Dehydrofluorination of 245FA to 1234ZE
A method of producing a fluoropropane fluoropropene of formula CF 3 CH═CHF, comprising contacting a starting feed mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the gas phase with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated Cr 2 O 3 or Cr/Ni on fluoride alumina, in the presence of an oxygen containing gas, to form a mixture comprising Z-1,3,3,3-tetrafluoropropane Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3,-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane, separating the E-1,3,3,3-tetrafluoropropene from the Z-isomer and any unreacted 1,1,1,3,3-pentafluoropropane, if present, and recovering said E-1,3,3,3-tetrafluoropropene.
1 . A method of producing a fluoropropane of formula CF 3 CH═CHF, comprising:
a) contacting a mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in the gas phase with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated Cr 2 O 3 or Cr/Ni on fluorided alumina, in the presence of an oxygen containing gas, to form a mixture comprising Z-1,3,3,3-tetrafluoropropane, E-1,3,3,3,-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane,
b) separating the E-1,3,3,3-tetrafluoropropene from the Z-isomer and any unreacted 1,1,1,3,3-pentafluoropropane, if present, and
c) recovering said E-1,3,3,3-tetrafluoropropene.
2 . The method of claim 1 , wherein said mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene comprises at least 7% by weight Z-1,3,3,3-tetrafluoropropene.
3 . The method of claim 1 , wherein said mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene comprises at least 10% by weight Z-1,3,3,3-tetrafluoropropene.
4 . The method of claim 1 wherein at least 94% of the 1,1,1,3,3-pentafluoropropane is converted to E-isomer of 1,3,3,3-tetrafloropropene.
5 . The method of claim 1 , wherein at least 98% of the 1,1,1,3,3-pentafluoropropane is converted to E-isomer of 1,3,3,3-tetrafloropropene.
6 . The method of claim 1 , further comprising recovering Z-1,3,3,3-tetrafluoropropene, or a mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, and recycling Z-1,3,3,3-tetrafluoropropene, or a mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane back to step a).
7 . The process of claim 1 , wherein said hydrogen fluoride produced in step a) is separated and recovered.
8 . The process of step 1 wherein said oxygen containing gas is oxygen, or air.
9. A method of producing a fluoropropene of formula CF 3 CH═CHF, comprising:
a) vaporizing a starting feed mixture of 1,1,1,3,3-pentafluoropropane (HFC-245fa) and between about 9% to about 13% by weight Z-1,3,3,3-tetrafluoropropene (HFO-Z-1234ze),
b) contacting the vaporized starting feed mixture and an oxygen containing gas with a catalyst in a reaction zone operated at a temperature between 200° C. and 325° C., wherein the reaction zone contains the catalyst and wherein the catalyst is selected from one of fluorinated Cr 2 O 3 or Cr/Ni on fluorided alumina, to form a product mixture comprising E-1,3,3,3-tetrafloropropene (Z-1,3,3,3-tetrafluoropropene), Z-1,3,3,3-tetrafluoropropene, hydrogen fluoride, unreacted HFC-245fa, if present,
c) separating the E-1,3,3,3-tetrafluoropropene from said Z-1,3,3,3-tetrafluoropropene and any unreacted 1,1,1,3,3-pentafluoropropane, if present,
d) separating and recovering one or more of Z-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane from the product mixture, and
e) providing at least the recovered E-1,3,3,3-tetrafluoropropene as a low ozone depletion potential (GDP) and global warming potential (GWP) compound.
10. The process of claim 9 wherein step e) comprises including the recovered E-1,3,3,3-tetrafluoropropene compound in or as one of a refrigerant, a solvent, a fire extinguishing agent, a blowing agent or a propellant.
11. The method of claim 9 wherein the starting mixture comprises between about 10% to about 13% by weight Z-1,3,3,3-tetrafluoropropene.
12. The method of claim 9 wherein the reaction zone is a single gas-phase catalytic reactor.
13. The method of claim 9 further comprising separating and recovering Z-1,3,3,3-tetrafluoropropene to further fluorinate or recycle the recovered Z-1,3,3,3-tetrafluoropropene.
14. The method of claim 10 further comprising separating and recovering Z-1,3,3,3-tetrafluoropropene and fluorinating or recycling the recovered Z-1,3,3,3-tetrafluoropropene.
15. The method of claim 9 , wherein hydrogen fluoride in the product mixture is removed by one of scrubbing and distillation.
