Process for producing 1,2-difluoroethylene from tetrachloroethylene and the composition thereof

Abstract

An integrated process is provided for producing the E and Z isomers of 1,2-difluoroethylene using tetrachloroethylene. Compositions formed by the integrated process and compositions formed during the integrated process are also provided.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 541,333, filed on 29 September 2023, the disclosure of which is incorporated herein by reference in its entirety. [Background technology]

[0002] Hydrofluoroolefins (HFOs), which have low ozone depletion potential (ODP) and low global warming potential (GWP), have replaced saturated chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) in various applications for several years, due to the tendency for saturated hydrohalocarbons to have high GWP values. For example, HFC-32 (CH2F2), HFC-125 (C2HF5), and HFC-134a (CH2FCF3) have GWPs of 675, 3500, and 1430, respectively. As a result, materials with low ODP and GWP continue to be of interest for use as refrigerants, solvents, foaming agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle working fluids.

[0003] The regulatory landscape is constantly evolving, and properties beyond ODP and GWP are now being considered. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have a low global warming potential, but also exhibit low or no flammability, provide excellent performance in a variety of applications, and meet evolving regulatory standards. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Patent Provisional Application No. 63 / 541,333 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In this technological field, there is a need for new refrigerants that meet evolving regulations and provide heat transfer and cooling properties that meet or exceed the effectiveness of conventional refrigerants.

[0006] To meet these growing demands, existing and novel haloolefins continue to be developed, evaluated, and produced using more efficient processes. One such candidate is the E and / or Z isomers of 1,2-difluoroethylene (HFO-1132), which are suitable as blending components due to their environmentally friendly decomposition profile in the atmosphere. Current processing generally favors the production of the Z isomer, which requires a considerable amount to be isomerized to the E isomer. Thus, the need for new refrigerant candidates to produce these new candidates remains. [Means for solving the problem]

[0007] The present invention relates to a process for producing E and Z isomers (HFO-E-1132 and HFO-Z-1132) of 1,2-difluoroethylene through an intermediate, a composition thereof, and a method for using the isomers.

[0008] Certain embodiments disclosed herein relate to an integrated process for producing the E and Z isomers of HFO-1132 using tetrachloroethylene (CCl2=CCl2, PCE) as a starting material, according to the following reaction. (1): Tetrachloroethylene (PCE) + 3HF + Cl2 → 1,1,2-Trichloro-1,2,2-Trifluoroethane (CFC-113) + 3HCl (2): CFC-113 + Zn → Chlorotrifluoroethylene (CFO-1113) + ZnCl2 (3): CFO-1113 + 2H2 → 1,1,2-trifluoroethane (HFC-143) + HCl (4):HFC-143→HFO-E-1132+HFO-Z-1132+HF

[0009] Certain embodiments disclosed herein relate to an integration process involving a series of first, second, third, and fourth chemical reactions, which originate from the conversion of PCE to a mixture of HFO-E-1132 and HFO-Z-1132.

[0010] Certain embodiments disclosed herein relate to an integrated process for producing the E and Z isomers of HFO-1132 using PCE as a starting material, according to the above reactions (1), (2), (3), and (4), as well as the following isomerization reactions. (5):HFO-Z-1132→HFO-E-1132(E)

[0011] In certain embodiments disclosed herein, reactions (1), (2), (3), and (4) produce first, second, third, and fourth mixed product compositions, respectively, which form reactant feeds for subsequent reactions (2), (3), (4), and (5), respectively.

[0012] In certain embodiments disclosed herein, reactions (1), (2), (3), and (4) are part of an integrated process, and each reaction is carried out in a separate and individual reactor.

[0013] In certain embodiments disclosed in the present specification, Reactions (2) and (3) are each carried out in separate reactors / reactor systems that are close to each other, because CFO-1113 is extremely unstable in the absence or presence of air. CFO-1113 should be handled similarly to tetrafluoroethylene, and therefore, it is desirable that the system for producing CFO-1113 is in close proximity to the system for hydrogenating CFO-1113. This can be achieved by integrating the two processes at the same location with minimal transportation, either by directly coupling the two process steps together, or by constructing the hydrogenation process system at the location where CFO-1113 is produced (optionally with common plant equipment).

[0014] In certain embodiments disclosed in the present specification, Reactions (2) and (3) are combined in the same reactor, and CFC-113 is directly converted to HFC-143 in a single process step.

[0015] In certain embodiments, Reactions (1), (2), (3), (4), and (5) are part of an integrated process, and each reaction is performed in a separate and distinct reactor, optionally with common plant equipment.

[0016] In certain embodiments, Reactions (1), (2), (3), (4), and (5) are part of an integrated process, Reactions (1), (4), and (5) are each performed in a separate and distinct reactor, optionally with common plant equipment, while Reactions (2) and (3) are combined in the same reactor, and CFC-113 is directly converted to HFC-143 in a single process step.

