Processes for the production of z-1,1,1,4,4,4-hexafluoro-2-butene intermediates and compositions thereof

Abstract

Methods of synthesis of intermediates, such as 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene, which can be used in the production fluorinated olefins, such as 1,1,1,4,4,4-hexafluoro-2-butene, from hexafluorobutadiene, are provided.

Description

TITLE OF THE INVENTIONPROCESSES FOR THE PRODUCTION OF Z-1 ,1 ,1 ,4,4,4-HEXAFLUORO-2- BUTENE INTERMEDIATES AND COMPOSITIONS THEREOFFIELD

[0001] This disclosure relates in general to methods of synthesis of fluorinated olefins. More particularly, this invention relates to processes and systems for making intermediates, such as 2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene and 2,3- dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene, which can be used in the production fluorinated olefins, such as 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene, from hexafluorobutadiene.BACKGROUND

[0002] The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents and propellants. These new compounds, such as HFC refrigerants, HFC-134a and HFC-125 being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase-out as a result of the Montreal Protocol.

[0003] In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. Thus, there is a need for compositions that meet both low ozone depletion standards as well as having low global warming potentials. Certain hydrofluoroolefins are believed to meet both goals. Thus, there is a need for manufacturing processes that provide hydrofluoroolefins that contain no chlorine that also have a low global warming potential.

[0004] (Z)-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) is an example of such a hydrofluoroolefin. The present invention provides economical systems and processes for manufacturing intermediate compounds from hexachlorobutadiene (HCBD) which can then be converted to form the desired Z- HFO-1336mzz hydrofluoroolefin.

[0005] HCBD is primarily produced in chlorinolysis plants as a by-product in the production of carbon tetrachloride and tetrachloroethene. These two commodities are manufactured on such a large scale, that enough HCBD can generally be obtained to meet industrial demand. Thus, HCBD may constitute a low cost and obtainable starting material for manufacturing processes that provides halogenated hydrocarbons and fluoroolefins.

[0006] Further, as a by-product in the production of carbon tetrachloride and tetrachloroethene, HCBD constitutes a waste that must be disposed of to prevent environmental pollution. Thus, the manufacturing processes of the present invention, which utilize HCBD as a starting material for producing hydrofluoroolefins convert a potential environmental pollutant waste into environmentally friendly product.SUMMARY

[0007] Any of the embodiments of the invention discussed herein can be used alone or in combination with each other. It will be understood by those skilled in the art that different embodiments discussed herein can be combined and form part of the invention. It will also be understood by those skilled in the art that certain aspects of different embodiments discussed herein can be combined and form part of the invention.

[0008] Embodiment 1 : A process of preparing a compound of the formula CF3CR=CCICF3, wherein R is H or Cl, the processing comprising reacting a composition comprising hexachlorobutadiene (HCBD) and one or more additional compounds in the presence of a catalyst to obtain a product mixture comprising the compound of the formula CF3CR=CCICF3, wherein the one or moreadditional compounds are selected from 1 ,1 ,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3-pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 ,1 ,1 ,2,2,3, 3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2, 3, 3-tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene.

[0009] Embodiment 2: The process of Embodiment 1 , wherein the compound of the formula CF3CR=CCICF3 is 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene.

[0010] Embodiment 3: The process of any of Embodiments 1 to 2, individually or any combination thereof, the process comprising reacting the composition comprising HCBD and one or more additional compounds with HF in the presence of a fluorination catalyst to produce a product mixture comprising 2- chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

[0011] Embodiment 4: The process of any of Embodiments 2 to 3, individually or any combination thereof, wherein greater than about 99 mole percent of the 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

[0012] Embodiment 5: The process of any of Embodiments 2 to 4, individually or any combination thereof, wherein the fluorination catalyst is a transition metal catalyst selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

[0013] Embodiment 6: The process of Embodiment 5, wherein the transition metal catalyst is selected from tantalum (V) chloride, niobium (V) chloride, niobium (IV) chloride, and combinations of two or more.

[0014] Embodiment 7: The process of any of Embodiments 2 to 4, individually or any combination thereof, wherein the fluorination catalyst is ametal halide selected from antimony halides, tin halides, thallium halides, iron halides and combinations of two or more.

[0015] Embodiment s: The process of Embodiment 7, wherein the metal halide catalyst is selected from SbCIs, SbCIs, SbFs, SnCl4, TiCU, NiFs, FeCIs, and combinations of two or more, and preferably the metal halide catalyst is SbCIs or SbF5.

[0016] Embodiment 9: The process of any of Embodiments 3 to 8, individually or any combination thereof, wherein a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene.

[0017] Embodiment 10: The process of any of Embodiments 3 to 8, individually or any combination thereof, wherein the process is performed a temperature of from about 80°C to about 150°C.

[0018] Embodiment 11 : The process of any of Embodiments 2 to 8, individually or any combination thereof, wherein the 2-chloro-1 , 1 ,1 , 4,4,4- hexafluoro-2-butene of the product mixture is Z-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene.

[0019] Embodiment 12: The process of any of Embodiments 2 to 11 , individually or any combination thereof, wherein the product mixture further comprises one or more additional compounds selected from E-2-chloro- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene; E-CFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene); Z-CFO-1316mxx (Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut- 2-ene); HFO-1327mz (1 ,1 ,1 ,2,4,4,4-heptafluorobut-2-ene); HCFO-1325lxz (1 ,2- dichloro-1 , 1 ,4,4,4-pentafluorobut-2-ene); HCFO-1325dx (1 , 2-dichloro-3 ,3, 4,4 , 4- pentafluorobut-1-ene); HCFC-336mdd (2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluorobutane); HCFC-336maf (2,2-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane); HCFC-336lbf (1 , 2-dichloro-1 , 1 ,2,4,4,4-hexafluorobutane); HCFC-337mbf (2- chloro-1 , 1 ,1 ,2,4,4,4-heptafluorobutane); HCFC-337mde (2-chloro-1 ,1 , 1 , 3, 4,4,4- heptafluorobutane); HFC-356mff (1 , 1 ,1 ,4,4,4-hexafluorobutane); HCFC-346mdf (2-chloro-1 ,1 , 1 ,4,4,4-hexafluorobutane); HFC-338mf (1 ,1 ,1 , 2, 2, 4,4,4-octafluorobutane); HCFC-1122 (2-chloro-1 ,1 -difluoroethylene); HCFC-124 (2- chloro-1 ,1 ,1 ,2-tetrafluoroethane); CFC-114 (1 , 2-dichloro-1 , 1 ,2,2- tetrafluoroethane); CFC-113 (1 ,1 ,2-trichloro-1 ,2,2-trifluoroethane); CFC-133a (2- chloro-1 ,1 ,1 -trifluoroethane); HCFC-123 (2,2-dichloro-1 ,1 ,1 -trifluoroethane); HCFC-123a (1 ,2-dichloro-1 ,1 ,2-trifluoroethane); HCFC-122 (1 ,2,2-trichloro-1 , 1 - difluoroethane); CFC-112a (1 ,1 ,1 ,2-tetrachloro-2,2-difluoroethane); HCFC-224db (1 ,1 ,1 ,3-tetrafluoro-2,3,3-trichloropropane); 33dichloro-1 , 1 ,3,3,3- pentafluoropropane); HCFC-235da (2-chloro-1 , 1 , 1 ,3,3-pentafluoropropane);CFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane); and HFC-236fa (1 , 1 ,1 , 3,3,3- hexafluoropropane).

[0020] Embodiment 13: The process of any of Embodiments 2 to 11 , individually or any combination thereof, wherein the product mixture further comprises one or more additional compounds selected from E-2-chloro- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene, E-CFO-1317mx (E-2-chloro-1 ,1 ,1 , 3, 4,4,4- heptafluorobut-2-ene), Z-CFO-1317mx (Z-2-chloro-1 ,1 ,1 , 3,4,4, 4-heptafluorobut- 2-ene) and HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane).

[0021] Embodiment 14: The process of any of Embodiments 2 to 11 , individually or any combination thereof, wherein the product mixture further comprises HCFC-336mdd (2,3-dichloro-1 ,1 , 1 ,4,4,4-hexafluorobutane).

[0022] Embodiment 15: The process of any of Embodiments 2 to 14, individually or any combination thereof, the process further comprising sequential dehydrochlorination of the Z-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene to produce hexafluoro-2-butyne, followed by hydrogenation of the hexafluoro-2-butyne to produce (Z)-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

[0023] Embodiment 16: The process of any of Embodiments 2 to 14, individually or any combination thereof, the process further comprising sequential dechlorination of a mixture of the Z-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene and 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane to produce hexafluoro-2-butyne, followed by hydrogenation of the hexafluoro-2-butyne to produce (Z)-1 , 1 ,1 , 4,4,4- hexafluoro-2-butene.

[0024] Embodiment 17: The process of any of Embodiments 2 to 14, individually or any combination thereof, wherein the process is conducted in the liquid phase.

[0025] Embodiment 18: The process of Embodiment 1 , wherein the compound of the formula CF3CR=CCICF3 is 2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluorobut-2-ene.

[0026] Embodiment 19: The process of any of Embodiments 1 and 18, individually or any combination thereof, the process comprising reacting the composition comprising HCBD and one or more additional compounds with HF and chlorine in the presence of metal oxide or metal halide catalyst to produce a product mixture comprising 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene.

[0027] Embodiment 20: The process of any of Embodiments 1 , 18 and 19, individually or any combination thereof, wherein the 2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluorobut-2-ene comprises the Z and E isomers.

[0028] Embodiment 21 : The process of any of Embodiments 19 and 20, wherein the metal halide catalyst is selected from nickel halides, chromium halides, iron halides, scandium halides, yttrium halides, lanthanum halides, titanium halides, zirconium halides, hafnium halides, vanadium halides, molybdenum halides, tungsten halides, manganese halides, rhenium halides, ruthenium halides, osmium halides, cobalt halides, palladium halides, copper halides, zinc halides, antimony halides, tantalum halides, aluminum halides, tin halides, lead halides, and mixtures thereof.

[0029] Embodiment 22: The process of Embodiment 21 , wherein the metal halide catalyst is unsupported or supported on activated carbon.

[0030] Embodiment 23: The process of Embodiment 22, wherein the activated carbon may optionally be acid washed or caustic washed.

[0031] Embodiment 24: The process of any of Embodiments 19 to 20, wherein the metal oxide catalyst is selected from chromium oxide, aluminum oxide and mixtures thereof.

[0032] Embodiment 25: The process of Embodiment 24, wherein the metal oxide catalyst is unsupported or supported on activated carbon.

[0033] Embodiment 26: The process of Embodiment 25, wherein the activated carbon may optionally be acid washed or caustic washed.

[0034] Embodiment 27: The process of any of Embodiments 19 to 26, wherein the catalyst comprises a chloride source for the process of Embodiment 19.

[0035] Embodiment 28: The process of any of Embodiments 19 to 27, wherein a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene.

[0036] Embodiment 29: The process of any of Embodiments 19 to 28, wherein a molar excess of chlorine is used based on 1 molar equivalent of hexachlorobutadiene.

[0037] Embodiment 30: The process of any of Embodiments 1 and 18 to 29, wherein the process is performed a temperature of from about 230°C to about 480°C.

[0038] Embodiment 31 : The process of any of Embodiments 1 and 18 to 30, wherein the product mixture comprises E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut- 2-ene and Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene.

[0039] Embodiment 32: The process of any of Embodiments 1 and 18 to 31 , wherein the product mixture further comprises one or more additional compounds selected from Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO- 1326mxz); E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2- chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z- 2-chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1 ,2, 3-trichloro-1 ,1 ,4,4,4- pentafluoro-2-butene (E-CFO-1315lxx); Z-1 ,2 ,3-trichloro- 1 , 1 ,4,4,4-pentafluoro-2-butene (Z-CFO-1315lxx); E-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (E- CFO-1314kxx); Z-1 , 1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (Z-CFO- 1314kxx); HCFC-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane (HFC-346mdf); and1.1.1 .3.3.3-hexafluoropropane (HFC-236fa).

[0040] Embodiment 33: The process of any of Embodiments 1 and 18 to 32, wherein the product mixture further comprises one or more additional compounds selected from Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO- 1326mxz) and E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz).

[0041] Embodiment 34: The process of any of Embodiments 1 and 18 to 33, wherein the product mixture further comprises Z-2-chloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene (Z-HCFO-1326mxz).

[0042] Embodiment 35: The process of any of Embodiments 18 to 34, the process further comprising sequential dechlorination of the 2,3-dichloro-1.1.1.4.4.4-hexafluorobut-2-ene to produce hexafluoro-2-butyne, followed by hydrogenation of the hexafluoro-2-butyne to produce (Z)-1 ,1 ,1 ,4,4,4-hexafluoro- 2-butene.

[0043] Embodiment 36: The process of any of Embodiments 18 to 35, wherein the process is conducted in the gas phase.

[0044] Embodiment 37: A composition comprising hexachlorobutadiene and one or more additional compounds selected from 1 ,1 , 3,3,4, 4-hexachloro-1- butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC- 120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3-pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 ,1 ,1 ,2,2,3, 3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2, 3, 3-tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene.

