Catalyst complex and use thereof in alkane oligomerization

Patent metadata

Field	Value
Publication number	US-9828310-B2
Application number	US-201715412523-A
Country	US
Kind code	B2
Filing date	Jan 23, 2017
Priority date	Sep 10, 2013
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

Provided is a Group 9 novel metal catalyst complex further comprising a ketone-containing cocatalyst. The metal catalyst complex is useful in generating olefins from alkanes with great efficiency. In one embodiment, provided is an iridium catalyst complex useful in the dehydrogenation of alkanes comprising a ketone-containing cocatalyst and iridium complexed with a tridentate ligand. Also provided is a novel dehydrogenation method which utilizes the catalyst composition. In other embodiments, a novel process for preparing oligomers from alkanes utilizing the catalyst composition is provided.

First claim

That which is claimed is:

1. A method of dehydrogenating alkanes which comprises contacting an alkane under dehydrogenation conditions in the presence of a catalyst composition comprising a ketone containing cocatalyst and a Group 9 metal complex, wherein the metal complex is a composition of the formula LMX(X′) n , where n=0, 1 or 2;
X and X′ are moieties into which a monomer can insert or which can be eliminated from the metal center to generate a fragment LM;
M is a Group 9 metal; and
L is a tridentate ligand with L having the formula:

wherein A and A′ are independently selected from the group consisting of:

R 1 , R 2 , R 3 and R* are independently selected from the group consisting of halide, hydride, triflate, acetate, borate, C 1 through C 12 alky, C 1 through C 12 alkoxy, C 3 through C 12 cycloalkyl, C 3 through C 12 cycloalkoxy, C 6 through C 14 aryl, C 7 through C 17 aralkyl and olefins;
and Y is selected from the group consisting of C—H, C—Cl, C—Br, C—I, N, P, C—OR 4 , wherein R 4 is hydrogen, an optionally substituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or other leaving group; and p=0, 1 or 2.

2. The method of claim 1 wherein the ligand is 2, 6-bis (di-iso-propylphosphino) phenyl-1.

3. The method of claim 1 , wherein the reaction is run with a high boiling alkane having a boiling point of at least 200° C., in an open reactor.

4. The method of claim 3 , wherein the alkane is a C 12 or higher alkane.

5. The method of claim 1 , wherein the dehydrogenation reaction is run in the presence of oxygen.

6. The method of claim 1 , wherein the reaction is run in a closed system.

7. The method of claim 6 , wherein the reaction is run with an alkane which is lower than a C 12 alkane.

8. The method of claim 1 , wherein an olefin product is recovered.

9. The method of claim 5 , wherein the contacting is conducted in the gaseous phase.

10. The method of claim 5 , wherein an olefin product is further reacted within the reactor system.

11. A process for preparing oligomers from an alkane, comprising
(a) contacting an alkane under dehydrogenation conditions in accordance with the method of claim 1 to form olefins,
(b) contacting the olefins prepared in step (a) under oligomerization conditions with an oligomerization catalyst to prepare oligomers of the olefins, and
(c) hydrogenating the olefin oligomers,
with all reactions occurring in a single reactor.

12. The process of claim 11 , wherein the oligomerization catalyst of step (b) comprises a nickel, platinum or palladium metal catalyst complex comprising the metal complexed with a nitrogen containing bi- or tridentate ligand.

13. The process of claim 12 , wherein the metal catalyst complex of step (b) is of the formula LMX(X′) n , where n=0, 1 or 2;
X and X′ are moieties into which a monomer can insert;
M is selected from the group consisting of nickel, platinum and palladium; and
L is a nitrogen containing bi- or tridentate ligand.

14. The process of claim 13 , wherein L is a benzimidazolyl based ligand.

15. The process of claim 13 , wherein X and X′ are independently selected from the group consisting of halides, hydride, triflate, acetates, borates, C 1 through C 12 alky, C 1 through C 12 alkoxy, C 3 through C 12 cycloalkyl, C 3 through C 12 cycloalkoxy, C 6 through C 14 aryl, C7 through C17 aralkyl and olefins.

16. The process of claim 13 , wherein L has the formula

wherein A and A′ are independently selected from the group consisting of:

R 1 , R 2 , R 3 and R* are independently selected from the group consisting of halide, hydride, triflate, acetate, borate, C 1 through C 12 alky, C 1 through C 12 alkoxy, C 3 through C 12 cycloalkyl, C 3 through C 12 cycloalkoxy, C 6 through C 14 aryl, C 7 through C 17 aralkyl and olefins;
and Y is selected from the group consisting of C—H, C—Cl, C—Br, C—I, N, P, C—OR 4 , wherein R 4 is hydrogen, an optionally substituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or other leaving group; and p=0, 1 or 2.

17. The process of claim 13 , wherein the olefins of step (b) are contacted with a combination of the metal catalyst complex and a co-catalyst.

18. The process of claim 11 , wherein said alkane is selected from the group consisting of straight chain alkanes, branched chain alkanes and cycloalkanes.

19. The process of claim 18 , wherein said alkane is a straight chain or branched chain alkane.

20. The process of claim 11 , wherein the oligomerization catalyst is a nickel, platinum or palladium metal catalyst complex, and the ligands are the same as in the Group 9 metal catalyst complex.

21. The method of claim 1 , wherein the Group 9 metal is iridium.

22. The method of claim 1 , wherein the ketone cocatalyst comprises benzophenone.

Assignees

• Chevron Usa Inc
• Univ Rutgers

Inventors

• Goldman Alan Stuart
• Stibrany Robert Timothy
• Saxton Robert J
• Mironov Oleg

Classifications

• C07C2531/24

  Phosphines · CPC title

• B01J31/183

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title

• C07C5/333

  Catalytic processes · CPC title

• C07C2531/02

  containing organic compounds or metal hydrides · CPC title

• C07C5/48

  with oxygen as an acceptor · CPC title