Process for the production of chlorofluorinated aromatic hydrocarbons

• US 4,012,453 A
• Filed: 12/22/1975
• Issued: 03/15/1977
• Est. Priority Date: 12/22/1975
• Status: Expired due to Term

• Current Assignee: Allied Chemical Corporation (Honeywell International Inc.)
• Original Assignee: Allied Chemical Corporation (Honeywell International Inc.)
• Inventors: Eibeck, Richard E., Berenbaum, Morris B., Robinson, Martin A., Nychka, Henry R.
• Primary Examiner(s): Horwitz, D.
• Application Number:
  US05/642,873
• Time in Patent Office: 449 Days
• Field of Search: 260/653.7, 260/650 F, 260/649 F, 260/651 F
• US Class Current: 570/143
• CPC Class Codes: C07C 17/15 with oxygen as auxiliary reagent, e.g. oxychlorination
• CPC Class Codes: C07C 17/156 of unsaturated hydrocarbons
• CPC Class Codes: C07C 25/13 containing fluorine

Abstract

Chlorofluorinated aromatic hydrocarbons may be effectively produced by an oxychlorofluorination process by reacting a gaseous mixture of a starting material selected from an aromatic hydrocarbon and an aromatic hydrohalocarbon in which the halo atoms are selected from chloro and fluoro, or mixtures thereof, an oxygen-containing gas, a chlorinating agent selected from the group consisting of HCl and Cl₂ and mixtures thereof, and HF, in the presence of a Deacon catalyst supported by a stable, inert metal salt carrier.

Claims

1. The process for the production of chlorofluorinated aromatic hydrocarbons by the oxychlorofluorination of aromatic hydrocarbons which comprises reacting a gaseous mixture of a starting material selected from an aromatic hydrocarbon and an aromatic hydrohalocarbon in which the halo atoms are selected from chloro and fluoro, or mixtures thereof, at least 0.10 mole oxygen in an oxygen-containing gas, at least 0.25 mole HCl or equivalent of Cl₂ for each C--H bond and C=C bond desired to be reacted in the starting material, and HF, in the presence of a Deacon catalyst supported by a stable, inert metal salt carrier, with the weight percentage of cation in the Deacon catalyst ranging from about 0.6-20 based on the total cation content of the Deacon catalyst and metal salt carrier, at elevated temperatures and with a contact time of from about 0.1-20 seconds.

2. The process according to claim 1 in which the starting material is an aromatic hydrocarbon.

3. The process according to claim 1 in which the catalyst bed is maintained as a fixed bed and in which the contact time is from about 0.1-18 seconds.

4. The process according to claim 3 in which the contact time is from about 2-5 seconds.

5. The process according to claim 1 in which the catalyst bed is maintained as a dynamic bed.

6. The process according to claim 5 in which the catalyst bed is maintained as a fluidized bed and in which the contact time is from about 3-20 seconds.

7. The process according to claim 6 in which the contact time is from about 6-12 seconds.

8. The process according to claim 1 in which at least 0.25 mole oxygen in an oxygen-containing gas and at least 0.25 mole HCl or equivalent of Cl₂ for each C--H bond and non-aromatic C=C bond present in the starting material is employed.

9. The process according to claim 1 in which at least 0.50 mole oxygen in an oxygen containing gas and at least 0.50 mole HCl or equivalent of Cl₂ for each C--H bond and non-aromatic C=C bond present in the starting material is employed.

10. The process according to claim 1 in which the Deacon catalyst is a metal halide.

11. The process according to claim 10 in which the Deacon catalyst is promoted with a metal salt in which the metal is selected from the group consisting of Li, Na, K, Rb, La and Cs.

12. The process according to claim 1 in which the Deacon catalyst is a copper halide.

13. The process according to claim 1 in which the Deacon catalyst is CuCl₂.

14. The process according to claim 1 in which the carrier is a metal salt in which the metal is selected from the group consisting of Al, Mg, Ca, Ba, V, Th, Sr, Co, Ni, Cd, Pb, Cr and Fe, or combinations thereof.

15. The process according to claim 14 in which the anion of the salt is a fluoride.

16. The process according to claim 15 in which the metal salt is AlF₃.

17. The process according to claim 16 in which the AlF₃ is substantially in alpha form.

18. The process according to claim 2 in which at least 0.75 mole oxygen in an oxygen-containing gas per C--H bond in the starting material is employed.