[0045] Embodiment 38: The composition of Embodiment 37, wherein the one or more additional compounds are present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

[0046] Embodiment 39: A composition comprising Z-chloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene and one or more additional compounds selected from E-2- chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene; E-CFO-1316mxx (E-2,3-dichloro-1.1.1 .4.4.4-hexafluorobut-2-ene); Z-CFO-1316mxx (Z-2,3-dichloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene); HFO-1327mz (1 ,1 ,1 ,2,4,4,4-heptafluorobut-2-ene); HCFO- 1325lxz (1 ,2-dichloro-1 ,1 ,4,4,4-pentafluorobut-2-ene); HCFO-1325dx (1 ,2- dichloro-3,3,4,4,4-pentafluorobut-1 -ene); HCFC-336mdd (2,3-dichloro-1.1.1 .4.4.4-hexafluorobutane); HCFC-336maf (2,2-dichloro-1 ,1 ,1 ,4,4,4- hexafluorobutane); HCFC-336lbf (1 , 2-dichloro-1 , 1 ,2,4,4,4-hexafluorobutane); HCFC-337mbf (2-chloro-1 ,1 ,1 ,2,4,4,4-heptafluorobutane); HCFC-337mde (2- chloro-1 , 1 ,1 ,3,4,4,4-heptafluorobutane); HFC-356mff (1 , 1 ,1 ,4,4,4- hexafluorobutane); HCFC-346mdf (2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane); HFC- 338mf (1 ,1 ,1 ,2,2,4,4,4-octafluorobutane); HCFC-1122 (2-chloro-1 , 1 - difluoroethylene); HCFC-124 (2-chloro-1 ,1 ,1 ,2-tetrafluoroethane); CFC-114 (1 ,2- dichloro-1 , 1 ,2,2-tetrafluoroethane); CFC-113 (1 ,1 , 2-trichloro-1 ,2,2- trifluoroethane); CFC-133a (2-chloro-1 , 1 ,1 -trifluoroethane); HCFC-123 (2,2- dichloro-1 ,1 ,1 -trifluoroethane); HCFC-123a (1 ,2-d ichloro-1 , 1 ,2-trifluoroethane); HCFC-122 (1 , 2, 2-trichloro-1 ,1 -difluoroethane); CFC-112a (1 , 1 , 1 ,2-tetrachloro- 2,2-difluoroethane); HCFC-224db (1 ,1 ,1 ,3-tetrafluoro-2,3,3-trichloropropane); E- CFO-1317mx (E-2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobut-2-ene); Z-CFO-1317mx (Z-2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobut-2-ene); HCFC-225da (1 ,2-dichloro- 1 ,1 ,3,3,3-pentafluoropropane); HCFC-235da (2-chloro-1 , 1 , 1 ,3,3- pentafluoropropane); CFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane); and HFC-236fa (1 , 1 ,1 ,3,3,3-hexafluoropropane).

[0047] Embodiment 40: The composition of Embodiment 39, wherein the one or more additional compounds are present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

[0048] Embodiment 41 : A composition comprising Z-chloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene and one or more additional compounds selected from E-2- chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1.1.1 .4.4.4-hexafluorobutane).

[0049] Embodiment 42: The composition according to Embodiment 41 , wherein the one or more additional compounds are present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

[0050] Embodiment 43: A composition comprising Z-chloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene and HCFC-336mdd (2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluorobutane), wherein the HCFC-336mdd is present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

[0051] Embodiment 44: A composition comprising E-2,3-dichloro-1 , 1 ,1 , 4,4,4- hexafluorobut-2-ene; Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene; and one or more additional compounds selected from Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut- 2-ene (Z-HCFO-1326mxz); E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (E-HCFO- 1326mxz); E-2-chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z-2- chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1 ,2,3-trichloro-1 .1 .4.4.4-pentafluoro-2-butene (E-CFC-1315lxx); Z-1 ,2, 3-trichloro-1 ,1 ,4,4,4- pentafluoro-2-butene (Z-CFC-1315lxx); E-1 , 1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro- 2-butene (E-CFC-1314kxx); Z-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (Z- CFC-1314kxx); 2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane (HFC-346mdf); and1 ,1 ,1 ,3,3,3-hexafluoropropane (HFC-236fa).

[0052] Embodiment 45: The composition according to Embodiment 44, wherein the one or more additional compounds are present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

[0053] Embodiment 46: The process according to any of Embodiments 1 to 36, individually or any combination thereof, wherein the composition comprising HCBD is supplied from a reactor without being stored.

[0054] Embodiment 47: An integrated system for preparing a compound of the formula CF3CR=CCICF3, wherein R is H or Cl, the system comprising: a first reactor configured to produce a composition comprising hexachlorobutadiene (HCBD) and one or more additional compounds in the presence of a catalyst to obtain a product mixture comprising the compound of the formula CF3CR=CCICF3, wherein the one or more additional compounds are selected from 1 ,1 ,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3- pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 , 1 ,1 , 2, 2,3,3- heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2,3,3- tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH- CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene; and a second reactor coupled to the first reactor and configured to convert the composition comprising HCBD into a compound of the formula CF3CR=CCICF3.

[0055] Embodiment 48: The integrated system according to Embodiment 47, wherein the composition comprising HCBD is supplied to the second reactor from the first reactor without being stored.

[0056] Embodiment 49: The integrated system of Embodiment 47 or 48, wherein the compound of the formula CF3CR=CCICF3 is 2-chloro-1 ,1 ,1 ,4,4,4- hexafluoro-2-butene.

[0057] Embodiment 50: The integrated system of any of Embodiments 47 to49, individually or any combination thereof, wherein in the second reactor, the composition comprising HCBD and one or more additional compounds is reacted with HF in the presence of a fluorination catalyst to produce a product mixture comprising 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

[0058] Embodiment 51 : The integrated system of any of Embodiments 49 to50, individually or any combination thereof, wherein greater than about 99 mole percent of the 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

[0059] Embodiment 52: The integrated system of any of Embodiments 49 to51 , individually or any combination thereof, wherein the fluorination catalyst is a transition metal catalyst selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

[0060] Embodiment 53: The integrated system of Embodiment 52, wherein the transition metal catalyst is selected from tantalum (V) chloride, niobium (V) chloride, niobium (IV) chloride, and combinations of two or more.

[0061] Embodiment 54: The integrated system of any of Embodiments 49 to 51 , individually or any combination thereof, wherein the fluorination catalyst is a metal halide selected from antimony halides, tin halides, thallium halides, iron halides and combinations of two or more.

[0062] Embodiment 55: The integrated system of Embodiment 54, wherein the metal halide catalyst is selected from SbCIs, SbCh, SbFs, SnCl4, TiCU, NiFs, FeCh, and combinations of two or more, and preferably the metal halide catalyst is SbCIs or SbFs.

[0063] Embodiment 56: The integrated system of any of Embodiments 50 to55, individually or any combination thereof, wherein a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene.

[0064] Embodiment 57: The integrated system of any of Embodiments 50 to 55, individually or any combination thereof, wherein the second reactor operates at a temperature of from about 80°C to about 150°C.

[0065] Embodiment 58: The integrated system of any of Embodiments 49 to 55, individually or any combination thereof, wherein the 2-chloro-1 , 1 ,1 , 4,4,4- hexafluoro-2-butene of the product mixture is Z-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene.

[0066] Embodiment 59: The integrated system of any of Embodiments 49 to 58, individually or any combination thereof, wherein the product mixture further comprises one or more additional compounds selected from E-2-chloro- 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene; E-CFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene); Z-CFO-1316mxx (Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut- 2-ene); HFO-1327mz (1 ,1 ,1 ,2,4,4,4-heptafluorobut-2-ene); HCFO-1325lxz (1 ,2- dichloro-1 , 1 ,4,4,4-pentafluorobut-2-ene); HCFO-1325dx (1 , 2-dichloro-3 ,3, 4,4 , 4- pentafluorobut-1-ene); HCFC-336mdd (2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluorobutane); HCFC-336maf (2,2-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane); HCFC-336lbf (1 , 2-dichloro-1 , 1 ,2,4,4,4-hexafluorobutane); HCFC-337mbf (2- chloro-1 , 1 ,1 ,2,4,4,4-heptafluorobutane); HCFC-337mde (2-chloro-1 ,1 , 1 , 3, 4,4,4- heptafluorobutane); HFC-356mff (1 , 1 ,1 ,4,4,4-hexafluorobutane); HCFC-346mdf (2-chloro-1 ,1 , 1 ,4,4,4-hexafluorobutane); HFC-338mf (1 ,1 ,1 , 2, 2, 4,4,4- octafluorobutane); HCFC-1122 (2-chloro-1 ,1 -difluoroethylene); HCFC-124 (2- chloro-1 ,1 ,1 ,2-tetrafluoroethane); CFC-114 (1 , 2-dichloro-1 , 1 ,2,2- tetrafluoroethane); CFC-113 (1 ,1 ,2-trichloro-1 ,2,2-trifluoroethane); CFC-133a (2- chloro-1 ,1 ,1 -trifluoroethane); HCFC-123 (2,2-dichloro-1 ,1 ,1 -trifluoroethane); HCFC-123a (1 ,2-dichloro-1 ,1 ,2-trifluoroethane); HCFC-122 (1 ,2,2-trichloro-1 , 1 - difluoroethane); CFC-112a (1 ,1 ,1 ,2-tetrachloro-2,2-difluoroethane); HCFC-224db (1 ,1 ,1 ,3-tetrafluoro-2,3,3-trichloropropane); 33dichloro-1 , 1 ,3,3,3- pentafluoropropane); HCFC-235da (2-chloro-1 , 1 , 1 ,3,3-pentafluoropropane);CFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane); and HFC-236fa (1 , 1 ,1 , 3,3,3- hexafluoropropane).

[0067] Embodiment 60: The integrated system of any of Embodiments 49 to 58, individually or any combination thereof, wherein the product mixture further comprises one or more additional compounds selected from E-2-chloro-1.1.1 .4.4.4-hexafluoro-2-butene, E-CFO-1317mx (E-2-chloro-1 ,1 ,1 , 3, 4,4,4- heptafluorobut-2-ene), Z-CFO-1317mx (Z-2-chloro-1 ,1 ,1 , 3,4,4, 4-heptafluorobut- 2-ene) and HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane).

[0068] Embodiment 61 : The integrated system of any of Embodiments 49 to 58, individually or any combination thereof, wherein the product mixture further comprises HCFC-336mdd (2,3-dichloro-1 ,1 , 1 ,4,4,4-hexafluorobutane).

[0069] Embodiment 62: The integrated system of any of Embodiments 49 to 61 , individually or any combination thereof, wherein the second reactor is a liquid phase reactor.

[0070] Embodiment 63: The integrated system of Embodiment 47, wherein the compound of the formula CF3CR=CCICF3 is 2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluorobut-2-ene.

[0071] Embodiment 64: The integrated system of any of Embodiments 47 and 63, individually or any combination thereof, wherein the second reactor, the composition comprising HCBD and one or more additional compounds is reacted with HF and chlorine in the presence of metal oxide or metal halide catalyst to produce a product mixture comprising 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2- ene.

[0072] Embodiment 65: The integrated system of any of Embodiments 47, 63 and 64, individually or any combination thereof, wherein the 2,3-dichloro-1.1.1.4.4.4-hexafluorobut-2-ene comprises the Z and E isomers.

[0073] Embodiment 66: The integrated system of any of Embodiments 64-65, wherein the metal halide catalyst is selected from nickel halides, chromium halides, iron halides, scandium halides, yttrium halides, lanthanum halides, titanium halides, zirconium halides, hafnium halides, vanadium halides, molybdenum halides, tungsten halides, manganese halides, rhenium halides,ruthenium halides, osmium halides, cobalt halides, palladium halides, copper halides, zinc halides, antimony halides, tantalum halides, aluminum halides, tin halides, lead halides, and mixtures thereof.

[0074] Embodiment 67: The integrated system of Embodiment 66, wherein the metal halide catalyst is unsupported or supported on activated carbon.

[0075] Embodiment 68: The integrated system of Embodiment 67, wherein the activated carbon may optionally be acid washed or caustic washed.

[0076] Embodiment 69: The integrated system of any of Embodiments 64 to 65, wherein the metal oxide catalyst is selected from chromium oxide, aluminum oxide and mixtures thereof.

[0077] Embodiment 70: The integrated system of Embodiment 69, wherein the metal oxide catalyst is unsupported or supported on activated carbon.

[0078] Embodiment 71 : The integrated system of Embodiment 70, wherein the activated carbon may optionally be acid washed or caustic washed.

[0079] Embodiment 72: The integrated system of any of Embodiments 64 to71 , wherein the catalyst comprises a chloride source for the system of Embodiment 64.

[0080] Embodiment 73: The integrated system of any of Embodiments 63 to72, wherein the second reactor operates a temperature of from about 230°C to about 480°C.

[0081] Embodiment 74: The integrated system of any of Embodiments 63 to73, wherein the product mixture comprises E-2,3-dichloro-1 , 1 ,1 , 4,4,4- hexafluorobut-2-ene and Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene.

