Processes for selective dehydrohalogenation of halogenated alkanes

• US 9,663,424 B2
• Filed: 08/16/2013
• Issued: 05/30/2017
• Est. Priority Date: 07/25/2003
• Status: Expired due to Term

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Wang, Haiyou, Mukhopadhyay, Sudip, Tung, Hsueh Sung
• Primary Examiner(s): Brooks, Clinton
• Application Number:
  US13/968,801
• Publication Number:
  US 20140012049A1
• Time in Patent Office: 1,383 Days
• Field of Search: None
• 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 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 selected from the group consisting of LiCl/C, KCl/C, MgCl2/C, NiCl2/C, LiF/C, MgF₂/C, AlF₃, Fe/C, Co/C, Ni/C, Cu/C and combinations of these.

2. The process of claim 1, wherein the catalyst is a metal-based catalyst comprising Li, Na, K, Mg or a combination of these.

3. The process of claim 1, wherein the catalyst is a metal-based catalyst component selected from the group consisting of LiCl, KCl/C and MgCl₂/C.

4. The process of claim 1, wherein the dehydrohalogenation is conducted in a gas phase.

5. The process of claim 1 wherein said HFO-1234ze consists essentially of a mixture of cis-HFO-1234ze and trans-HFO-1234ze.

6. The process of claim 1 wherein said catalyst is LiCl supported on by a carbon substrate.

7. The process of claim 1 wherein said dehydrohalogenation step is conducted under a reaction temperature condition of from about 300°

C. to less than about 400°

C.

8. The process of claim 1 wherein said dehydrohalogenation step is conducted under a reaction temperature condition of from about 325°

C. to about 375°

C.

9. The process of claim 1 wherein said dehydrohalogenation step is conducted under a reaction temperature condition of about 350°

C.

10. The process of claim 1 wherein said dehydrohalogenation step is conducted under a reaction pressure condition of from about 5 torr to about 200 psig.

12. The process of claim 1 wherein said dehydrohalogenation step comprises conditions effective to convert at least about 80% by weight of said HCFC-244fa to said olefin stream comprising HFO-1234ze.

13. The process of claim 1 wherein said dehydrohalogenation step comprises conditions effective to convert at least about 90% by weight of said HCFC-244fa to said HFO-1234ze.

14. The process of claim 1 wherein said HFO-1234ze comprises trans-HFO-1234ze.

15. The process of claim 1 wherein said HFO-1234ze comprises cis-HFO-1234ze.

11. 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 comprising one or more of Li, Na, K, Mg or a combination of these and wherein the metal-based catalyst component is selected from the group consisting of LiCl, KCl/C and MgCl2/C.

16. The process of claim 11 wherein said dehydrohalogenation step comprises conditions effective to convert at least about 80% by weight of said HCFC-244fa to said HFO-1234ze.

17. The process of claim 11 wherein said dehydrohalogenation step comprises conditions effective to convert at least about 90% by weight of said HCFC-244fa to said olefin stream comprising HFO-1234ze.

18. The process of claim 11 wherein said HFO-1234ze comprises trans-HFO-1234ze.

19. The process of claim 11 wherein said HFO-1234ze comprises cis-HFO-1234ze.

20. The process of claim 11 wherein said HFO-1234ze consists essentially of a mixture of cis-HFO-1234ze and trans-HFO-1234ze.

21. The process of claim 11 wherein said catalyst is LiCl supported on by a carbon substrate.

22. The process of claim 11 wherein said dehydrohalogenation step is conducted under a reaction temperature condition of from about 300°

C. to less than about 400°

C.

23. The process of claim 11 wherein said dehydrohalogenation step is conducted under a reaction temperature condition of from about 325°

C. to about 375°

C.

24. The process of claim 11 wherein said dehydrohalogenation step is conducted under a reaction temperature condition of about 350°

C.

25. The process of claim 11 wherein said dehydrohalogenation step is conducted under a reaction pressure condition of from about 5 torr to about 200 psig.