16. The process of claim 9 wherein the vaporizing is conducted at a temperature of 30° C. to 100° C.
17. The process of claim 9 wherein the vaporizing is conducted at a temperature of 30° C. to 80° C.
18. The process of claim 9 wherein the vaporizing is conducted at a temperature of 40° C. to 60° C.
19. The process of claim 9 wherein selectivity to E-1,3,3,3-tetrafluoropropene is selected from one of at least 94% or 98%.
20. The method of claim 10 wherein step e) comprises including the recovered E-1,3,3,3-tetrafluoropropene in a refrigerant.
21. The method of claim 10 wherein step e) comprises including the recovered E-1,3,3,3-tetrafluoropropene in a solvent.
22. The method of claim 10 wherein step e) comprises including the recovered E-1,3,3,3-tetrafluoropropene in a fire extinguishing agent.
23. The method of claim 10 wherein step e) comprises including the recovered E-1,3,3,3-tetrafluoropropene in a blowing agent.
24. The method of claim 10 wherein step e) comprises including the recovered E-1,3,3,3-tetrafluoropropene in a propellant.
25. The method of claim 9 , further comprising recovering a mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, and recycling Z-1,3,3,3-tetrafluoropropene, or a mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane back to step a).
26. A method of producing CF 3 CH═CHF, comprising:
a) contacting a vaporized starting mixture of 1,1,1,3,3-pentafluoropropane and between about 7.5% to about 13% by weight Z-1,3,3,3-tetrafluoropropene in a gas phase, at a temperature between 200° C. and 300° C., in the presence of an oxygen containing gas and with a fluorinated Cr 2 O 3 or Cr/Ni on fluorided alumina catalyst,
b) forming a product mixture comprising mainly E-1,3,3,3-tetrafluoropropene, and Z-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, if present,
c) separating the E-1,3,3,3-tetrafluoropropene from said Z-1,3,3,3-tetrafluoropropene and any unreacted 1,1,1,3,3-pentafluoropropane,
d) recovering said E-1,3,3,3-tetrafluoropropene, and
e) returning said Z-1,3,3,3-tetrafluoropropene to step (a) with additional 1,1,1,3,3-pentafluoropropane,
wherein step (b) provides a product mixture comprising Z-1,3,3,3-tetrafluoropropene at about 10-13 mol %, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and 1,1,1,3,3-pentafluoropropane.
27. The method of claim 9 wherein step (b) provides a product mixture comprising between about 10-11 mole % Z-1,3,3,3-tetrafluoropropene, between about 60 to about 64 mol % E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and between about 24-27% mol % 1,1,1,3,3-pentafluoropropane.
28. The method of claim 11 wherein step (b) provides a product mixture comprising between about 10-11 mole % Z-1,3,3,3-tetrafluoropropene, between about 60 to about 64 mol % E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and between about 24-27% mol % 1,1,1,3,3-pentafluoropropane.
29. The method of claim 26 wherein step (b) provides a product mixture comprising between about 10-11 mole % Z-1,3,3,3-tetrafluoropropene, between about 60 to about 64 mol % E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and between about 24-27% mol % 1,1,1,3,3-pentafluoropropane.
30. The method of claim 9 , wherein step (b) increases the Z-1,3,3,3-tetrafluoropropene content by at most an additional 0.3 mol %.
31. The method of claim 11 , wherein steps (b) increase the Z-1,3,3,3-tetrafluoropropene content by at most an additional 0.3 mol %.
32. The method of claim 26 , wherein step (b) increases the Z-1,3,3,3-tetrafluoropropene content by at most an additional 0.3 mol %.
33. The method of claim 9 wherein the starting feed mixture comprises between about 10-11 mol % Z-1,3,3,3-tetrafluoropropene, and between about 87 and 92.5 mol % 1,1,1,3,3-pentafluoropropane.
34. The method of claim 11 wherein the starting feed mixture comprises between about 10-11 mol % Z-1,3,3,3-tetrafluoropropene, and between about 87 and about 92.5 mol % 1,1,1,3,3-pentafluoropropane.
35. The method of claim 26 wherein the starting feed mixture comprises between about 10-11 mol % Z-1,3,3,3-tetrafluoropropene, and between about 87 and about 92.5 mol % 1,1,1,3,3-pentafluoropropane.
36. The method of claim 9 wherein the reaction zone further comprises a co-catalyst selected from one of cobalt, manganese and zinc.
