Dehydrofluorination of 245FA to 1234ZE

A method of producing a fluoropropene of formula CF3CH═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 Cr2O3 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.

A method of producing CF3CH═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 Cr2O3 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.

A method of producing CF3CH═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 Cr2O3 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.

A method of producing CF3CH═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 Cr2O3 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.

A method of producing CF3CH═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 Cr2O3 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.