Upgrading ethane-containing light paraffins streams

Patent metadata

Field	Value
Publication number	US-10464864-B2
Application number	US-201715834209-A
Country	US
Kind code	B2
Filing date	Dec 7, 2017
Priority date	Dec 20, 2016
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

In a process for upgrading an ethane-containing C5- paraffin stream, the paraffin stream is contacted with an oxygen containing gas in the presence of a selective oxidation catalyst under conditions to selectively oxidize at least part of the ethane in the paraffin stream and produce a first product stream comprising ethylene. At least part of the first product stream is then with an oligomerization catalyst under conditions to oligomerize at least part of the ethylene and produce a second product stream comprising gasoline and/or distillate boiling range hydrocarbons. Gasoline and/or distillate boiling range hydrocarbons are then recovered from the second product stream and at least a part of any residual C5- paraffin stream is recycled to the selective oxidation step.

First claim

The invention claimed is:

1. A process for upgrading an ethane-containing C 5 - paraffin stream, the process comprising:
(a) contacting the ethane-containing C 5 -paraffin stream, wherein the ethane-containing C 5 -paraffin stream comprises at least about 80 wt % ethane and less than about 20 wt % methane, propane, butane, and pentane, with an oxygen containing gas in the presence of a selective oxidation catalyst under conditions to selectively oxidize at least part of the ethane in the C 5 -paraffin stream and produce a first product stream comprising ethylene and oxygenates selected from carboxylic acids and esters thereof, alcohols, aldehydes, ketones and mixtures thereof;
(b) contacting the first product stream which contains ethylene and oxygenates selected from carboxylic acids and esters thereof, alcohols, aldehydes, ketones and mixtures thereof with at least one oligomerization catalyst, without intermediate separation, under conditions to oligomerize at least part of the ethylene and produce a second product stream comprising gasoline and/or distillate boiling range hydrocarbons and a residual C 5 -paraffin stream; and
(c) recovering the gasoline boiling range hydrocarbons and/or distillate boiling range hydrocarbons from the second product stream and recycling at least a part of the residual C 5 - paraffin stream of the second product stream to the contacting step (a).

2. The process of claim 1 , wherein the ethane-containing C 5 -paraffin stream comprises ethane and propane.

3. The process of claim 1 , wherein the ethane-containing C 5 -paraffin stream comprises a natural gas liquid containing less than 20 wt % methane.

4. The process of claim 1 , where the ethane-containing C 5 -paraffin stream comprises less than 20 wt % propane.

5. The process of claim 1 , wherein the selective oxidation catalyst comprises a mixed metal oxide.

6. The process of claim 5 , wherein the mixed metal oxide is a mixed metal oxide of at least molybdenum and vanadium.

7. The process of claim 6 , wherein the mixed metal oxide is a mixed oxide of at least molybdenum, vanadium, and niobium.

8. The process of claim 1 , wherein the conditions in the contacting step (a) include a temperature from 200° C. to 700° C. and a pressure from 100 kPa-a to 6895 kPa-a.

9. The process of claim 1 , wherein at least 50% of the ethane selectively oxidized in the contacting step (a) is converted to ethylene.

10. The process of claim 1 , wherein the oligomerization catalyst comprises a molecular sieve.

11. The process of claim 10 , wherein the molecular sieve has a Constraint Index of 1-12.

12. The process of claim 10 , wherein the molecular sieve is selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.

13. The process of claim 10 , wherein the molecular sieve comprises ZSM-5.

14. The process of claim 10 , wherein the oligomerization catalyst further comprises a hydrogenation-dehydrogenation component.

15. The process of claim 14 , wherein the hydrogenation-dehydrogenation component comprises at least one of Ga, Pt, Pd, Zn, Ni, and Co or a compound thereof.

16. The process of claim 1 , wherein the oligomerization catalyst comprises a mixed metal oxide.

17. The process of claim 16 , wherein the mixed metal oxide is a mixed metal oxide of at least zirconium and tungsten.

18. The process of claim 1 , wherein the conditions in the contacting step (b) include a temperature from 300° C. to 550° C. and a pressure from 100 kPa-a to 5000 kPa-a.

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Cao Guang
• Dakka Jihad

Classifications

• C07C2529/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 · CPC title

• C07C2529/48

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

• C07C2529/072

  Iron group metals or copper · CPC title

• C07C2523/28

  Molybdenum · CPC title

• C07C2/24

  with metals · CPC title