[0082] Embodiment 75: The integrated system of any of Embodiments 63 to74, wherein the product mixture further comprises one or more additional compounds selected from Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO- 1326mxz); E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2- chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z- 2-chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1 , 2 , 3-trichloro- 1 ,1 ,4,4,4- pentafluoro-2-butene (E-CFO-1315lxx); Z-1 ,2 , 3-trichloro- 1 , 1 ,4,4,4-pentafluoro-2- butene (Z-CFO-1315lxx); E-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (E- CFO-1314kxx); Z-1 , 1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (Z-CFO- 1314kxx); HCFC-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane (HFC-346mdf); and 1 ,1 ,1 ,3,3,3-hexafluoropropane (HFC-236fa).

[0083] Embodiment 76: The integrated system of any of Embodiments 63 to 74, wherein the product mixture further comprises one or more additional compounds selected from Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO- 1326mxz) and E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz).

[0084] Embodiment 77: The integrated system of any of Embodiments 63 to 74, wherein the product mixture further comprises Z-2-chloro-1 , 1 ,1 , 4,4,4- hexafluorobut-2-ene (Z-HCFO-1326mxz).

[0085] Embodiment 78: The integrated system of any of Embodiments 63 to 77, wherein the second reactor is a gas phase reactor.BRIEF DESCRIPTION OF THE DRAWINGS

[0086] The following detailed description of preferred embodiments of the present invention will be better understood when read in conjunction with the appended drawings. For the purposes of illustrating the invention, there is shown in the drawings embodiments which are presently preferred. It is understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown. In the drawings:

[0087] Fig. 1 is a schematic illustration of an integrated system and process for producing a compound of the formula CF3CR=CCICF3 from hexachlorobutadiene, according to one embodiment of the present invention.DETAILED DESCRIPTION

[0088] The present invention generally relates to processes and intermediates for preparing a compound of the formula CF3CR=CCICF3, where R is Cl or H, using hexachlorobutadiene (HCBD) as a raw material.

[0089] In some embodiments, the reactor and associated equipment for carrying out these processes to convert HCBD to a compound of the formula CF3CR=CCICF3, where R is Cl or H, may be integrated with, coupled to or built on-site with a chlorocarbon plant, such as one that produces carbon tetrachloride and tetrachloroethylene. As such, the by-product HCBD would not need to be disposed of or otherwise handled and / or transported, and could instead be utilized directly in the processes. More particularly, the HCBD waste stream from a first system and process, such as a system and process for producing carbon tetrachloride and tetrachloroethylene, may be directly supplied from the first system / process to a second system or process for producing a compound of the formula CF3CR=CCICF3, where R is Cl or H. As described in greater detail herein, the second process may comprise fluorination or chlorofluorination of the HCBD to produce the compound of the formula CF3CR=CCICF3. Such an integrated system would eliminate the need for and risks associated with additional material storage, handling and transportation of HCBD, thereby greatly minimizing human and environmental exposure to HCBD.

[0090] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0091] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0092] The transitional phrase "consisting essentially of is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”. -

[0093] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of.”

[0094] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0095] As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value). All measurements reported herein are understood to be modified by the term “about”, whether or not the term is explicitly used, unless explicitly stated otherwise.

[0096] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

[0097] The term “compound” as used herein is meant to include all stereoisomers, geometric isomers, tautomers, and isotopes of the structures or chemical described. Compounds herein identified by name or structure as one particular tautomeric form are intended to include other tautomeric forms unless otherwise specified.

[0098] As used herein, the term “catalyst”, refers to a substance that speeds up the chemical reaction, but is not consumed by the reaction; thus it can be recovered chemically unchanged at the end of the reaction.

[0099] Disclosed are processes for the preparation of compounds represented by the formula CF3CR=CCICF3, where R is Cl or H, from a reactant composition comprising, consisting of or consisting essentially of hexachlorobutadiene (HCBD).

[0100] In one embodiment, the reactant composition comprising HCBD is supplied directly from a facility which produces HCBD, for example as a waste stream or as a by-product.

[0101] In some embodiments, the reactant composition comprises HCBD and one or more additional compounds selected from the compounds of Table 1 .TABLE 1 : COMPOUNDS OF HCBD COMPOSITION

[0102] In some embodiments, the reactant composition comprises HCBD and more than one of the additional compounds (e.g., two or more; three or more; five or more; ten or more; and the like) of Table 1 . In some embodiments, reactant composition comprises HCBD and each of the additional compounds of Table 1. In some embodiments, reactant composition comprises HCBD and from one to ten of the additional compounds of Table 1 . In some embodiments, reactant composition comprises HCBD and from one to five of the additional compounds of Table 1. In some embodiments, reactant composition comprises HCBD and from one to four of the additional compounds of Table 1 . In someembodiments, reactant composition comprises HCBD and from one to three of the additional compounds of Table 1. In some embodiments, reactant composition comprises HCBD and from one to two of the additional compounds of Table 1.

[0103] In some embodiments, the present invention provides a process comprising reacting a composition comprising HCBD to produce a compound of the formula CF3CR=CCICF3, where R is H or Cl. In some embodiments, the reactant composition comprises HCBD and one or more additional compounds selected from the compounds of Table 1 .

[0104] In some embodiments, when R is H in the formula CF3CR=CCICF3, the compound prepared from HCBD according to the present invention is E- and / or Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2butene (E- and / or Z-HCFO-1326mxz) (CF3- CCI=CH-CF3), preferably Z-HCFO-1326mxz, as shown below:

[0105] In some embodiments, the present invention is directed to a process of preparing E- and / or Z-HCFO-1326mxz, preferably Z-HCFO-1326mxz, from HCBD. The process comprises fluorinating a composition comprising HCBD and one or more additional compounds of Table 1 in the presence of a fluorination catalyst to obtain a product mixture comprising Z-HCFO-1326mxz. The additional compounds of the HCBD starting composition are selected from 1 ,1 ,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3- pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 , 1 ,1 , 2, 2,3,3- heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2,3,3-tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH- CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene.

[0106] Reactions for this process embodiment are as follows:

[0107] While not shown in the above reaction, it will be understood by those skilled in the art that while the additional compounds of Table 1 are not shown in the above reaction, the feed material for the catalytic hydrofluorination reaction of HCBD may further comprise one or more additional compounds selected from 1 ,1 ,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3- pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 , 1 ,1 , 2, 2,3,3- heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2,3,3- tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH- CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene.

[0108] In some embodiments, a reactant or raw material composition comprising HCBD and one or more additional compounds of Table 1 is introduced into a reactor. Anhydrous hydrogen fluoride (HF) is also introduced into the reactor. In some embodiments, an oxidizing agent may be fed to the reactor. It will be understood by those skilled in the art that the oxidizing agent need not be utilized in all circumstances. In the reactor, the HCBD is subjectedto fluorination in the presence of a catalyst comprising a catalytically effective amount to produce a product mixture comprising Z-HCFO-1326mxz.

[0109] In some embodiments, the fluorination of the HCBD is conducted in the reactor and processing conditions are set in accordance with the disclosure of International Application Publication No. WO2019 / 023572, the entire disclosure of which is incorporated herein by reference.

[0110] In some embodiments, the reactor and associated equipment for the fluorination process to convert HCBD to HCFO-1326mxz may be integrated with or built on-site with a chlorocarbon plant, such as one that produces carbon tetrachloride and tetrchloroethylene. As such, the by-product HCBD would not need to be disposed of or otherwise handled and / or transported, and could instead be utilized directly in the fluorination process.

[0111] In some embodiments, the process of preparing 2-chloro-1 , 1 ,1 , 4,4,4- hexafluoro-2-butene provided herein is performed as a liquid phase process. In some embodiments, the process of preparing 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene (e.g., the liquid phase process) is performed in the absence of an additional solvent component.

[0112] In some embodiments, the fluorination process is conducted by flowing HF, HCBD, one or more of the additional compounds of Table 1 , and optionally an oxidizing agent into a catalyst bed in the reactor at a specified temperature. In some embodiments the process is conducted by flowing HF, HCBD, one or more of the additional compounds of Table 1 , optionally an oxidizing agent, and a carrier gas into the catalyst bed in the reactor. Examples of carrier gases include inert gases such as nitrogen, argon and helium.

[0113] The desired reaction results may be achieved through proper selection of operating conditions such as temperature, contact time and HF to HCBD ratios.

[0114] In some embodiments, the reaction zone temperature for the liquidphase catalytic fluorination of HCBD is in the range of from about 30°C to about150°C, or about 50°C to about 150°C, about 50°C to about 140°C, about 70°C to about 140°C, about 90°C to about 130°C. In some embodiments, the process is performed a temperature of from about 80°C to about 150°C. The formation of byproducts can be reduced, and the deactivation of the catalyst can be suppressed by maintaining the reaction temperature within these ranges. However, it will be understood by those skilled in the art that catalytic fluorination of HCBD is an exothermic reaction and temperatures higher than the range of from about 30°C to about 150°C may occur locally within the reactor or catalyst.

[0115] In some embodiments, the contact time (CT) of the reactants and catalyst within the reactor is determined by the following equation:CT = VR / VF,

[0116] where VR is the volume (m3) of the reactor in cubic meters and VF is the total liquid volumetric flow rate (m3 / hr) of the reactor feeds. In one embodiment, the contact time is in the range of from about 0.1 to about 10 hours, inclusive of all values and ranges therebetween. It will be understood by those skilled in the art that the contact time may impact selectivity and conversion of the HCBD, and thus adjustment of the contact time, either to a target time within the range of about 0.1 to about 10 hours or to a target time shorter or longer than this range, may be carried out as needed to achieve the desired reaction results.

[0117] In some embodiments, the reactions in the reactor are typically conducted at atmospheric pressure, or at a pressure lower than atmospheric pressure, or at a pressure higher than atmospheric pressure. That is, the reaction pressure in the reactor for the fluorination reaction is not critical and may be adjusted as needed to achieve the desired reaction results. In one embodiment, the catalytic fluorination reaction in the reactor is carried out at pressures greater than atmospheric pressure, for example, because increased pressure reduces the size of equipment proceeding the reaction. In one embodiment, the pressure within the reactor is in a range from about 0 to 2.0 MPaG (gauge pressure).

[0118] In some embodiments, greater than about 90 mole percent, or greater than about 95 mole percent, greater than about 97 mole percent, greater than about 99 mole percent, greater than about 99.5 mole percent, or greater than about 99.9 mole percent of the HCBD is converted to HCFO-1326mxz.

[0119] In some embodiments, greater than about 99 mole percent, greater than about 99.5 mole percent, or greater than about 99.7 mole percent, or greater than about 99.9 mole percent, of the 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene produced by the processes provided herein is Z-HCFO-1326mxz.

[0120] In some embodiments, the catalytic fluorination processes of this disclosure produce desired products with high selectivity. In some embodiments of this invention, the product selectivity to the compound of formula CF3CR=CCICF3, such as HCFO-1326mxz, is at least 90 mol% (Z to E ratio 1 :1), preferably at least 95 mol%, more preferably at least 99 mol%.

[0121] In some embodiments, the process may be conducted in a batchwise process or a continuous process.

[0122] In some embodiments, greater than about 90 mole percent, or greater than about 95, or greater than about 97, or greater than about 99, or greater than about 99.5, or greater than about 99.9 mole percent, of the hexachlorobutadiene is converted to the 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene in less than about 10 hours of reacting (e.g., less than about 8 hours, less than about 6 hours, less than about 5 hours of reacting).

[0123] In some embodiments, the catalyst for the fluorination of the HCBD is a transition metal catalyst, and more preferably a Group V transition metal catalyst. In some embodiments, the Group V transition metal is niobium or tantalum. In some embodiments, the transition metal catalyst is selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

[0124] In some embodiments, the transition metal catalyst is a tantalum catalyst. In some embodiments, the transition metal catalyst is a tantalum halide catalyst. In some embodiments, the transition metal catalyst is tantalum (V)chloride. In some embodiments, the transition metal catalyst is a niobium catalyst. In some embodiments, the transition metal catalyst is a niobium halide catalyst. In some embodiments, the transition metal catalyst is selected from niobium (IV) chloride, niobium (V) chloride, or a mixture thereof. In some embodiments, the transition metal catalyst is tantalum (V) chloride, niobium (IV) chloride, niobium (V) chloride, or any mixture thereof.

[0125] In some embodiments, the transition metal catalyst is a mixture of a tantalum catalyst and a niobium catalyst. In some embodiments, the transition metal catalyst is a mixture of a tantalum halide catalyst and a niobium halide catalyst. In some embodiments, the transition metal catalyst is a mixture of tantalum chloride and niobium chloride.

[0126] In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride and niobium (IV) chloride. In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride and niobium (V) chloride. In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride, niobium (IV) chloride, and niobium (V) chloride.

[0127] In some embodiments, the catalyst for the fluorination of the HCBD is a Lewis acid catalyst, such as a metal halide catalyst, including but not limited to antimony halides, tin halides, thallium halides, iron halides and combinations of two or more. In certain embodiments, metal chlorides and metal fluorides are employed, including but not limited to SbCIs, SbCh.SbFs, SnCl4, TiCk, NiFs, FeCh, and combinations of two or more of these.

