PROCESSES FOR SELECTIVE DEHYDROHALOGENATION OF HALOGENATED ALKANES

• US 20140012049A1
• Filed: 08/16/2013
• Published: 01/09/2014
• Est. Priority Date: 07/25/2003
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: WANG, HAIYOU, TUNG, HSUEH SUNG, MUKHOPADHYAY, SUDIP
• Granted Patent: US 9,663,424 B2
• Time in Patent Office: Days
• US Class Current: 570/157
• CPC Class Codes: C07C 17/206 the other compound being HX
• CPC Class Codes: C07C 17/25 by splitting-off hydrogen halides from halogenated hydrocarbons
• CPC Class Codes: C07C 19/08 containing fluorine
• CPC Class Codes: C07C 21/18 containing fluorine

Abstract

Disclosed are processes for producing halogenated olefins, and preferably tetrafluorinated propene(s), from one or more alkanes having both fluorine substituents and non-fluorine substituents, preferably with a high degree of conversion and selectivity. Preferably the process comprises the use of a catalyzed reaction in which the catalyst is selected from the group consisting of activated carbons, halogentated mono- and di-valent metal oxides, mono- and di-valent Lewis acid metal halides, zero-valent metals, and combinations of these.

Claims

1. A process for the production fluorinated olefin having from three to six carbon atoms, the process comprising exposing a fluorinated and chlorinated alkane having from two to six carbon atoms and a degree of non-fluorine halogen substitution of N and a degree of fluorine substitution of M to conditions effective to convert at least about 20% by weight of said alkane to one or more olefins having a degree of non-fluorine halogen substitution of a N−

1 and a degree of fluorine substitution of M.

2. The process of claim 1 wherein said fluorinated olefins has the same number of carbon atoms as said alkane.

7. The process of claim 1 wherein said alkane is a compound in accordance with Formula (I) below:

CF₃CHYCHFY 

 

(I).

where Y is H or a halogen other than F, provided that at least one of said Y is H.

8. The process of claim 7 wherein said one or more olefins comprises a compound of Formula (II):

CF₃CX═

CHX 

 

(II)

where one of said X is H and the other of said X is F.

11. The process of claim 8 wherein said exposing step comprises conditions effective to convert at least about 70% by weight of said compounds of Formula (I) to one or more compounds of Formula (II).

12. The process of claim 8 wherein said exposing step comprises conditions effective to convert at least about 80% by weight of said compounds of Formula (I) to one or more compounds of Formula (II).

13. The process of claim 8 wherein said exposing step comprises conditions effective to convert at least about 90% by weight of said compounds of Formula (I) to one or more compounds of Formula (II).

15. The process of claim 1 wherein said fluorinated olefin having a degree of substitution of N+1 comprises hexafluorpropene.

16. The process of claim 1 wherein said fluorinated olefin having a degree of substitution of N+1 comprises pentafluorpropene.

17. The process of claim 1 wherein said alkane comprises chlorotrifluorpropane (HCFC-244).

18. The process of claim 1 wherein said at least one or more fluorinated olefins comprises CFH═

CFCF₃.

19. The process of claim 1 wherein said alkane comprises HCFC-244fa.

20. The process of claim 19 wherein said at least one or more olefins comprises HFO-1234ze.

21. The process of claim 1 wherein said exposing step comprises exposing said alkane to catalyst selected from the group consisting of activated carbons and/or metal-based catalyst.

22. The process of claim 21 wherein said exposing step comprises exposing said alkane to metal-based catalyst.

23. The process of claim 22 wherein said metal-based catalyst is selected from the group consisting of halogentated mono- and di-valent metal oxides, mono- and di-valent Lewis acid metal halides, zero-valent metals, and combinations of these.

24. The process of claim 22 wherein said metal-based catalyst comprises a catalyst containing at least one transition metal contained in one or more of Group VIIIA, Group IB and Group IIB of the periodic table.

28. The process of claim 22 wherein said metal-based catalyst is a zero valent metal based catalyst.

29. The process of claim 28 wherein said zero valent metal based catalyst comprises a catalyst containing at least one transition metal.

30. The process of claim 29 wherein said at least one transition metal comprises at least one transition metal contained in Group VIIIA and Group IB of the periodic table.

33. The process of claim 1 wherein said exposing step comprises exposing said alkane to catalyst selected from the group consisting of activated carbons and/or metal-based catalyst in which the metal(s) are in an oxidation state of 0, +1 or +2.

34. The process of claim 1 wherein said exposing step comprises a gas phase reaction in the presence of metal based catalyst, carbon catalyst, and combinations of these.

3. (canceled)

4. (canceled)

5. (canceled)

6. (canceled)

9. (canceled)

10. (canceled)

14. (canceled)

25. (canceled)

26. (canceled)

27. (canceled)

31. (canceled)

32. (canceled)

35. A process for the production of a fluorinated olefin comprising CF₃CH═

CFH (HFO-1234ze) comprising dehydrohalogenation of a fluorinated and chlorinated alkane comprising CF₃CH₂CHClF (HCFC-244fa), in the presence of a catalyst comprising activated carbon and one or more metal-based catalysts components comprising an alkali metal or alkali earth metal.

36. The process of claim 35, wherein the metal-based catalyst component comprises Li, Na, K, Mg or a combination of these.

37. The process of claim 35, wherein the metal-based catalyst component is selected from the group consisting of LiCl, KCl/C and MgCl₂/C.

38. The process of claim 35, wherein the dehydrohalogenation is conducted in a gas phase.