Catalysts for 2-chloro-1,1,1,2-tetrafluoropropane dehydrochlorination

• US 9,180,433 B2
• Filed: 03/12/2014
• Issued: 11/10/2015
• Est. Priority Date: 03/14/2013
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Wang, Haiyou, Tung, Hsueh Sung
• Primary Examiner(s): Johnson, Edward
• Application Number:
  US14/206,587
• Publication Number:
  US 20140275649A1
• Time in Patent Office: 608 Days
• Field of Search: 502/328
• US Class Current: 1/1
• CPC Class Codes: B01J 21/10 Magnesium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 23/44 Palladium
• CPC Class Codes: B01J 23/58 with alkali- or alkaline earth metals
• CPC Class Codes: B01J 23/96 of catalysts comprising metals, oxides or hydroxides of the noble metals
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B01J 38/02 Heat treatment
• CPC Class Codes: B01J 38/10 using elemental hydrogen
• CPC Class Codes: B01J 38/12 Treating with free oxygen-containing gas
• CPC Class Codes: B01J 38/18 with subsequent reactive gas treating
• CPC Class Codes: C07C 17/087 to unsaturated halogenated hydrocarbons
• 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 19/10 and chlorine
• CPC Class Codes: C07C 21/18 containing fluorine
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

The present invention relates to a provides a catalyst comprising (a) a solid support comprising an alkaline earth metal oxide, fluoride, or oxyfluoride, and (b) at least one elemental metal disposed on or within said support, preferably wherein said elemental metal is present in an amount from about 0.01 to about 10 weight percent based upon the total weight of the metal and support. It also relates to the use of the catalyst for the dehydrochlorination of a hydrochlorofluorocarbon.

Claims

1. A catalyst comprising (a) a solid support comprising an alkaline earth metal oxide or oxyfluoride or combination thereof and (b) at least one elemental metal disposed on or within said support, wherein said elemental metal is present in an amount ranging from about 0.01 to about 10 weight percent based upon the total weight of the elemental metal and support, said elemental metal being one or more metals from Groups 7, 8, 9, 10, or 11 of the periodic table.

2. The catalyst according to claim 1 wherein the solid support comprises an alkaline earth oxide.

3. The catalyst according to claim 2 wherein the alkaline earth metal is magnesium, calcium, strontium or barium.

4. The catalyst according to claim 2 wherein the alkaline earth metal is magnesium.

5. The catalyst according to claim 1 wherein the elemental metal is an element of groups 8, 9, 10, or 11 of the periodic table.

6. The catalyst according to claim 1 wherein the elemental metal is an element of groups 9, 10, or 11 of the periodic table.

7. The catalyst according to claim 1, wherein the elemental metal is Pd, Ru, Pt, Rh, Ir, Fe, Co, Ni, Cu, Ag, Re, Os, Au or combination thereof.

8. The catalyst according to claim 7 wherein the elemental metal is Co, Rh, Ni, Pd, Pt or Ir or combination thereof.

9. The catalyst according to claim 7 wherein the elemental metal is Ru, Rh, Pd, Pt, or Ir or combination thereof.

10. The catalyst according to claim 9 wherein the elemental metal is present on or within said support in an amount ranging from about 0.1% to about 5% by weight.

11. The catalyst according to claim 10 wherein the elemental metal is present on or within said support in an amount ranging from about 0.1% to about 0.9 wt %.

12. A process for preparing a fluoroolefin from a hydrochlorofluorocarbon having at least one hydrogen atom and at least one chlorine atom on adjacent carbon atoms comprising dehydrochlorinating said hydrochlorofluorocarbon in the presence of a catalyst, said catalyst comprising (a) a solid support comprising an alkaline earth metal fluoride, oxide or oxyfluoride or combination thereof, and (b) at least one elemental metal disposed on or within said support, wherein said elemental metal is present in an amount from about 0.01 to about 10 weight percent based upon the total weight of the elemental metal and said solid support, said elemental metal being one or more metals from Groups 7, 8, 9, 10, or 11 of the periodic table or combination thereof.

13. The process according to claim 12 wherein the solid support comprises an alkaline earth oxide.

14. The process according to claim 12 wherein the alkaline earth metal is magnesium, calcium, strontium or barium.

15. The process according to claim 12 wherein the alkaline earth metal is magnesium.

16. The process according to claim 12 wherein the solid support comprises magnesium oxide.

17. The process according to claim 12, wherein the elemental metal is an element of groups 8, 9, 10, or 11 of the periodic table.

18. The process according to claim 17 wherein the elemental metal is an element of groups 9, 10, or 11 of the periodic table.