[0128] In some embodiments, examples of liquid phase fluorination catalysts include but are not limited to antimony halide, tin halide, tantalum halide, titanium halide, niobium halide, molybdenum halide, iron halide, fluorinated chrome halide, fluorinated chrome oxide or combinations thereof. In some embodiments, examples of liquid phase fluorination catalysts include but are not limited to SbCIs, SbCh, SbFs, SnCk, TaCIs, TiCk, NbCIs, MoCk, FeCk, fluorinated species of SbCIs, fluorinated species of SbCk, fluorinated species of SnCk, fluorinated species of TaCIs, fluorinated species of TiCk, fluorinated species of NbCIs,fluorinated species of MoCle, fluorinated species of FeC , or combinations thereof. These catalysts can be readily regenerated by any means known in the art if they become deactivated.

[0129] In one embodiment, the liquid phase fluorination catalyst is selected from SbFs, SnCl4, TaCIs, TiCU, NbCIs, and fluorinated species thereof. In another embodiment, the liquid phase fluorination catalyst is selected from SbFs, SnCl4, TaCIs, TiCk and / or fluorinated species thereof. In another embodiment the liquid phase fluorination catalyst is SbFs or SbCIs.

[0130] In some embodiments, a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene, for example, greater than 1 molar equivalent, greater than 2 molar equivalents, greater than 5 molar equivalents, greater than 10 molar equivalents, greater than 20 molar equivalents, greater than 50 molar equivalents, or greater than 100 molar equivalents of HF is used based on 1 molar equivalent of hexachlorobutadiene.

[0131] In some embodiments, about 10 to about 50 molar equivalents of HF is used based on 1 molar equivalent of hexachlorobutadiene, for example about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 50, about 30 to about 40, or about 40 to about 50 molar equivalents of HF. In some embodiments, about 15 to about 20 molar equivalents of HF is used based on 1 molar equivalent of hexachlorobutadiene.

[0132] In some embodiments, a catalytic amount of the transition metal catalyst is used based on 1 molar equivalent of hexachlorobutadiene, for example, less than 0.85 molar equivalent, less than 0.6 molar equivalents, less than 0.4 molar equivalents, less than 0.2 molar equivalents, of transition metal catalyst is used based on 1 molar equivalent of hexachlorobutadiene.

[0133] In some embodiments, about 0.05 to about 0.5 molar equivalents of the metal halide catalyst is used based on 1 molar equivalent of hexachlorobutadiene, for example, about 0.05 to about 0.3, about 0.05 to about0.2, about 0.05 to about 0.1 , about 0.1 to about 0.5, about 0.1 to about 0.3, about 0.1 to about 0.2, about 0.2 to about 0.5, about 0.2 to about 0.3, or about 0.3 to about 0.5 molar equivalents of metal halide catalyst is used based on 1 molar equivalent of hexachlorobutadiene. In some embodiments, about 0.1 to about 0.3 molar equivalents of the metal halide catalyst is used based on 1 molar equivalent of hexachlorobutadiene.

[0134] In some embodiments, the process may comprise adding the fluorination catalyst to the HF to form a first mixture and adding the hexachlorobutadiene to the first mixture to form a second mixture, and then introducing the second mixture into the reactor for the fluorination of the HCBD.

[0135] In an embodiment, the fluorination reaction is conducted in the absence of water. In some embodiments, if water is present, it is present in less than 1000 ppm in an embodiment, or in another embodiment, less than 500 by weight. In some embodiments, if water is present, it is present in less than about 50 ppm, or less than about 25 ppm, or preferably less than about 15 ppm.

[0136] In some embodiments, the composition produced by the system and process from fluorination of the above-disclosed HCBD composition comprises: i) (Z)-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (Z-HCFO-1326mxz); and ii) one or more additional compounds selected from: E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene, E-HFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene), Z-HFO-1316mxx (Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene), HFO-1327mz (1 ,1 ,1 ,2,4,4,4-heptafluorobut-2-ene),HFO-1325lxz (1 , 2-dichloro- 1 ,1 ,4,4,4-pentafluorobut-2-ene), HFO-1325dx (1 ,2-dichloro-3,3,4,4,4-pentafluorobut-1 -ene), HCFC-336mdd (2,3-dichloro-1 , 1 ,1 ,4,4,4-hexafluorobutane), HFC-336maf (2,2-dichloro-1 ,1 , 1 ,4,4,4-hexafluorobutane), HFC-336lbf (1 ,2-dichloro-1 ,1 ,2,4,4,4-hexafluorobutane),HFC-337mbf (2-chloro-1 ,1 ,1 ,2,4,4,4-heptafluorobutane), HFC-337mde (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobutane), HFC-356mff (1 ,1 ,1 ,4,4,4-hexafluorobutane), HFC-346mdf (2-chloro-1 , 1 ,1 ,4,4,4-hexafluorobutane), HFC-338mf (1 , 1 ,1 ,2,2,4,4,4-octafluorobutane, HCFC-1122 (2-chloro-1 , 1 -difluoroethylene), HCFC-124 (2-chloro-1 ,1 ,1 ,2-tetrafluoroethane), CFC-114 (1 , 2-d i ch I oro- 1 , 1 ,2,2-tetrafluoroethane), CFC-113 (1 ,1 ,2-trichloro-1 ,2,2-trifluoroethane), CFC-133a (2-chloro-1 ,1 ,1 -trifluoroethane), CFC-123 (2,2-dichloro-1 ,1 ,1 -trifluoroethane), CFC-123a (1 , 2-d i ch I oro- 1 , 1 ,2-trifluoroethane), CFC-122 (1 , 2 , 2-tri ch I oro- 1 , 1 -difluoroethane), CFC-112a (1 , 1 , 1 ,2-tetrachloro-2,2-difluoroethane), HCFC-224db (1 ,1 ,1 ,3-tetrafluoro-2,3,3-trichloropropane, HFC-225da (1 ,2-dichloro-1 ,1 ,3,3,3-pentafluoropropane), HFC-235da (2-chloro-1 , 1 ,1 ,3,3-pentafluoropropane), HFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane), HFC-236fa (1 ,1 ,1 ,3,3,3-hexafluoropropane), and E- and Z-CFO-1317mx (2-chloro-1 ,1 ,1 , 3,4,4, 4-heptafluorobut-2- ene). wherein the composition comprises greater than about 95 mole percent Z-HCFO- 1326mxz.

[0137] In some embodiments, one or more additional compounds of the composition comprising Z-HCFO-1326mxz are selected from the compounds of Table 2.TABLE 2: COMPOUNDS OF Z-HCFO-1326MXZ COMPOSITION

[0138] In some embodiments, the composition produced by the system and process from fluorination of the above-disclosed HCBD composition comprises Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene; and one or more additional compounds selected from: E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane), E- and Z-CFO- 1317mx (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobut-2-ene). Wherein the composition comprises greater than about 95 mole percent Z-HCFO-1326mxz.

[0139] In some embodiments, the composition produced by the system and process from fluorination of the above-disclosed HCBD composition comprises Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane), wherein the composition comprises greater than about 95 mole percent Z-HCFO-1326mxz, or greater than about 96 mole percent Z-HCFO-1326mxz, greater than about 97 mole percent Z-HCFO-1326mxz, greater than about 98 mole percent Z-HCFO-1326mxz, greater than about 99 mole percent Z-HCFO-1326mxz, greater than about 99.2 mole percent Z-HCFO- 1326mxz, greater than about 99.5 mole percent Z-HCFO-1326mxz, greater than about 99.7 mole percent Z-HCFO-1326mxz, or greater than about 99.9 mole percent Z-HCFO-1326mxz, with the balance being HCFC-336mdd.

[0140] In some embodiments, the composition produced by the system and process from fluorination of the above-disclosed HCBD composition comprises: i) (Z)-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene; and ii) one or more additional compounds selected from:1 ,1 ,1 ,3,3,3-hexafluoropropane;1.1.1 .2.2.4.4.4-octafluorobutane;1.1.1 .4.4.4-hexafluorobutane;1 , 2-d i ch I oro- 1 , 1 ,2,2-tetrafluoroethane;2-chloro-1 ,1 ,1 -trifluoroethane;2-chloro-1 ,1 ,1 ,2,4,4,4-heptafluorobutane;2-chloro-1 , 1 ,1 ,3,4,4,4-heptafluorobutane;2-chloro-1 , 1 ,1 ,3,3-pentafluoropropane;1 -chloro-1 , 1 ,3,3,3-pentafluoropropane;(E)-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene;1 .2-dichloro-3,3,4,4-tetrafluorocyclobut-1 -ene;2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane;2.2-dichloro-1 ,1 ,1 -trifluoroethane;1 .2-dichloro-1 ,1 ,2-trifluoroethane;1 .2-dichloro-1 ,1 ,3,3,3-pentafluoropropane;(E)-2,3-dichloro-1 ,1 , 1 ,4,4,4-hexafluorobut-2-ene;1 .1 .2-trichloro-1 ,2,2-trifluoroethane;(Z)-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene;1 .2-dichloro-3,3,3-trifluoroprop-1 -ene;(Z)-1 ,2-dichloro-1 ,1 ,4,4,4-pentafluorobut-2-ene;2.2-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane; d I-2 , 3-d i ch I oro- 1 ,1 ,1 ,4,4,4-hexafluorobutane; meso-2,3-dichloro-1 ,1 , 1 ,4,4,4-hexafluorobutane;1 .2-dichloro-3,3,4,4,4-pentafluorobut-1 -ene;2.3-dichloro-1 ,1 ,1 ,3-tetrafluoropropane;1 .2-dichloro-1 ,1 ,2,4,4,4-hexafluorobutane;1 .2.2-trichloro-1 , 1 -difluoroethane;1 ,1 ,1 -trichloro-2,2-difluoroethane;1 .1 .2.2-tetrachloro-1 ,2-difluoroethane;1.1.1 .2-tetrachloro-2,2-difluoroethane;1 .2.3-trichloro-1 ,1 ,4,4,4-pentafluorobutane; and1.1.2.3-tetrachloro-4,4,4-trifluorobut-1-ene; wherein the composition comprises greater than about 95 mole percent Z-HCFO- 1326mxz.

[0141] In some embodiments, the composition comprises Z-HCFO-1326mxz and one of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and more than one of the additional compounds (e.g., two or more; three or more; five or more; ten or more; and the like) of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and each of the additional compounds of Table 2. In some embodiments, the composition comprises Z-1326mxz and from one to twenty- five of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and from one to twenty of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and from one to ten of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and from one to five of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and from one to four of the additional compounds of Table 2. In some embodiments, the composition comprises Z-HCFO-1326mxz and from one to three of the additional compounds of Table 2. In some embodiments, the composition comprises Z- HCFO-1326mxz and from one to two of the additional compounds of Table 2.

[0142] In some embodiments, the composition comprises greater than about 97 mole percent Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2. In some embodiments, the composition comprises greater than about 98 mole percent Z-HCFO-1326mxzHCFO- 1326mxz, with the remainder being one or more of the additional compounds of Table 2. In some embodiments, the composition comprises greater than about 99 mole percent Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2. In some embodiments, the composition comprises greater than about 99.5 mole percent Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2. In some embodiments, the composition comprises greater than about 99.9 mole percent Z-HCFO-1326mxz, with the remainder being one or more of the additional compounds of Table 2.

[0143] In some embodiments, the composition consists essentially of or consists of the Z-HCFO-1326mxz and the one or more additional compounds of Table 2.

[0144] In one embodiment, upon completion of a batchwise or continuous fluorination process, the Z-HCFO-1326mxz is of sufficient purity to not require further purification steps.

[0145] In another embodiment, upon completion of a batchwise or continuous fluorination process, the Z-HCFO-1326mxz can be purified and recovered through any conventional process, including for example, fractional distillation.

[0146] The process according to the present invention may further comprise sequential dehydrochlorination of the Z-HCFO-1326mxz to produce hexafluoro-2- butyne (HFB), followed by hydrogenation of the HFB to produce Z-HFO- 1336mzz, as disclosed in International Application Publication No.WO201 9 / 023572, the entire disclosure of which is incorporated herein by reference.

[0147] In one embodiment, the additional compound HCFC-336mdd can be retained with Z-1326mxz in the product mixture, without further purification, and the process may comprise sequential dehydrochlorination of the Z-1326mxz / HCFC-336mdd composition to form HFB followed by hydrogenation of the HFB to produce Z-HFO-1336mzz, as disclosed in International Application Publication No. WO2019 / 023572, the entire disclosure of which is incorporated herein by reference.

[0148] In some embodiments, when R is Cl in the formula CF3CR=CCICF3, the compound prepared from HCBD according to the present invention is E- and / or Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (E- and / or Z-CFO-1316mxx), as shown below:

[0149] In some embodiments, the present invention is directed to a process of preparing E- and / or Z-CFO-1316mxz from HCBD. Preferably, the processaccording to the present invention forms both E-CFO-1316mxz and Z-CFO- 1316mxz from HCBD. The process comprises reacting a composition comprising HCBD and one or more additional compounds with HF and chlorine in the presence of a catalyst to obtain a product mixture comprising Z-CFO- 1316mxx and E-CFO-1316mxx. The additional compounds of the HCBD starting composition are listed in Table 1 and are selected from 1 ,1 , 3,3,4, 4-hexachloro-1- butene (C4H2CI6), carbon tetrachloride (CCk), pentachloroethane (C2HCI5, HCC- 120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3-pentachloro-1-propene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 ,1 ,1 ,2,2,3, 3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2, 3, 3-tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene.

