Dehydrofluorination of 245FA to 1234ZE

Abstract

A method of producing a fluoropropane fluoropropene of formula CF 3 CH═CHF, comprising 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 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.

What is claimed is: 
     
       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) contacting a 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 reactor containing 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-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, if present, 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) recovering said E-1,3,3,3-tetrafluoropropene, and d) returning said Z-1,3,3,3-tetrafluoropropene to the reactor with additional 1,1,1,3,3-pentafluoropropane. 
     
     
       10. A method of producing CF 3 CH═CHF, comprising: a) contacting a starting mixture of 1,1,1,3,3-pentafluoropropane and between about 10% to 13% by weight Z-1,3,3,3-tetrafluoropropene in a single gas-phase catalytic reactor 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-tetrafluoropropene, 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-1,3,3,3-tetrafluoropropene and any unreacted 1,1,1,3,3-pentafluoropropane and, c) recovering at least said E-1,3,3,3-tetrafluoropropene and Z-1,3,3,3-tetrafluoropropene and fluorinating said Z-1,3,3,3-tetrafluoropropene to form 1,1,1,3,3-pentafluoropropene. 
     
     
       11. A method of producing CF 3 CH═CHF in the vapor phase, comprising: a) contacting a mixed starting feed combination of 1,1,1,3,3-pentafluoropropane and at least 10% by weight Z-1,3,3,3-tetrafluoropropene in a single reactor containing 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, wherein the reactor is held at a temperature held between 275° C. and 350° C., to form a product mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, b) separating the E-1,3,3,3-tetrafluoropropene from the Z-1,3,3,3-tetrafluoropropene and unreacted 1,1,1,3,3-pentafluoropropane, c) recovering at least said E-1,3,3,3-tetrafluoropropene and Z-1,3,3,3-tetrafluoropropene, and d) fluorinating or recycling said recovered Z-1,3,3,3-tetrafluoropropene. 
     
     
       12. A method of producing a fluoropropene of formula CF 3 CH═CHF, comprising: a) contacting a combined starting feed of 1,1,1,3,3-pentafluoropropane and at least 10% by weight Z-1,3,3,3-tetrafluoropropene in a single catalytic gas phase reactor held at about 300° C. 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 product mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, b) separating the E-1,3,3,3-tetrafluoropropene from the Z-1,3,3,3-tetrafluoropropene and unreacted 1,1,1,3,3-pentafluoropropane, and c) recovering said E-1,3,3,3-tetrafluoropropene. 
     
     
       13. A method of producing a fluoropropene of formula CF 3 CH═CHF, comprising: a) contacting a starting mixture of 1,1,1,3,3-pentafluoropropane and between about 10% to about 13% by weight Z-1,3,3,3-tetrafluoropropene in a gas phase reactor containing 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-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, if present, wherein at most an additional 0.3 mol % Z-1,3,3,3-tetrafluoropropene is produced, b) separating the E-1,3,3,3-tetrafluoropropene from the Z-1,3,3,3-tetrafluoropropene and any unreacted 1,1,1,3,3-pentafluoropropane, c) recovering at least said E-1,3,3,3-tetrafluoropropene and Z-1,3,3,3-tetrafluoropropene, and d) fluorinating or recycling said recovered Z-1,3,3,3-tetrafluoropropene. 
     
     
       14. A method of producing a fluoropropene of formula CF 3 CH═CHF, comprising: a) contacting a starting mixture of 1,1,1,3,3-pentafluoropropane and between about 10% to about 13% by weight Z-1,3,3,3-tetrafluoropropene in a gas phase reactor for about 45 seconds, wherein the reactor contains 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-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, if present, wherein at most an additional 0.3 mol % Z-1,3,3,3-tetrafluoropropene is produced, 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) recovering at least said E-1,3,3,3-tetrafluoropropene and Z-1,3,3,3-tetrafluoropropene, and d) subsequently fluorinating or recycling said recovered Z-1,3,3,3-tetrafluoropropene, wherein when said Z-1,3,3,3-tetrafluoropropene is fluorinated to 1,1,1,3,3-pentafluoropropane, said 1,1,1,3,3-pentafluoropropane is recycled to the reactor. 
     
     
       15. The method of claim 9, wherein said hydrogen fluoride produced in step a) is removed by one of scrubbing and distillation. 
     
     
       16. The method of claim 10, wherein said hydrogen fluoride produced in step a) is removed by one of scrubbing and distillation. 
     
     
       17. The method of claim 11, wherein said hydrogen fluoride produced in step a) is removed by one of scrubbing and distillation. 
     
     
       18. The method of claim 12, wherein said hydrogen fluoride produced in step a) is removed by one of scrubbing and distillation. 
     
     
       19. The method of claim 13, wherein said hydrogen fluoride produced in step a) is removed by one of scrubbing and distillation. 
     
