanes and alkyl aromatic hydrocarbons

Patent metadata

Field	Value
Publication number	US-11680029-B2
Application number	US-202117166082-A
Country	US
Kind code	B2
Filing date	Feb 3, 2021
Priority date	Mar 6, 2020
Publication date	Jun 20, 2023
Grant date	Jun 20, 2023

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 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. The process can also include (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. The process can also include (III) contacting an additional quantity of the hydrocarbon-containing feed with at least a portion of the regenerated 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 catalyst in step (III) can be ≤5 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 Pt 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 alkanes, or one or more C 5 -C 16 alkyl aromatics, or a mixture thereof;
the hydrocarbon-containing feed and 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 and any C 5 -C 16 alkyl aromatics in the hydrocarbon-containing feed;
the hydrocarbon-containing feed and catalyst are contacted in the presence of 0.1 vol % to 30 vol % steam, based on a total volume of the hydrocarbon-containing feed;
the catalyst comprises from >0.025 wt % to 6 wt % of Pt 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 Pt in the regenerated catalyst is at a higher oxidized state as compared to the Pt 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 Pt in the regenerated and reduced catalyst is reduced to a lower oxidation state as compared to the Pt 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 ≤30 minutes.

2. The process of claim 1 , wherein in step (I), the hydrocarbon-containing feed and catalyst are contacted in the presence of 0.5 vol % to 20 vol % steam, based on a total volume of the hydrocarbon-containing feed.

3. 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%.

4. 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%.

5. The process of claim 1 , wherein in step (IIa), at least one of the following is met:
(i) the regenerated catalyst and reducing gas are contacted at a temperature in a range from 450° C. to 900° C.; and
(ii) the regenerated catalyst and reducing gas are contacted at a reducing agent partial pressure of 20 kPa-absolute to 10,000 kPa-absolute.

6. The process of claim 1 , wherein the hydrocarbon-containing feed further comprises an inert gas.

7. The process of claim 1 , wherein in step (I), at least one of the following is met:
(i) the hydrocarbon-containing feed and catalyst are contacted at a temperature in a range from 600° C. to 900° C.; and
(ii) the hydrocarbon-containing feed and 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 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 total 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 1 , wherein the catalyst further comprises up to 5 wt % of an alkali metal element based on the total 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.

11. The process of claim 1 , wherein the support comprises at least 3 wt % of a Group 2 element.

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

13. 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.

14. 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.

15. 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.

16. 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.

17. 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.

18. The process of claim 1 , wherein in step (IIa), the regenerated catalyst and the reducing gas are contacted at a temperature >720° C. for a time period of <1 minute.

19. The process of claim 1 , wherein:
in step (I), the hydrocarbon-containing feed and catalyst are contacted in the presence of 0.5 vol % to 20 vol % steam, based on a total volume of the hydrocarbon-containing feed; and
in step (IIa), the regenerated catalyst and the reducing gas are contacted at a temperature >720° C. for a time period of <1 minute.

20. A process for upgrading a hydrocarbon, comprising:
(I) contacting a hydrocarbon-containing feed with a catalyst comprising Pt 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 alkanes, or one or more C 5 -C 16 alkyl aromatics, or a mixture thereof;
the hydrocarbon-containing feed and 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 and any C 8 -C 16 alkyl aromatics in the hydrocarbon-containing feed;
the hydrocarbon-containing feed and

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Bao Xiaoying

Classifications

• B01J23/96

  of catalysts comprising metals, oxides or hydroxides of the noble metals · CPC title

• C07C5/3337 Primary

  of the platinum group · CPC title

• C07C2523/42

  Platinum · CPC title

• B01J38/10

  using elemental hydrogen · CPC title

• B01J38/12

  Treating with free oxygen-containing gas · CPC title