[0150] Reactions for this process embodiment are as follows:1316mxx(E) 1316mxx(Z)

[0151] While not shown in the above reaction, it will be understood by those skilled in the art that while the additional compounds are not shown in the above reaction, the feed material for the catalytic chlorofluorination reaction of HCBD may further comprise one or more additional compounds selected from 1 ,1 ,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3- pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 , 1 ,1 , 2, 2,3,3- heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2,3,3- tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH- CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene.

[0152] In some embodiments, the reactant composition comprises HCBD and more than one of the additional compounds (e.g., two or more; three or more; five or more; ten or more; and the like) of Table 1 . In some embodiments, reactant composition comprises HCBD and each of the additional compounds of Table 1. In some embodiments, reactant composition comprises HCBD and from one to ten of the additional compounds of Table 1 . In some embodiments, reactant composition comprises HCBD and from one to five of the additional compounds of Table 1. In some embodiments, reactant composition comprises HCBD and from one to four of the additional compounds of Table 1 . In some embodiments, reactant composition comprises HCBD and from one to three of the additional compounds of Table 1. In some embodiments, reactant composition comprises HCBD and from one to two of the additional compounds of Table 1.

[0153] In some embodiments, a reactant or raw material composition comprising HCBD and one or more additional compounds of Table 1 is introduced into a reactor. Anhydrous HF and chlorine (Ch) are also introduced into the reactor. In some embodiments, an oxidizing agent may be fed to the reactor. It will be understood by those skilled in the art that the oxidizing agent need not be utilized in all circumstances. In the reactor, the HCBD is subjected to fluorination and chlorination in the presence of a catalyst comprising a catalytically effective amount to produce a product mixture comprising Z-CFO- 1316mxx and E-CFO-1316mxx.

[0154] In some embodiments, the reactor and associated equipment for the chlorofluorination process to convert HCBD to CFO-1316mxx may be integrated with or built on-site with a chlorocarbon plant, such as one that produces carbon tetrachloride and tetrachloroethylene. As such, the by-product HCBD would not need to be disposed of or otherwise handled and / or transported, and could instead be utilized directly in the chlorofluorination process.

[0155] In some embodiments, the process of preparing CFO-1316mxx (E and Z) provided herein is performed as a vapor phase process.

[0156] In some embodiments, the reaction to produce Z-CFO-1316mxx and E- CFO-1316mxx is conducted by flowing HF, CI2, HCBD, one or more of the additional compounds of Table 1 , and optionally an oxidizing agent into a catalyst bed in the reactor at a specified temperature. In some embodiments, the process is conducted by flowing HF, CI2, HCBD, one or more of the additional compounds of Table 1 , optionally an oxidizing agent such as an oxygen containing gas

[0157] , and a carrier gas into the catalyst bed in the reactor. Examples of carrier gases include inert gases such as nitrogen, argon and helium.

[0158] The desired reaction results may be achieved through proper selection of operating conditions such as temperature, contact time and HF, CI2, and HCBD ratios.

[0159] In some embodiments, the reaction zone temperature for the catalytic fluorination / chlorination of HCBD is in the range of from about 200°C to about 500°C, or about 210°C to about 490°C, about 220°C to about 480°C, or about 230°C to about 480°C. In some embodiments, the process is performed a temperature of from about 230°C to about 480°C. The formation of byproducts can be reduced, and the deactivation of the catalyst can be suppressed by maintaining the reaction temperature within these ranges. However, it will be understood by those skilled in the art that catalytic fluorination / chlorination of HCBD is an exothermic reaction and temperatures higher than the range of from about 230°C to about 480°C may occur locally within the reactor or catalyst.

[0160] In some embodiments, the contact time (CT) of the reactants and catalyst within the reactor is determined by the following equation:CT = VR / VF,

[0161] where VR is the volume (m3) of the reactor in cubic meters and VF is the total liquid volumetric flow rate (m3 / hr) of the reactor feeds. In one embodiment, the contact time is in the range of from about 1 to about 60 seconds, inclusive of all values and ranges therebetween. It will be understoodby those skilled in the art that the contact time may impact selectivity and conversion of the HCBD, and thus adjustment of the contact time, either to a target time within the range of about 1 to about 60 seconds or to a target time shorter or longer than this range, may be carried out as needed to achieve the desired reaction results.

[0162] In some embodiments, the reactions in the reactor are typically conducted at atmospheric pressure, or at a pressure lower than atmospheric pressure, or at a pressure higher than atmospheric pressure. That is, the reaction pressure in the reactor for the fluorination reaction is not critical and may be adjusted as needed to achieve the desired reaction results. In one embodiment, the catalytic fluorination reaction in the reactor is carried out at pressures greater than atmospheric pressure, for example, because increased pressure reduces the size of equipment proceeding the reaction. In one embodiment, the pressure within the reactor is in a range from about 0 to 2.0 MPaG (gauge pressure).

[0163] In some embodiments, greater than about 90 mole percent, or greater than about 95 mole percent, greater than about 97 mole percent, greater than about 99 mole percent, greater than about 99.5 mole percent, or greater than about 99.9 mole percent of the HCBD is converted to CFO-1316mxx (E and Z) (Z to E ratio 1 :9 to 9:1 , or Z to E ratio 3:7 to 7:3).

[0164] In some embodiments, greater than about 99 mole percent, greater than about 99.5 mole percent, or greater than about 99.7 mole percent, or greater than about 99.9 mole percent, of the 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene produced by the processes provided herein is CFO-1316mxx (E and Z) (Z to E ratio 1 :9 to 9:1 , or Z to E ratio 3:7 to 7:3).

[0165] In some embodiments, the catalytic chlorofluorination processes of this disclosure produce desired products with high selectivity. In some embodiments of this invention, the product selectivity to the compound of formula CF3CR=CCICF3, such as CFO-1316mxx (E and Z), is at least 90 mol% (Z to Eratio 1 :9 to 9:1 , or Z to E ratio 3:7 to 7:3), preferably at least 95 mol%, more preferably at least 99 mol%.

[0166] In some embodiments, the process may be conducted in a batchwise process or a continuous process.

[0167] In some embodiments, greater than about 90 mole percent, or greater than about 95, or greater than about 97, or greater than about 99, or greater than about 99.5, or greater than about 99.9 mole percent, of the hexachlorobutadiene is converted to the Z-CFO-1316mxx and E-CFO-1316mxx in less than about 60 seconds hours of reacting.

[0168] In some embodiments, the catalyst for the chlorofluorination of the HCBD is a catalyst comprising at least one metal halide, metal oxide or metal oxyhalide. As used herein, the term “halide” refers to fluorides, chlorides, and bromides.

[0169] Examples of suitable metals include nickel, chromium, iron, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum, antimony, aluminum, tin, and lead. It is noted, as defined herein, antimony is a metal.

[0170] Examples of metal halides include nickel halides, chromium halides, iron halides, scandium halides, yttrium halides, lanthanum halides, titanium halides, zirconium halides, hafnium halides, vanadium halides, molybdenum halides, tungsten halides, manganese halides, rhenium halides, ruthenium halides, osmium halides, cobalt halides, palladium halides, copper halides, zinc halides, antimony halides, tantalum halides, aluminum halides, tin halides, and lead halides. In an embodiment, the metal halide is nickel halide, iron halide, or chromium halide or combination thereof is used as a catalyst with or without support on activated carbon. In another embodiment, the metal halide is a bromide or chloride. In still another embodiment, the halide is a chloride. Inanother embodiment, the metal halide is nickel chloride, iron chloride, or chromium chloride or combination thereof.

[0171] Examples of metal oxides include chromium oxide, aluminum oxide and the like. Metal oxyhalides may also be used as chlorofluorination catalysts.

[0172] The chlorofluorination catalysts may be unsupported or supported on activated carbon. The activated carbon may be unwashed or be acid washed or base washed.

[0173] The term "activated carbon" includes any carbon with a relatively high surface area such as from about 50 to about 3000 m2or from about 100 to about 2000 m2(e.g. from about 200 to about 1500 m2or about 300 to about 1000 m2). The activated carbon may be derived from any carbonaceous material, such as coal (e.g. charcoal), nutshells (e.g. coconut) and wood. Any form of activated carbon may be used, such as powdered, granulated and pelleted activated carbon.

[0174] In some embodiments, the activated carbon has been washed with at least one basic solution to remove silicates. For example, the activated carbon is washed with alkali hydroxide or alkaline earth hydroxide or ammonium hydroxide. Examples of basic solutions which have been used to wash the activated carbon include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like.

[0175] The chlorofluorination process is performed in the presence of a chlorine source. In some embodiments, the chlorine source may be chosen from (i) a catalyst comprising a metal chloride or a metal oxychloride, such as a catalyst comprising chromium chloride (CrCh) either as the metal chloride or as chromium chloride supported on carbon, or (ii) chlorine (Ch), which is added to the process when the fluorination catalyst comprises a metal halide or metal oxyhalide wherein the halide is fluoride or bromide or when the catalyst is a metal oxide. Optionally chlorine (CI2) is added when the catalyst is a metal chloride or metal oxychloride.

[0176] In one embodiment, the chlorofluorination catalyst comprises a metal chloride or metal oxychloride. In another embodiment the chlorofluorination catalyst does not comprise a metal chloride or metal oxychloride and the process is performed in the presence of chlorine (CI2).

[0177] In other embodiments, the chlorine is present in the gaseous state. Either chlorine gas is used or chlorine gas is generated in situ from the reaction of hydrogen chloride in the gaseous state and oxygen.

[0178] In an embodiment, the chlorofluorination reaction is conducted in the absence of water. If water is present, it is present in less than 1 % by weight in an embodiment, or in another embodiment, less than 0.5% by weight.

[0179] In some embodiments, a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene, for example, greater than 1 molar equivalent, greater than 2 molar equivalents, greater than 5 molar equivalents, greater than 10 molar equivalents, greater than 20 molar equivalents, greater than 50 molar equivalents, or greater than 100 molar equivalents of HF is used based on 1 molar equivalent of hexachlorobutadiene.

[0180] In some embodiments, about 10 to about 50 molar equivalents of HF is used based on 1 molar equivalent of hexachlorobutadiene, for example about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 50, about 30 to about 40, or about 40 to about 50 molar equivalents of HF. In some embodiments, about 20 to about 30 molar equivalents of HF is used based on 1 molar equivalent of hexachlorobutadiene.

[0181] In some embodiments, a molar excess of chlorine is used based on 1 molar equivalent of hexachlorobutadiene, for example, greater than 1 molar equivalent, greater than 2 molar equivalents, greater than 5 molar equivalents, greater than 10 molar equivalents, greater than 20 molar equivalents, greater than 50 molar equivalents, or greater than 100 molar equivalents of chlorine is used based on 1 molar equivalent of hexachlorobutadiene.

[0182] In some embodiments, the composition produced by the system and process from fluorination and chlorination of the above-disclosed HCBD composition comprises: i) Z-HFO-1316mxx (Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2- ene); ii) E-HFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2- ene); and iii) one or more additional compounds selected from:Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z- 2-chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1 ,2,3-trichloro-1 ,1 ,4,4,4-pentafluoro-2-butene (E-CFC- 1315lxx);Z-1 ,2,3-trichloro-1 , 1 ,4,4,4-pentafluoro-2-butene (Z-CFC- 1315lxx);E-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (E-CFC- 1314kxx);Z-1 ,1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (Z-CFC- 1314kxx);2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane (HFC-346mdf); and 1 , 1 ,1 ,3,3,3-hexafluoropropane (HFC-236fa). wherein the composition comprises greater than about 95 mole percent, or greater than about 96 mole percent, greater than about 97 mole percent, greater than about 98 mole percent, greater than about 99 mole percent, greater than about 99.2 mole percent, greater than about 99.5 mole percent, greater than about 99.7 mole percent, or greater than about 99.9 mole percent Z-CFO- 1316mxx and E-CFO-1316mxx, with the balance being one or more of the additional compounds.

[0183] In some embodiments, one or more additional compounds of the composition comprising Z-HCFO-1316mxx are selected from the compounds of Table 3.TABLE 3: COMPOUNDS OF Z-HCFO-1316MXX COMPOSITION

[0184] In some embodiments, the composition produced by the system and process from fluorination and chlorination of the above-disclosed HCBD composition comprises Z-HFO-1316mxx (Z-2,3-dichloro-1 , 1 ,1 , 4,4,4- hexafluorobut-2-ene); E-HFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut- 2-ene); and one or more additional compounds selected from Z-2-chloro- 1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz), E-2-chloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene (E-HCFO-1326mxz), E-2-chloro-1 ,1 ,1 , 3,4,4, 4-hexafluoro-2- butene, and Z-2-chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene, wherein the composition comprises greater than about 95 mole percent, or greater than about 96 mole percent, greater than about 97 mole percent, greater than about 98 mole percent, greater than about 99 mole percent, greater than about 99.2 mole percent, greater than about 99.5 mole percent, greater than about 99.7 mole percent, or greater than about 99.9 mole percent Z-CFO-1316mxx and E-CFO- 1316mxx, with the balance being one or more of the additional compounds.