37. A method of producing CF 3 CH═CHF fluoropropene isomers in the gas phase, comprising:
(a) providing a vaporized starting feed mixture of 1,1,1,3,3-pentafluoropropane (HFC-245fa) and between about 7.5% to about 13% by weight Z-1,3,3,3-tetrafluoropropene (HFO-Z-1234ze);
(b) contacting the vaporized starting feed mixture and an oxygen containing gas with a catalyst in a gas reaction zone containing a catalyst selected from one of fluorinated Cr 2 O 3 or Cr/Ni on fluorided alumina, to form a product mixture comprising, E-1,3,3,3-tetrafluoropropene (HFO-E-1234ze), hydrogen fluoride, unreacted HFC-245fa, and Z-1,3,3,3-tetrafluoropropene,
(c) separating the E-1,3,3,3-tetrafluoropropene from said Z-1,3,3,3-tetrafluoropropene and unreacted 1,1,1,3,3-pentafluoropropane,
(d) separating and recovering E-1,3,3,3-tetrafluoropropene and one or more of Z-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and 1,1,1,3,3-pentafluoropropane from the product mixture, and
(e) including at least the recovered E-1,3,3,3-tetrafluoropropene as or in a refrigerant, a solvent, a fire extinguishing agent, a blowing agent or a propellant.
38. The process of claim 37 including E-1,3,3,3-tetrafluoropropene in a refrigerant, a solvent, a fire extinguishing agent, a blowing agent or a propellant in a system therefor.
39. A method of producing CF 3 CH═CHF, comprising:
a) contacting a starting feed mixture of 1,1,1,3,3-pentafluoropropane and from about 7.5% to about 13% by weight Z-1,3,3,3-tetrafluoropropene in the gas phase with a catalyst comprising at least one catalyst selected from the group consisting of fluorinated Cr 2 O 3 or Cr/Ni on fluorided alumina, in the presence of an oxygen containing gas, to form a mixture comprising Z-1,3,3,3-tetrafluoropropane, E-1,3,3,3,-tetrafluoropropene, hydrogen fluoride, and optionally unreacted 1,1,1,3,3-pentafluoropropane,
b) separating the E-1,3,3,3-tetrafluoropropene from said Z-1,3,3,3-tetrafluoropropene and any unreacted 1,1,1,3,3-pentafluoropropane, if present,
c) separating and recovering E-1,3,3,3-tetrafluoropropene, Z-1,3,3,3-tetrafluoropropene, and one or more of hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane from the product mixture, and
d) providing at least the recovered E-1,3,3,3-tetrafluoropropene as a low ozone depletion potential (GDP) and global warming potential (GWP) compound.
40. A method of producing CF 3 CH═CHF isomers in the gas phase, comprising:
a) contacting a vaporized starting mixture of 1,1,1,3,3-pentafluoropropane and an amount of Z-1,3,3,3-tetrafluoropropene sufficient to suppress additional formation of Z-1,3,3,3-tetrafluoropropene with a catalyst in a reactor held at gas phase temperature, in the presence of an oxygen containing gas, where the reactor contains the catalyst, which is selected from at least one of a fluorinated Cr 2 O 3 or Cr/Ni on fluorided alumina, to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and, if present, unreacted 1,1,1,3,3-pentafluoropropane,
b) separating the E-1,3,3,3-tetrafluoropropene from said Z-1,3,3,3-tetrafluoropropene and any unreacted 1,1,1,3,3-pentafluoropropane,
c) respectively recovering separated E-1,3,3,3-tetrafluoropropene and Z-1,3,3,3-tetrafluoropropene, and
d) converting said Z-1,3,3,3-tetrafluoropropene from step c) to E-1,3,3,3-tetrafluoropropene.
41. The process of claim 40 further including and using the recovered E-1,3,3,3-tetrafluoropropene in a refrigerant, a solvent, a fire extinguishing agent, a blowing agent or a propellant.
42. The process of claim 41 wherein additional formation of Z-1,3,3,3-tetrafluoropropene comprises at most about 0.3 mol %.
43. The process of claim 10 wherein step e) comprises including and operating a system with the recovered E-1,3,3,3-tetrafluoropropene as a refrigerant, a solvent, a fire extinguishing agent, a blowing agent or a propellant.
44. The process of claim 26 wherein step d) comprises including and operating a system with the recovered E-1,3,3,3-tetrafluoropropene as a refrigerant, a solvent, a fire extinguishing agent, a blowing agent or a propellant.
45. The process of claim 40 wherein step c) comprises including and operating a system with the recovered E-1,3,3,3-tetrafluoropropene as a refrigerant, a solvent, a fire extinguishing agent, a blowing agent or a propellant.