CATALYTIC GAS PHASE FLUORINATION

• US 20140012051A1
• Filed: 01/21/2011
• Published: 01/09/2014
• Est. Priority Date: 01/21/2011
• Status: Active Grant

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Pigamo, Anne, Wendlinger, Laurent, Doucet, NIcloas
• Granted Patent: US 9,302,961 B2
• Time in Patent Office: Days
• US Class Current: 570/160
• CPC Class Codes: B01J 23/866 Nickel and chromium
• CPC Class Codes: B01J 23/90 Regeneration or reactivation
• CPC Class Codes: B01J 23/92 of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
• CPC Class Codes: B01J 23/94 of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
• CPC Class Codes: B01J 27/125 with scandium, yttrium, aluminium, gallium, indium or thallium
• CPC Class Codes: B01J 37/14 with gases containing free oxygen
• CPC Class Codes: B01J 37/26 Fluorinating
• CPC Class Codes: B01J 38/12 Treating with free oxygen-containing gas
• CPC Class Codes: C07C 17/20 of halogen atoms by other halogen atoms
• 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 21/18 containing fluorine
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

The invention relates to a fluorination process, alternately comprising reaction stages and regeneration stages, wherein the reaction stages comprise reacting a chlorinated compound with hydrogen fluoride in gas phase in the presence of a fluorination catalyst to produce a fluorinated compound, and the regeneration stages comprise contacting the fluorination catalyst with an oxidizing agent-containing gas flow.

Claims

1-20. -20. (canceled)

21. A fluorination process, alternately comprising reaction stages and regeneration stages, wherein the reaction stages comprise reacting a chlorinated compound with hydrogen fluoride in gas phase in the presence of a fluorination catalyst to produce a fluorinated compound, and the regeneration stages comprise contacting the fluorination catalyst with an oxidizing agent-containing gas flow.

22. The fluorination process of claim 21, further comprising a preliminary activation stage which comprises contacting the fluorination catalyst with an oxidizing agent-containing gas flow.

23. The process of claim 21, wherein the oxidizing agent-containing gas flow of the regeneration stage is an oxygen-containing gas flow.

24. The process of claim 21, wherein the regeneration stage comprises contacting the fluorination catalyst with the oxidizing agent-containing gas flow for at least 2 hours.

25. The process of claim 21, wherein the oxidizing agent-containing gas flow of the regeneration stage contains hydrogen fluoride in addition to the oxidizing agent, and wherein the proportion of oxidizing agent in the oxidizing agent-containing gas flow of the regeneration stage is from 2 to 98 mol %, relative to the total amount oxidizing agent and hydrogen fluoride.

26. The process of claim 21, wherein the oxidizing agent-containing gas flow of the regeneration stage does not contain hydrogen fluoride.

27. The process of claim 26, wherein the oxidizing agent-containing gas flow of the regeneration stage is air.

28. The process of claim 21, wherein the regeneration stage comprises contacting the fluorination catalyst with a hydrogen fluoride gas flow, either:

before contacting the fluorination catalyst with the oxidizing agent-containing gas flow;

or

after contacting the fluorination catalyst with the oxidizing agent-containing gas flow.

29. The process of claim 22, wherein the activation stage comprises a preliminary step of reacting the chlorinated compound with hydrogen fluoride in gas phase in the presence of the fluorination catalyst, prior to contacting the chlorinated compound with the oxidizing agent-containing gas flow.

30. The process of claim 21, wherein the oxidizing agent-containing gas flow is contacted with the fluorination catalyst during the regeneration stage at a temperature of from 250 to 500°

C.

31. The process of claim 21, wherein the fluorinated compound is a fluoroolefin.

32. The process of claim 21, wherein the chlorinated compound is selected from the group consisting of hydrochlorocarbons, hydrochlorofluorocarbons and hydrochlorofluoroolefins.

33. The process of claim 21, wherein the fluorination catalyst is supported on a support comprising fluorinated alumina, fluorinated chromia, fluorinated activated carbon or graphite carbon.

34. The process of claim 21, wherein the fluorination catalyst is an unsupported catalyst.

35. The process of claim 21, wherein the fluorination catalyst further comprises a co-catalyst comprising Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P, Ni or mixtures thereof, and wherein said co-catalyst is present in an amount from about 1-10 wt % of said fluorination catalyst.

36. The process of claim 21, wherein the fluorination catalyst is a mixed chromium/nickel catalyst, the atomic ratio of nickel to chromium being from 0.5 to 2.

37. The process of claim 21, wherein the chlorinated compound is 2-chloro-3,3,3-trifluoro-1-propene, and wherein the molar ratio of hydrogen fluoride to 2-chloro-3,3,3-trifluoro-1-propene is from 3:

1 to 150;

1.

38. The process of claim 21, wherein the reaction stages are carried out at a pressure of from 1 to 20 bars.

39. The process of claim 21, wherein the reaction stages are carried out at a temperature of from 200 to 450°

C.

40. The process of claim 21, wherein the contact time between hydrogen fluoride and the chlorinated compound during the reaction stages is from 6 to 100 s.

41. The process of claim 21, wherein the reaction stages are carried out in the presence of oxygen as the oxidizing agent, the ratio of oxygen being from 0.05 to 15 mole %, with respect to the total amount of chlorinated compound and oxygen.