     
       20. The method of claim 14, wherein said hydrogen fluoride produced in step a) is removed by one of scrubbing and distillation. 
     
     
       21. The method of claim 13, 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). 
     
     
       22. A method of producing a fluoropropene of formula CF 3 CH═CHF, comprising: a) contacting a starting feed mixture of 1,1,1,3,3-pentafluoropropane and at least 9% 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 product mixture comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, b) separating and recovering the E-1,3,3,3-tetrafluoropropene from the Z-1,3,3,3-tetrafluoropropene and unreacted 1,1,1,3,3-pentafluoropropane, and c) recovering a mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, and recycling the mixture of Z-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane to step a), and wherein said hydrogen fluoride is separated and recovered. 
     
     
       23. A method of producing a fluoropropene of formula CF 3 CH═CHF, comprising: a) contacting a 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 reactor containing 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-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, if present, 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) recovering said E-1,3,3,3-tetrafluoropropene, and d) returning said Z-1,3,3,3-tetrafluoropropene to the reactor with additional 1,1,1,3,3-pentafluoropropane, wherein step (a) provides a composition 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. 
     
     
       24. The method of claim 10 wherein step (a) provides a composition 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. 
     
     
       25. The method of claim 11 wherein step (a) provides a composition 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. 
     
     
       26. The method of claim 9, wherein step (a) increases the Z-1,3,3,3-tetrafluoropropenecontent by at most an additional 0.3 mol %. 
     
     
       27. A method of producing a fluoropropene of formula CF 3 CH═CHF, comprising: a) contacting a starting mixture of 1,1,1,3,3-pentafluoropropane and Z-1,3,3,3-tetrafluoropropene in a gas phase reactor containing 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-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, hydrogen fluoride, and unreacted 1,1,1,3,3-pentafluoropropane, if present, wherein at most an additional 0.3 mol % Z-1,3,3,3-tetrafluoropropene is produced, 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) recovering at least said E-1,3,3,3-tetrafluoropropene and Z-1,3,3,3-tetrafluoropropene, and d) returning said Z-1,3,3,3-tetrafluoropropene to the reactor with additional 1,1,1,3,3-pentafluoropropane. 
     
     
       28. The method of claim 10 wherein the starting 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. 
     
     
       29. The method of claim 11 wherein the starting feed 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. 
     
     
       30. A method of producing CF 3 CH═CHF, comprising: a) contacting a starting mixture of 1,1,1,3,3-pentafluoropropane and between about 10% to 13% by weight Z-1,3,3,3-tetrafluoropropene in a single gas-phase catalytic reactor comprising at least one catalyst selected from the group consisting of fluorinated Cr 2 O 3  or Cr/Ni on fluorided alumina, and optionally a co-catalyst selected from one of cobalt, manganese and zinc, in the presence of an oxygen containing gas, to form a mixture comprising Z-1,3,3,3-tetrafluoropropene, 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-1,3,3,3-tetrafluoropropene and any unreacted 1,1,1,3,3-pentafluoropropane and, c) recovering at least said E-1,3,3,3-tetrafluoropropene and said Z-1,3,3,3-tetrafluoropropene. 
     
     
       31. The method of claim 9, further providing the E-1,3,3,3-tetrafluoropropene to a refrigerant system. 
     
     
       32. The method of claim 10, further providing the E-1,3,3,3-tetrafluoropropene to a refrigerant system. 
     
     
       33. The method of claim 11, further providing the E-1,3,3,3-tetrafluoropropene to a refrigerant system. 
     
     
       34. The method of claim 12, further providing the E-1,3,3,3-tetrafluoropropene to a refrigerant system. 
     
     
       35. The method of claim 13, further providing the E-1,3,3,3-tetrafluoropropene to a refrigerant system. 
     
     
       36. The method of claim 14, further providing the E-1,3,3,3-tetrafluoropropene to a refrigerant system. 
     
     
       37. The method of claim 31, the method including operating the refrigerant system, wherein the refrigerant system comprises the E-1,3,3,3-tetrafluoropropene. 
     
     
       38. The method of claim 32, the method including operating the refrigerant system, wherein the refrigerant system comprises the E-1,3,3,3-tetrafluoropropene. 
     
     
       39. The method of claim 33, the method including operating the refrigerant system, wherein the refrigerant system comprises the E-1,3,3,3-tetrafluoropropene. 
     
     
       40. The method of claim 34, the method including operating the refrigerant system, wherein the refrigerant system comprises the E-1,3,3,3-tetrafluoropropene. 
     
     
       41. The method of claim 35, the method including operating the refrigerant system, wherein the refrigerant system comprises the E-1,3,3,3-tetrafluoropropene. 
     
     
       42. The method of claim 36, the method including operating the refrigerant system, wherein the refrigerant system comprises the E-1,3,3,3-tetrafluoropropene.