19. The process according to claim 17 elemental metal is elemental metal is wherein the elemental metal is Pd, Ru, Pt, Rh, Ir, Fe, Co, Ni, Cu, Ag, Os, Au or combination thereof.

20. The process according to claim 19 wherein the elemental metal is Co, RhNi, Pd, Pt or Ir or combination thereof.

21. The process according to claim 19 wherein the elemental metal is Ru, Rh, Pd, Pt, or Ir or combination thereof.

22. The process according to claim 21 wherein the elemental metal is present on or within said support in an amount ranging from about 0.1% to about 5% by weight.

23. The process according to claim 21 the elemental metal is present on or within said support in an amount ranging from about 0.1% to about 0.9 wt %.

24. The process according to claim 12 wherein the dehydrochlorinating takes place in the vapor phase and is conducted at a temperature ranging from about 200°

C. to about 800°

C.

25. The process according to claim 24 where the temperature of the dehydrochlorination reaction ranges from about 300°

C. to about 600°

C.

26. The process according to claim 12 where the dehydrochlorination reaction takes place in the vapor phase and is conducted at a pressure ranging from about 0 psig to about 200 psig.

27. The process according to claim 26 wherein the dehydrochlorination reaction is conducted at a pressure of about 10 psig to about 150 psig.

28. The process according to claim 12 wherein the hydrochlorofluorocarbon is 1,1,1,2-tetrafluoro-2-chloropropane and the fluoroolefin is 2,3,3,3-tetrafluoropropene.

29. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CHFCH₂Cl and the fluoroolefin is CF₃CF═

CH₂.

30. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CH₂CHFCl and the fluoroolefin is CF₃CH═

CHF (Z/E).

31. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CHClCH₂F and the fluoroolefin is CF₃CH═

CHF (Z/E).

32. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CFClCH₂F and the fluoroolefin is CF₃CF═

CHF (Z/E).

33. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CHFCHFCl and the fluoroolefin is CF₃CF═

CHF/(Z/E).

34. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CH₂CF₂Cl and the fluoroolefin is CF₃CH═

CF₂.

35. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CHClCHF₂ and the fluoroolefin is CF₃CH═

CF₂.

36. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CFClCHF₂ and the fluoroolefin is CF₃CF═

CF₂.

37. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CH₂CHCl₂ and the fluoroolefin is CF₃CH═

CHCl (Z/E).

38. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CHClCH₂Cl and the fluoroolefin is CF₃CCl═

CH₂ or CF₃CH═

CHCl (Z/E).

39. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CCl₂CH₃ and the fluoroolefin is CF₃CCl═

CH₂.

40. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CHFCHCl₂ and the fluoroolefin is CF₃CF═

CHCl (Z/E).

41. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CHClCHCl₂ (233da) and the fluoroolefin is CF₃CCl═

CHCl (Z/E) or CF₃CH═

CCl₂.

42. The process according to claim 12 wherein the hydrochlorofluorocarbon is CF₃CCl₂CH₂Cl and the fluoroolefin is CF₃CCl═

CHCl (Z/E).

43. A process for preparing 2,3,3,3-tetrafluoropropene comprising:

(i) providing a starting composition comprising a compound of Formulae I, II, or III;

CX₂═

CCl—

CH₂X 

 

(I);

CX₃—

CCl═

CH₂ 

 

(II);

or

CX₃—

CHCl—

CH₂X 

 

(III)

wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine;

(ii) contacting the starting composition with a first fluorinating agent to produce a first intermediate composition comprising 2-chloro-3,3,3-trifluoropropene and a first chlorine-containing byproduct;

(iii) contacting the first intermediate composition with a second fluorinating agent to produce a second intermediate composition comprising 2-chloro-1,1,1,2-tetrafluoropropane; and

(iv) dehydrochlorinating in the presence of a catalyst, at least a portion of the second intermediate composition comprising 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product comprising 2,3,3,3-tetrafluoropropene, said catalyst comprising (a) a solid support comprising an alkaline earth metal fluoride, oxide or oxyfluoride or combination thereof, and (b) at least one elemental metal disposed on or within said support, wherein said elemental metal is present in an amount ranging from about 0.01 to about 10 weight percent based upon the total weight of the metal and support, said elemental metal being one or more metals from Groups 7, 8, 9, 10, or 11 of the periodic table.

44. The process according to claim 43 wherein the solid support comprises an alkaline earth metal oxide.

45. The process according to claim 43 wherein the alkaline earth metal is magnesium, calcium, strontium or barium.

46. The process according to claim 43 wherein the alkaline earth metal is magnesium.

47. The process according to claim 43 wherein the elemental metal is Pd, Ru, Pt, Rh, Ir, Fe, Co, Ni, Cu, Ag, Re, Os, Au or combination thereof.