[0185] In some embodiments, the composition produced by the system and process from fluorination and chlorination of the above-disclosed HCBD composition comprises Z-HFO-1316mxx (Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene); E-HFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene); Z-2- chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro- 1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene, and Z-2-chloro-1 ,1 ,1 , 3,4,4, 4-hexafluoro-2- butene, wherein the composition comprises greater than about 95 mole percent, or greater than about 96 mole percent, greater than about 97 mole percent, greater than about 98 mole percent, greater than about 99 mole percent, greater than about 99.2 mole percent, greater than about 99.5 mole percent, greater than about 99.7 mole percent, or greater than about 99.9 mole percent Z-CFO- 1316mxx and E-CFO-1316mxx, with the balance being E-HCFO-1326mxz.

[0186] In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and one of the additional compounds. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and more than one of the additional compounds (e.g., two or more; three or more; five or more; ten or more; and the like) of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and each of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and from one to twenty-five of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and from one to twenty of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and from one to ten of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and from one to five of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and from one to four of the additional compounds of Table 3. In some embodiments, the composition comprises Z-CFO-1316mxx and E-CFO-1316mxx and from one to three of the additional compounds of Table 3. In some embodiments, the compositioncomprises Z-CFO-1316mxx and E-CFO-1316mxx and from one to two of the additional compounds of Table 3.

[0187] In some embodiments, the composition comprises greater than about 97 mole percent Z-CFO-1316mxx and E-CFO-1316mxx, with the remainder being one or more of the additional compounds of Table 3. In some embodiments, the composition comprises greater than about 98 mole percent Z- CFO-1316mxx and E-CFO-1316mxx, with the remainder being one or more of the additional compounds of Table 3. In some embodiments, the composition comprises greater than about 99 mole percent Z-CFO-1316mxx and E-CFO- 1316mxx, with the remainder being one or more of the additional compounds of Table 3. In some embodiments, the composition comprises greater than about 99.5 mole percent Z-CFO-1316mxx and E-CFO-1316mxx, with the remainder being one or more of the additional compounds of Table 3. In some embodiments, the composition comprises greater than about 99.9 mole percent Z-CFO-1316mxx and E-CFO-1316mxx, with the remainder being one or more of the additional compounds of Table 3.

[0188] In some embodiments, the composition consists essentially of or consists of the Z-CFO-1316mxx and E-CFO-1316mxx and the one or more additional compounds of Table 3.

[0189] In some embodiments, the composition produced by the chlorofluorination of HCBD has a moisture content of about 100 ppm or less.

[0190] In one embodiment, upon completion of a batchwise or continuous chlorination and fluorination process, the Z-CFO-1316mxx and E-CFO-1316mxx are of sufficient purity to not require further purification steps.

[0191] In another embodiment, upon completion of a batchwise or continuous fluorination process, the Z-CFO-1316mxx and E-CFO-1316mxx can be purified and recovered through any conventional process, including for example, fractional distillation.

[0192] The process according to the present invention may further comprise sequential hydrodechlorination of the Z-CFO-1316mxx and / or E-CFO-1316mxx to produce Z-HCFO-1326mxz; dehydrochlorination of the Z-HCFO-1326mxz to produce hexafluoro-2-butyne (HFB), followed by hydrogenation of the HFB to produce Z-HFO-1336mzz, as disclosed in International Application Publication No. WO2015 / 120250, the entire disclosure of which is incorporated herein by reference.

[0193] Alternatively, in one embodiment, the Z-CFO-1316mxx and / or E-CFO- 1316mxx can go through dichlorination to HFB by Zn in an organic solvent, such as DMF, ethylene glycol, or diglyme, in the liquid phase, or by ZnCI2on a carbon support or an alumina support in the gas phase.

[0194] In one embodiment, the additional compound Z-HCFO-1326mxz can be retained with Z-CFO-1316mxx and / or E-CFO-1316mxx in the product mixture, without further purification, and the process may comprise sequential hydrodechlorination of the Z-CFO-1316mxx / E-CFO-1316mxx / Z-HCFO-1326mxz mixture to produce Z-HCFO-1326mxz, dehydrochlorination of the Z-1326mxz to form HFB, and hydrogenation of the HFB to produce Z-HFO-1336mzz.

[0195] The present application further provides an integrated system for preparing a compound of the formula CF3CR=CCICF3, wherein R is H or Cl. Referring to Fig. 1 , the system comprises a first reactor 10 and a second reactor 20 coupled to the first reactor 10. The first reactor 10 is configured to produce a composition comprising HCBD and one or more additional compounds selected from the compounds of Table 1 . In some embodiments, the composition comprising HCBD is a waste stream or a by-product which has been separated from a desired product, such as carbon tetrachloride and tetrachloroethylene, for example by a distillation column 30 provided downstream of the first reactor 10 and upstream of the second reactor 20. The second reactor 20 receives the composition comprising HCBD and, in the presence of a catalyst, converts it to a product mixture comprising the compound of the formula CF3CR=CCICF3.

[0196] The present application further provides compositions comprising a major component of the formula CF3CR=CCICF3, where R is Cl or H, (e.g., E- or Z-HCFO-1326mxz, or E- or Z-CFO-1316mxx) in combination with one or more additional compounds. In some embodiments, the compositions are prepared according to one or more of the processes described herein.

[0197] The compositions provided herein ( / .e., the compositions of the invention) may be used as intermediates for the production of Z-HFO-1336mzz.

[0198] Z-HFO-1336mzz compositions may be useful, for example, in a wide range of applications, including their use as refrigerants, uses in high- temperature heat pumps, organic Rankine cycles, as fire extinguishing / fire suppression agents, propellants, foam blowing agents, solvents, and / or cleaning fluids.

[0199] The Z-HFO-1336mzz compositions may also useful as low global warming potential (GWP) heat transfer compositions, refrigerants, power cycle working fluids, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, expansion agents for polyolefins and polyurethane, gaseous dielectrics, fire extinguishing agents, and fire suppression agents, in liquid or gaseous form. In some embodiments, the Z-HFO-1336mzz compositions may be useful as a working fluid used to carry heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as a refrigerant in a cycle wherein the fluid undergoes a phase change (e.g., from a liquid to a gas and back or vice versa).

[0200] Examples of heat transfer systems include but are not limited to air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units and combinations thereof.

[0201] In some embodiments, the Z-HFO-1336mzz compositions may be useful in mobile heat transfer systems, including refrigeration, air conditioning, orheat pump systems or apparatus. In some embodiments, the Z-HFO-1336mzz compositions may be useful in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or apparatus.

[0202] As used herein, mobile heat transfer systems refers to any refrigeration, air conditioner, or heating apparatus incorporated into a transportation unit for the road, rail, sea or air. In addition, mobile refrigeration or air conditioner units, include those apparatus that are independent of any moving carrier and are known as “intermodal” systems. Such intermodal systems include “containers’ (combined sea / land transport) as well as “swap bodies” (combined road / rail transport).

[0203] As used herein, stationary heat transfer systems are systems that are fixed in place during operation. A stationary heat transfer system may be associated within or attached to buildings of any variety or may be stand-alone devices located out of doors, such as a soft drink vending machine. These stationary applications may be stationary air conditioning and heat pumps (including but not limited to chillers, high temperature heat pumps, including trans-critical heat pumps (e.g., with condenser temperatures above 50°C, above 70°C, above 80°C, above 100°C, above 120°C, above 140°C, above 160°C, above 180°C, or above 200°C), residential, commercial or industrial air conditioning systems, and including window, ductless, ducted, packaged terminal, chillers, and those exterior but connected to the building such as rooftop systems). In stationary refrigeration applications, the compositions provided herein may be useful in high temperature, medium temperature, and / or low temperature refrigeration equipment including commercial, industrial or residential refrigerators and freezers, ice machines, self-contained coolers and freezers, flooded evaporator chillers, direct expansion chillers, walk-in and reachin coolers and freezers, and combination systems. In some embodiments, the disclosed compositions may be used in supermarket refrigerator systems.

[0204] Therefore, in accordance with the present invention, the Z-HFO- 1336mzz compositions which may be produced from the reactive intermediates disclosed herein may be useful in methods for producing cooling, producing heating, and transferring heat.

[0205] In some embodiments, the present application provides a method for producing cooling comprising evaporating a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein in the vicinity of a body to be cooled, and thereafter condensing said composition.

[0206] In some embodiments, the present application provides a method for producing heating comprising condensing a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein in the vicinity of a body to be heated, and thereafter evaporating said compositions.

[0207] In some embodiments, the present application provides a method of using Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein as heat transfer fluid compositions. In some embodiments, the method comprises transporting said composition from a heat source to a heat sink.

[0208] The Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein may also be useful as low global warming potential (GWP) replacements for currently used refrigerants, including but not limited to, R-123 ( / .e., HFC-123, 2, 2-dichloro-1 , 1 ,1 -trifluoroethane), R-11 ( / .e., CFC-11 , trichlorofluoromethane), R-245fa ( / .e. HFC-245fa, 1 , 1 ,1 , 3,3- pentafluoropropane), R-114 ( / .e., CFC-114, 1 , 2-dichloro-1 , 1 ,2,2- tetrafluoroethane), R-236fa ( / .e., HFC-236a, 1 ,1 ,1 ,3,3,3-hexafluoropropane), R- 236ea ( / .e., HFC-236ea, 1 ,1 ,1 ,2,3,3-hexafluoropropane), R-124 ( / .e., HCFC-124, 2-chloro-1 ,1 ,1 ,2-tetrafluoroethane), among others.

[0209] In some embodiments, the Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein may be useful as refrigerants and provide at least comparable cooling performance ( / .e., cooling capacity andenergy efficiency) as the refrigerant for which a replacement is being sought. Additionally, the Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein may provide heating performance (i.e., heating capacity and energy efficiency) comparable to a refrigerant being replaced.

[0210] In some embodiments the present application provides a method for recharging a heat transfer system that contains a refrigerant to be replaced and a lubricant, said method comprising removing the refrigerant to be replaced from the heat transfer system while retaining a substantial portion of the lubricant in said system and introducing a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein to the heat transfer system. In some embodiments, the lubricant in the system is partially replaced (e.g., replace a portion of the mineral oil lubricant used with HCFC-123 with a POE lubricant).

[0211] In some embodiments, the Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein may be used to top-off a refrigerant charge in a chiller. For example, if a chiller using HCFC-123 has diminished performance due to leakage of refrigerant, the Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein may be added to bring performance back up to specification.

[0212] The present application further provides a heat exchange system containing any of the Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein, wherein said system is selected from the group consisting of air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units, and systems having combinations thereof. Additionally, the Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein may be useful in secondary loop systems wherein these compositions serve as the primary refrigerant thus providing cooling to a secondary heat transfer fluid that thereby cools a remote location.

[0213] Vapor-compression refrigeration, air-conditioning, or heat pump systems include an evaporator, a compressor, a condenser, and an expansion device. A vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows: Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator, by withdrawing heat from the environment, at a low temperature to form a vapor and produce cooling. The low-pressure vapor enters a compressor where the vapor is compressed to raise its pressure and temperature. The higher-pressure (compressed) vapor refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.

[0214] The present application further provides foam expansion agent compositions comprising a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein for use in preparing foams. In some embodiments, the present application provides foamable compositions, including but not limited to, thermoset (e.g., polyurethane, polyisocyanurate, or phenolic) foam compositions, thermoplastic (e.g., polystyrene, polyethylene, or polypropylene) foam compositions and methods of preparing foams. In some embodiments, one or more of the Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein may be included as a foam expansion agent in the foamable compositions, wherein foamable composition may include one or more additional components capable of reacting and / or mixing and foaming under the proper conditions to form a foam or cellular structure.

[0215] The present application further provides a method of forming a foam comprising: (a) adding to a foamable composition a Z-HFO-1336mzzcomposition produced from the reactive intermediates disclosed herein; and (b) processing the foamable composition under conditions effective to form a foam.

[0216] The present application further provides the use of the Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein as propellants in sprayable compositions. Additionally, the present application provides sprayable compositions of the invention. The active ingredient to be sprayed together with inert ingredients, solvents, and other materials may also be present in a sprayable composition. In some embodiments, the sprayable composition is an aerosol. The Z-HFO-1336mzz compositions produced from the reactive intermediates disclosed herein can also be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, mold release sprays, insecticides, and the like, and consumer aerosols such as personal care products (e.g., hair sprays, deodorants, and perfumes), household products (e.g., waxes, polishes, pan sprays, room fresheners, and household insecticides), and automotive products (e.g., cleaners and polishers), as well as medicinal materials such as anti-asthma and anti-halitosis medications. Examples include, but are not limited to, metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of medicaments to accessible mucous membranes or intra-nasally.