19. The process according to claim 18 in which the aromatic hydrocarbon is benzene.

20. The process according to claim 18 in which the aromatic hydrocarbon is an alkyl benzene containing from 1-6 carbon atoms in the alkyl group.

21. The process according to claim 18 in which the aromatic hydrocarbon is a dialkyl benzene containing from 1-6 carbon atoms in each alkyl group.

22. The process according to claim 18 in which the aromatic hydrocarbon is a fused ring compound.

23. The process according to claim 18 in which the aromatic hydrocarbon is a diphenylalkane containing from 1-6 carbon atoms in the alkane moiety.

24. The process according to claim 18 in which the aromatic hydrocarbon is toluene.

25. The process according to claim 18 in which the aromatic hydrocarbon is benzene.

26. The process according to claim 18 in which the aromatic hydrocarbon is xylene.

27. The process according to claim 18 in which the aromatic hydrocarbon is naphthalene.

28. The process according to claim 18 in which the contact time is from about 2-12 seconds.

29. The process according to claim 18 in which the starting material containing a gaseous mixture is diluted with an inert gas.

30. The process according to claim 18 in which one or more halogenated aromatic hydrocarbons from the product mixture are recycled to the reaction mixture.

31. The process according to claim 18 in which the weight percentage of cation in the Deacon catalyst ranges from about 1-16 based on the total cation content of the Deacon catalyst and metal salt carrier.

32. The process according to claim 18 in which the catalyst bed is maintained as a dynamic bed.

33. The process according to claim 31 in which the catalyst bed is maintained as a fluidized bed.

34. The process according to claim 31 in which the elevated temperatures range from about 300°

-500°

C.

35. The process according to claim 31 in which the Deacon catalyst is a metal halide.

36. The process according to claim 35 in which the Deacon catalyst is promoted with a metal salt in which the metal is selected from the group consisting of Li, Na, K, Rb, La and Cs.

37. The process according to claim 31 in which the Deacon catalyst is a copper halide.

38. The process according to claim 31 in which the Deacon catalyst is CuCl₂.

39. The process according to claim 31 in which the carrier is a metal salt in which the metal is selected from the group consisting of Al, Mg, Ca, Ba, V, Th, Sr, Co, Ni, Cd, Pb, Cr and Fe.

40. The process according to claim 39 in which the anion of the salt is a fluoride.

41. The process according to claim 40 in which the metal salt is AlF₃.

42. The process according to claim 31 in which the aromatic hydrocarbon is benzene.

43. The process according to claim 31 in which the aromatic hydrocarbon is toluene.

44. The process according to claim 33 in which the aromatic hydrocarbon is xylene.

45. The process according to claim 31 in which one or more halogenated aromatic hydrocarbons from the product mixture are recycled to the reaction mixture.

46. The process according to claim 31 in which the reaction gas mixture is diluted with an inert gas.

47. The process according to claim 31 in which the weight percent of cation in the Deacon catalyst ranges from about 2-8 based on the total cation content of the Deacon catalyst and metal salt.

48. The process according to claim 31 in which the Deacon catalyst is a metal halide and in which the carrier is a metal salt in which the metal is selected from the group consisting of Al, Mg, Ca, Ba, Th, Sr, Co, Ni, Cd, Pb, Cr and Fe.

49. The process according to claim 48 in which the Deacon catalyst is CuCl₂.

50. The process according to claim 48 in which the anion of the metal salt carrier is a fluoride.

51. The process according to claim 50 in which the metal salt is AlF₃.

52. The process according to claim 49 in which the metal salt carrier is AlF₃.

53. The process according to claim 51 in which the AlF₃ is substantially in the alpha form.

54. The process according to claim 48 in which one or more halogenated aromatic hydrocarbons from the product mixture are recycled to the reaction mixture.

55. The process for the production of chlorofluorinated aromatic hydrocarbons by the oxychlorofluorination of aromatic hydrocarbons which comprises reacting a gaseous mixture of a starting material selected from an aromatic hydrocarbon and an aromatic hydrohalocarbon in which the halo atoms are selected from chloro and fluoro, or mixtures thereof, at least 0.25 mole oxygen in an oxygen-containing gas for each C--H bond in the starting material, at least 2 mole HCl or equivalent Cl₂ per mole of starting material, and HF, in the presence of a Deacon catalyst supported by a stable, inert metal salt carrier, with the weight percentage of cation in the Deacon catalyst ranging from about 0.6-20 based on the total cation content of the Deacon catalyst and metal salt carrier, at elevated temperatures and with a contact time of from about 0.1-20 seconds.