[0217] The present invention further provides a process for producing aerosol products comprising the step of adding a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein to a formulation to an aerosol container, wherein said composition functions as a propellant. Additionally, the present application further provides a process for producing aerosol products comprising the step of adding a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein to a barrier type aerosol package (e.g., a bag-in-a-can or piston can) wherein said composition of the invention is kept separated from other formulation ingredients in an aerosol container, and wherein said composition functions as a propellant. Additionally, the presentapplication further provides a process for producing aerosol products comprising the step of adding only a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein to an aerosol package, wherein said composition functions as the active ingredient (e.g., a duster, or a cooling or freezing spray).

[0218] The present application further provides a process for converting heat from a heat source to mechanical energy, comprising heating a working fluid comprising a Z-HFO-1336mzz composition produced from the reactive intermediates disclosed herein and thereafter expanding the heated working fluid. In the process, heating of the working fluid uses heat supplied from the heat source; and expanding of the heated working fluid generates mechanical energy as the pressure of the working fluid is lowered.

[0219] The process for converting heat may be a subcritical cycle, a trans- critical cycle, or a supercritical cycle. In a transcritical cycle, the working fluid is compressed to a pressure above its critical pressure prior to being heated, and then during expansion the working fluid pressure is reduced to below its critical pressure. In a super critical cycle, the working fluid remains above its critical pressure for the complete cycle (e.g., compression, heating, expansion and cooling).

[0220] Heat sources may include, for example, low pressure steam, industrial waste heat, solar energy, geothermal hot water, low-pressure geothermal steam (primary or secondary arrangements), or distributed power generation equipment utilizing fuel cells or prime movers such as turbines, microturbines, or internal combustion engines. One source of low-pressure steam could be the process known as a binary geothermal Rankine cycle. Large quantities of low-pressure steam can be found in numerous locations, such as in fossil fuel powered electrical generating power plants. Other sources of heat include waste heat recovered from gases exhausted from mobile internal combustion engines (e.g., truck or rail diesel engines or ships), waste heat from exhaust gases from stationary internal combustion engines (e.g., stationary diesel engine powergenerators), waste heat from fuel cells, heat available at combined heating, cooling and power or district heating and cooling plants, waste heat from biomass fueled engines, heat from natural gas or methane gas burners or methane-fired boilers or methane fuel cells (e.g., at distributed power generation facilities) operated with methane from various sources including biogas, landfill gas and coal-bed methane, heat from combustion of bark and lignin at paper / pulp mills, heat from incinerators, heat from low pressure steam at conventional steam power plants (to drive "bottoming" Rankine cycles), and geothermal heat.

[0221] In some embodiments, the process of converting heat is performed using an organic Rankine power cycle. Heat available at relatively low temperatures compared to steam (inorganic) power cycles can be used to generate mechanical power through Rankine cycles using working fluids as described herein. In some embodiments, the working fluid is compressed prior to being heated. Compression may be provided by a pump which pumps working fluid to a heat transfer unit (e.g., a heat exchanger or an evaporator) where heat from the heat source is used to heat the working fluid. The heated working fluid is then expanded, lowering its pressure. Mechanical energy is generated during the working fluid expansion using an expander. Examples of expanders include, but are not limited to, turbo or dynamic expanders, such as turbines, and positive displacement expanders, such as screw expanders, scroll expanders, and piston expanders. Examples of expanders also include rotary vane expanders.

[0222] Mechanical power can be used directly (e.g., to drive a compressor) or be converted to electrical power through the use of electrical power generators. In a power cycle where the working fluid is re-used, the expanded working fluid is cooled. Cooling may be accomplished in a working fluid cooling unit (e.g., a heat exchanger or a condenser). The cooled working fluid can then be used for repeated cycles ( / .e., compression, heating, expansion, etc.). The same pump used for compression may be used for transferring the working fluid from the cooling stage.

[0223] The present application further provides a method for detecting a leak from a container comprising sampling the air in the vicinity of the container and detecting at least one additional compound of a composition provided herein with means for detecting the leak, wherein a composition of the present invention is contained inside the container. The term “in the vicinity of’ refers to within 12 inches of the outside surface of the container. Alternatively, in the vicinity may be within 6 inches, within 3 inches or within one inch of the outside surface of the container.

[0224] A container may be any known container or system or apparatus that is filled with a composition comprising a compound of the formula CF3CR=CCICF3, where R is Cl or H, such as Z- or E-HCFO-1326mxz and Z- or E-CFO-1316mxx. A container may include, but is not limited to, a storage container, a transport container, an aerosol can, a fire extinguishing system, a chiller apparatus, a heat pump apparatus, heat transfer container, and a power cycle apparatus (e.g., an organic Rankine cycle system).

[0225] Means for detecting a leak may be performed using any known sensor designed to detect leaks. In particular, means for detecting the leak includes, but is not limited to, electrochemical, corona discharge, and mass spectroscopic leak detectors.

[0226] Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.EXAMPLES

[0227] The invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes and are not intended to limit the invention in any manner.Example 1 : Liquid phase production of Z-HCFO-1326mxz

[0228] HCBD + 6HF HCFO-1326mxz(Z) + 5HCI CatZ- 326nwzSbCIs (10.5 g) is added to a 210 mL Hastelloy C reactor, followed by HF (49 g). The reaction mixture is heated at 100 °C for 1 hour and then cooled to 0°C. Hexachlorobutadiene (30 g) and one or more additional compounds selected from 1 ,1 ,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3- pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 , 1 ,1 , 2, 2,3,3- heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2,3,3- tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH- CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene are added to the reactor and the reaction mixture is heated to 100°C. The reaction rate is indicated by pressure increase and stabilization of the pressure indicated completion of the reaction. Similar reactions are also performed using TaCIs catalyst or NbCIs catalyst. The reactions stereoselectively produce a product mixture comprising (Z)-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene in a ratio of greater than about 99:1 (Z)-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene:(E)-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene. The product mixture further comprises about 5 mole percent or less of one or more additional compounds selected from:E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene,E-HFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro2-butene), Z-HFO-1316mxx (Z-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene), HFO-1327mz (1 ,1 ,1 ,2,4,4,4-heptafluoro2-butene),HFO-1325lxz (1 , 2-dichloro- 1 ,1 ,4,4,4-pentafluoro-2-butene), HFO-1325dx (1 ,2-dichloro-3,3,4,4,4-pentafluoro-2-butene), HCFC-336mdd (2,3-dichloro-1 , 1 ,1 ,4,4,4-hexafluorobutane), HFC-336maf (2,2-dichloro-1 ,1 , 1 ,4,4,4-hexafluorobutane), HFC-336lbf (1 ,2-dichloro-1 ,1 ,2,4,4,4-hexafluorobutane), HFC-337mbf (2-chloro-1 ,1 ,1 ,2,4,4,4-heptafluorobutane), HFC-337mde (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluorobutane), HFC-356mff (1 ,1 ,1 ,4,4,4-hexafluorobutane), HFC-346mdf (2-chloro-1 , 1 ,1 ,4,4,4-hexafluorobutane), 338mf (1 ,1 ,1 ,2,2,4,4,4-octafluorobutane) HCFC-1122 (2-chloro-1 , 1 -difluoroethylene), HCFC-124 (2-chloro-1 ,1 ,1 ,2-tetrafluoroethane), CFC-114 (1 , 2-d i ch I oro- 1 , 1 ,2,2-tetrafluoroethane), CFC-113 (1 ,1 ,2-trichloro-1 ,2,2-trifluoroethane), CFC-133a (2-chloro-1 ,1 ,1 -trifluoroethane), CFC-123 (2,2-dichloro-1 ,1 ,1 -trifluoroethane), CFC-123a (1 , 2-d i ch I oro- 1 , 1 ,2-trifluoroethane), CFC-122 (1 ,2,2-trichloro-1 , 1 -difluoroethane), CFC-112a (1 , 1 , 1 ,2-tetrachloro-2,2-difluoroethane), HCFC-224db (1 ,1 ,1 ,3-tetrafluoro-2,3,3-trichloropropane), HFC-225da (1 ,2-dichloro-1 ,1 ,3,3,3-pentafluoropropane), HFC-235da (2-chloro-1 , 1 ,1 ,3,3-pentafluoropropane), HFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane), and HFC-236fa (1 ,1 ,1 ,3,3,3-hexafluoropropane).Example 2: Gas phase production of Z- and E-CFO-1316mxx from HCBD

[0229]

[0230] An Inconel tube® (0.5 inch OD, 16 inch length, 0.34 in wall thickness) is filled with 12 cc (6.45 g) of 10% chrome chloride on carbon catalyst. The catalyst is activated with anhydrous HF at 300°C. The reactor is heated in a Lindberg furnace to 400°C and HCBD is fed at 0.16 ml / hour, HF gas at 8.2 seem (standard cubic centimeters per minute) through a vaporizer controlled at 220°C, followed by chlorine gas at 2.0 seem. The feed also includes one or more additional compounds selected from 1 ,1 ,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N),1.1.2.3.3-pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az),1.1.1 .2.2.3.3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2, 3, 3-tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene. The experiment is carried out at 1-2 psig. The effluent of the reactor is analyzed online using an Agilent® 6890 GC / 5973 MS and a Restek® PC2618 5% Krytox® CBK-D / 60 / 80 6-meter x 2mm ID 1 / 8” OD packed column purged with helium at 30 seem. The data shows 100% HCBD conversion, with CFO-1316mxx selectivity at 70% (Z to E ratio 1 :1). In addition to E- and Z-CFO-1316mxx, the product mixture comprises about 5 mole percent or less of one or more additional compounds selected from:Z-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (E-CFO-1317mx); Z- 2-chloro-1 ,1 ,1 ,3,4,4,4-hexafluoro-2-butene (Z-CFO-1317mx); E-1 ,2,3-trichloro-1 , 1 ,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx); Z-1 ,2,3-trichloro-1 , 1 ,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx); E-1 , 1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (E-CFC-1314kxx); Z-1 , 1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (Z-CFC-1314kxx); 2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane (HFC-346md); and1 ,1 ,1 ,3,3,3-hexafluoropropane (HFC-236fa).

[0231] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Claims

CLAIMSWhat is claimed is:1 . A process of preparing a compound of the formula CF3CR=CCICF3, wherein R is H or Cl, the processing comprising reacting a composition comprising hexachlorobutadiene (HCBD) and one or more additional compounds in the presence of a catalyst to obtain a product mixture comprising the compound of the formula CF3CR=CCICF3, wherein the one or more additional compounds are selected from the group consisting of 1 ,1 , 3, 3,4,4- hexachloro-1 -butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3- pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az),1 ,1 ,1 ,2,2,3, 3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2, 3, 3-tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene.

2. The process of claim 1 , wherein the compound of the formula CF3CR=CCICF3 is 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

3. The process of claim 2, the process comprising reacting the composition comprising HCBD and one or more additional compounds with HF in the presence of a fluorination catalyst to produce a product mixture comprising 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

4. The process of any of claims 2-3, wherein greater than about 99 mole percent of the 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene produced is (Z)-2- chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

5. The process of any of claims 3-4, wherein the fluorination catalyst is a transition metal catalyst selected from the group consisting of a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

6. The process of claim 5, wherein the transition metal catalyst is selected from the group consisting of tantalum (V) chloride, niobium (V) chloride, niobium (IV) chloride, and combinations of two or more.

7. The process of any of claims 3-4, wherein the fluorination catalyst is a metal halide selected from the group consisting of antimony halides, tin halides, thallium halides, iron halides and combinations of two or more.

8. The process of claim 7, wherein the metal halide catalyst is selected from the group consisting of SbCIs, SbCh, SbFs, SnCl4, TiCU, NiFs, FeCh, and combinations of two or more, and preferably the metal halide catalyst is SbCIs or SbFs.

9. The process of claim 3, wherein a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene.

10. The process of claim 3, wherein the process is performed a temperature of from about 80°C to about 150°C.11 . The process of claim 2, wherein the 2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- butene of the product mixture is Z-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

12. The process of any of claims 2-11 , wherein the product mixture further comprises one or more additional compounds selected from the group consisting of E-2-chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene; E-CFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene); Z-CFO-1316mxx (Z-2,3- dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene); H FO-1327mz (1 , 1 , 1 ,2, 4,4,4- heptafluoro-2-butene); HCFO-1325lxz (1 , 2-dichloro- 1 ,1 ,4,4,4-pentafluoro-2- butene); HCFO-1325dx (1 ,2-dichloro-3,3,4,4,4-pentafluoro-2-butene); HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane); HCFC-336maf (2,2-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane); HCFC-336lbf (1 ,2-dichloro-1 , 1 ,2,4,4,4-hexafluorobutane); HCFC-337mbf (2-chloro-1 ,1 ,1 , 2, 4,4,4- heptafluorobutane); HCFC-337mde (2-chloro-1 , 1 , 1 , 3, 4,4,4- heptafluorobutane); HFC-356mff (1 , 1 ,1 ,4,4,4-hexafluorobutane); HCFC- 346mdf (2-chloro-1 , 1 ,1 ,4,4,4-hexafluorobutane); HFC-338mf(1 ,1 ,1 ,2,2,4,4,4-octafluorobutane); HCFC-1122 (2-chloro-1 ,1- difluoroethylene); HCFC-124 (2-chloro-1 ,1 ,1 ,2-tetrafluoroethane); CFC-114 (1 ,2-d ichloro-1 , 1 ,2,2-tetrafluoroethane); CFC-113 (1 ,1 ,2-trichloro-1 ,2,2- trifluoroethane); CFC-133a (2-chloro-1 , 1 ,1 -trifluoroethane); HCFC-123 (2,2- dichloro-1 , 1 ,1 -trifluoroethane); HCFC-123a (1 ,2-dichloro-1 , 1 ,2- trifluoroethane); HCFC-122 (1 , 2, 2-trichloro-1 ,1 -difluoroethane); CFC-112a (1 ,1 ,1 ,2-tetrachloro-2,2-difluoroethane); HCFC-224db (1 ,1 ,1 ,3-tetrafluoro- 2,3,3-trichloropropane); E-CFO-1317mx (E-2-chloro-1 , 1 , 1 , 3, 4,4,4- heptafluorobut-2-ene); Z-CFO-1317mx (Z-2-chloro-1 ,1 ,1 , 3, 4,4,4- heptafluorobut-2-ene); HCFC-225da (1 ,2-dichloro-1 , 1 ,3,3,3- pentafluoropropane); HCFC-235da (2-chloro-1 , 1 , 1 ,3,3-pentafluoropropane); CFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane); and HFC-236fa (1 ,1 ,1 ,3,3,3-hexafluoropropane).

13. The process of claim 11 , wherein the product mixture further comprises one or more additional compounds selected from the group consisting of E-2- chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene, E-CFO-1317mx (2-chloro-1 ,1 ,1 ,3,4,4,4-heptafluoro-2-butene), Z-CFO-1317mx (2-chloro-1 ,1 ,1 , 3, 4,4,4- heptafluoro-2-butene) and HCFC-336mdd (2,3-dichloro-1 , 1 , 1 ,4,4,4- hexafluorobutane).

14. The process of claim 11 , wherein the product mixture further comprises HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane).

15. The process of any of claims 11-14, the process further comprising sequential dehydrochlorination of the Z-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2- ene to produce hexafluoro-2-butyne, followed by hydrogenation of the hexafluoro-2-butyne to produce (Z)-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

16. The process of any of claims 12-14, the process further comprising sequential dechlorination of a mixture of the Z-chloro-1 , 1 ,1 , 4,4,4- hexafluorobut-2-ene and 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane to produce hexafluoro-2-butyne, followed by hydrogenation of the hexafluoro- 2-butyne to produce (Z)-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

17. The process of claim 2, wherein the process is conducted in the liquid phase.

18. The process of claim 1 , wherein the compound of the formula CF3CR=CCICF3 is 2,3-dichloro-1 , 1 ,1 ,4,4,4-hexafluorobut-2-ene.

19. The process of claim 18, the process comprising reacting the composition comprising HCBD and one or more additional compounds with HF and chlorine in the presence of a metal oxide or metal halide catalyst to produce a product mixture comprising 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

20. The process of any of claims 18-19, wherein the 2,3-dichloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene comprises the Z and E isomers.21 . The process of any of claims 19-20, wherein the metal halide catalyst is selected from the group consisting of nickel halides, chromium halides, iron halides, scandium halides, yttrium halides, lanthanum halides, titanium halides, zirconium halides, hafnium halides, vanadium halides, molybdenum halides, tungsten halides, manganese halides, rhenium halides, ruthenium halides, osmium halides, cobalt halides, palladium halides, copper halides, zinc halides, antimony halides, tantalum halides, aluminum halides, tin halides, lead halides, and mixtures thereof.

22. The process of claim 21 , wherein the metal halide catalyst is unsupported or supported on activated carbon.

23. The process of claim 22, wherein the activated carbon may optionally be acid washed or caustic washed.

24. The process of any of claims 19-20, wherein the metal oxide catalyst is selected from the group consisting of chromium oxide, aluminum oxide and mixtures thereof.

25. The process of claim 24, wherein the metal oxide catalyst is unsupported or supported on activated carbon.

26. The process of claim 25, wherein the activated carbon may optionally be acid washed or caustic washed.

27. The process of any of claims 19-26, wherein the catalyst comprises a chloride source for the process of claim 19.

28. The process of claim 19, wherein a molar excess of HF is used based on 1 molar equivalent of hexachlorobutadiene.

29. The process of claim 19, wherein a molar excess of chlorine is used based on 1 molar equivalent of hexachlorobutadiene.

30. The process of claim 19, wherein the process is performed a temperature of from about 230°C to about 480°C.31 . The process of claim 19, wherein the product mixture comprises E-2,3- dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene and Z-2,3-dichloro-1 ,1 ,1 ,4,4,4- hexafluorobut-2-ene.

32. The process of claim 31 , wherein the product mixture further comprises one or more additional compounds selected from the group consisting of Z-2- chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1.1.1.4.4.4-hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1.1.1.3.4.4.4-hexafluoro-2-butene (E-CFO-1317mx); Z- 2-chloro-1.1.1 .3.4.4.4-hexafluoro-2-butene (Z-CFO-1317mx); E-1 ,2,3-trichloro-1 .1 .4.4.4-pentafluoro-2-butene (E-CFC-1315lxx); Z-1 ,2, 3-trichloro-1 ,1 ,4,4,4- pentafluoro-2-butene (Z-CFC-1315lxx); E-1 , 1 ,2,3-tetrachloro-1 ,4,4,4- tetrafluoro-2-butene (E-CFC-1314kxx); Z-1 , 1 ,2,3-tetrachloro-1 ,4,4,4- tetrafluoro-2-butene (Z-CFC-1314kxx); 2-chloro-1 , 1 ,1 , 4,4,4- hexafluorobutane (HFC-346mdf); and 1 ,1 ,1 ,3,3,3-hexafluoropropane (HFC- 236fa).

33. The process of claim 31 , wherein the product mixture further comprises one or more additional compounds selected from the group consisting of Z-2- chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz) and E-2-chloro- 1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (E-HCFO-1326mxz).

34. The process of claim 31 , wherein the product mixture further comprises Z-2- chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (Z-HCFO-1326mxz).

35. The process of claim 19, the process further comprising sequential dechlorination of the 2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene to produce hexafluoro-2-butyne, followed by hydrogenation of the hexafluoro- 2-butyne to produce (Z)-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene.

36. The process of claim 19, wherein the process is conducted in the gas phase.

37. A composition comprising hexachlorobutadiene and one or more additional compounds selected from the group consisting of 1 ,1 , 3,3,4, 4-hexachloro-1- butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC- 110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3-pentachloroprop-1-ene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 ,1 ,1 ,2,2,3, 3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2,3,3-tetrachloro-1- propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene.

38. The composition according to claim 37, wherein the one or more additional compounds are present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

39. A composition comprising Z-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene and one or more additional compounds selected from the group consisting of E-2- chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene; E-CFO-1316mxx (E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene); Z-CFO-1316mxx (Z-2,3-dichloro-1.1.1 .4.4.4-hexafluorobut-2-ene); HFO-1327mz (1 ,1 ,1 , 2, 4,4,4- heptafluorobut-2-ene); HCFO-1325lxz (1 ,2-dichloro-1 , 1 ,4,4,4- pentafluorobut-2-ene); HCFO-1325dx (1 , 2-dichloro-3, 3,4,4, 4-pentafluorobut- 1-ene); HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane); HCFC- 336maf (2,2-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane); HCFC-336lbf (1 ,2- dichloro-1 ,1 ,2,4,4,4-hexafluorobutane); HCFC-337mbf (2-chloro-1.1.1 .2.4.4.4-heptafluorobutane); HCFC-337mde (2-chloro-1 ,1 , 1 , 3, 4,4,4- heptafluorobutane); HFC-356mff (1 , 1 ,1 ,4,4,4-hexafluorobutane); HCFC- 346mdf (2-chloro-1 , 1 ,1 ,4,4,4-hexafluorobutane); HFC-338mf (1 ,1 ,1 ,2,2,4,4,4-octafluorobutane); HCFC-1122 (2-chloro-1 ,1- difluoroethylene); HCFC-124 (2-chloro-1 ,1 ,1 ,2-tetrafluoroethane); CFC-114 (1 ,2-d ichloro-1 , 1 ,2,2-tetrafluoroethane); CFC-113 (1 ,1 ,2-trichloro-1 ,2,2- trifluoroethane); CFC-133a (2-chloro-1 , 1 ,1 -trifluoroethane); HCFC-123 (2,2- dichloro-1 , 1 ,1 -trifluoroethane); HCFC-123a (1 ,2-dichloro-1 , 1 ,2- trifluoroethane); HCFC-122 (1 , 2, 2-trichloro-1 ,1 -difluoroethane); CFC-112a (1 ,1 ,1 ,2-tetrachloro-2,2-difluoroethane); HCFC-224db (1 ,1 ,1 ,3-tetrafluoro- 2,3,3-trichloropropane); CFO-1317mx (2-chloro-1 ,1 ,1 , 3, 4,4,4- heptafluorobut-2-ene); HCFC-225da (1 ,2-dichloro-1 , 1 ,3,3,3- pentafluoropropane); HCFC-235da (2-chloro-1 , 1 , 1 ,3,3-pentafluoropropane); CFC-235fa (1-chloro-1 ,1 ,3,3,3-pentafluoropropane); and HFC-236fa (1 ,1 ,1 ,3,3,3-hexafluoropropane).

40. The composition according to claim 39, wherein the one or more additional compounds are present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.41 . A composition comprising Z-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene and one or more additional compounds selected from the group consisting of E-2- chloro-1 ,1 ,1 ,4,4,4-hexafluoro-2-butene and HCFC-336mdd (2,3-dichloro-1.1.1 .4.4.4-hexafluorobutane).

42. The composition according to claim 41 , wherein the one or more additional compounds are present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

43. A composition comprising Z-chloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene and HCFC-336mdd (2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobutane), wherein the HCFC-336mdd is present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

44. A composition comprising E-2,3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene; Z-2.3-dichloro-1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene; and one or more additional compounds selected from the group consisting of Z-2-chloro-1 , 1 ,1 , 4,4,4- hexafluorobut-2-ene (Z-HCFO-1326mxz); E-2-chloro-1 , 1 ,1 , 4,4,4- hexafluorobut-2-ene (E-HCFO-1326mxz); E-2-chloro-1 , 1 , 1 , 3, 4,4,4- hexafluoro-2-butene (E-CFO-1317mx); Z- 2-chloro-1 ,1 ,1 , 3,4,4, 4-hexafluoro- 2-butene (Z-CFO-1317mx); E-1 , 2 , 3-trichloro-1 , 1 ,4,4,4-pentafluoro-2-butene (E-CFC-1315lxx); Z-1 , 2 ,3-trichloro-1 , 1 ,4,4,4-pentafluoro-2-butene (Z-CFC-1315lxx); E-1 , 1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (E-CFC- 1314kxx); Z-1 , 1 ,2,3-tetrachloro-1 ,4,4,4-tetrafluoro-2-butene (Z-CFC- 1314kxx); 2-chloro-1 ,1 ,1 ,4,4,4-hexafluorobutane (HFC-346mdf); and1.1.1 .3.3.3-hexafluoropropane (HFC-236fa).

45. The composition according to claim 44, wherein the one or more additional compounds are present in an amount of less than about 10 wt.%, preferably less than about 5 wt.%, more preferably less than about 1 wt%, most preferably less than about 0.5 wt.%.

46. The process according to any of claims 1 to 36, wherein the composition comprising HCBD is supplied from a reactor without being stored.

47. An integrated system for preparing a compound of the formula CF3CR=CCICF3, wherein R is H or Cl, the system comprising: a first reactor configured to produce a composition comprising hexachlorobutadiene (HCBD) and one or more additional compounds in the presence of a catalyst to obtain a product mixture comprising the compound of the formula CF3CR=CCICF3, wherein the one or more additional compounds are selected from the group consisting of 1 ,1 ,3,3,4,4-hexachloro-1-butene (C4H2CI6), carbon tetrachloride (CCI4), pentachloroethane (C2HCI5, HCC-120), tetrachloroethylene (CO-1110), hexachloroethane (C2CI6, CC-110), pentachloropyridine (C5CI5N), 1 ,1 ,2,3,3-pentachloropropene (C3HCI5, CCI2=CHCCI3, HCCO-1220az), 1 ,1 ,1 ,2,2,3, 3-heptachloropropane (C2CI5CHCI2), pentachlorocyclopropane (C3HCI5), 1 ,2, 3, 3-tetrachloro-1 -propene (C3H2CI4), pentachlorobutadiene isomers (CCI2=CH-CCI=CCI2, Z / E-CHCI=CCI-CCI=CCI2), tetrachlorothiophene (C4CI4S), and trichloroethylene, the first reactor having a discharge line for the composition comprising HCBD; and a second reactor coupled to the first reactor and configured to convert the composition comprising HCBD into a compound of the formula CF3CR=CCICF3.

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