[0017] In certain reaction embodiments, for Reactions (1), (2), (3), and (4), the feed compositions are respectively a. A PCE feed composition, which preferably comprises PCE and one or more additional compounds selected from CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane (HCC-250fb), b. A CFC-113 feed composition, which preferably comprises CFC-113 and one or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, and PCE, c. A CFO-1113 feed composition, which preferably comprises CFO-1113 and one or more additional compounds selected from 1,1,2-trifluoroethylene (HFO-1123), 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), 1-chloro-2,2,2-trifluoroethane (HCFC-133a), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1-chloro-1,2,2-trifluoroethane (HCFC-133), and d. A HFC-143 feed composition, which preferably comprises HFC-143 and one or more additional compounds selected from HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, HCFC-133, HCFC-133b, and HCO-1140.

[0018] In certain reaction embodiments, for reactions (1), (2), (3), and (4), the feed compositions are respectively a. A PCE supply composition, preferably comprising PCE and one or more additional compounds selected from CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane (HCC-250fb), b. A CFC-113 supply composition, preferably comprising CFC-113 and one or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, and PCE, c. A CFO-1113 supply composition, preferably comprising CFO-1113 and one or more additional compounds selected from 1,1,2-trifluoroethylene (HFO-1123), 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), 1-chloro-2,2,2-trifluoroethane (HCFC-133a), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1-chloro-1,2,2-trifluoroethane (HCFC-133), and a CFO-1113 supply composition, and d. An HFC-143 supply composition, preferably comprising HFC-143 and one or more additional compounds selected from HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, HCFC-133, HCFC-133b, and HCO-1140, Each of the supply compositions a), b), c), and d) is present independently in an amount selected from one of >95% by weight, >96% by weight, >97% by weight, >98% by weight, or >99% by weight, based on the total weight of the composition, with the corresponding remainder consisting of the total amount of the additional compounds a), b), c), and d) after purification (e.g., by distillation).

[0019] In a particular embodiment of the reaction, for reactions (1), (2), (3), and (4), the supply composition each comprises PCE, CFC-113, CFO-1113, or HFC-143 components, which are independently present in amounts selected from one of >50% by weight, >60% by weight, >70% by weight, >80% by weight, or >90% by weight and about <95% by weight, based on the total weight of the composition, with the corresponding remainder consisting of the total amount of the additional compounds a), b), c), and d) after purification (e.g., by distillation).

[0020] In a particular embodiment of the reaction, for reactions (1), (2), (3), and (4), the supply composition each comprises a PCE, CFC-113, CFO-1113, or HFC-143 component and an additional compound, wherein the amounts of each PCE, CFC-113, CFO-1113, or HFC-143 component and the corresponding additional compound are independently: Based on the total weight of the composition, >95% by weight of the component and <5% by weight of additional compounds. Based on the total weight of the composition, >96 weight percent of the component and <4 weight percent of additional compounds. Based on the total weight of the composition, >97 weight percent of the component and <3 weight percent of additional compounds. • >98 weight percent of the component and <2 weight percent of additional compounds, Selected from one of the following: >99 weight percent of the component and <1 weight percent of an additional compound.

[0021] In certain embodiments, the CFC-113 supply composition preferably comprises CFC-113 and one or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, and CFO-1112a.

[0022] In certain embodiments, the relative molar amounts of hydrogen and CFC-113 in reaction (3) are approximately 1:1 to approximately 3:1.

[0023] In a particular embodiment, the relative molar amounts of hydrogen and CFC-113 in reaction (3) contact are determined at a temperature of approximately 80°C to approximately 250°C.

[0024] In a particular embodiment, CFC-113 is brought into contact with hydrogen in the gas phase in the presence of a catalyst to form an HFC-143 composition.

[0025] In certain embodiments, CFC-113 is brought into contact with hydrogen in the gas phase in the presence of a catalyst comprising a catalyst metal selected from Pd, Pt, or a mixture thereof, preferably supported on Al2O3, alumina fluoride, AlF3, or chromium oxide, as disclosed in U.S. Patent Application Publications No. 20080207962 and No. 20080207963 (each of which disclosures is incorporated herein by reference).

[0026] In a particular embodiment, CFC-113 is brought into contact with hydrogen in the gas phase in the presence of a catalyst, and the amount of catalyst metal on the support constitutes about 0.5% to about 10% by weight of the catalyst composition.

[0027] In certain embodiments, the HFC-143 product comprises at least one compound selected from HCFC-123a, HCFC-132c, HCFC-133, HCFC-133b, C2H6, HFC-143a, HFC-134a, and HFC-152a.

[0028] In a particular embodiment involving reaction (5), the HFO-1132 composition comprises at least one of HFO-E-1132 or HFO-Z-1132, and acetylene, fluoroacetylene, difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), E-1-chloro-1,2-difluoroethylene (HCFO-E-1122a), Z-1-chloro-1,2-difluoroethylene (HCFO-Z-1122a), 1,1,2-trifluoroethylene (HFO-1123), fluoroethylene (HFO-1141), 1-chloro-1,2,2-trifluoroethane (HCFC-133), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1,1-dichloro-2, The present invention comprises one or more additional compounds selected from 2,2-trifluoroethane (HCFC-123), 1,2-difluoroethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene, 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (1140), 1-chloro-1-fluoroethene (HCFO-1131a), E-1-chloro-2-fluoroethene (HCFO-E-1131), Z-1-chloro-1-fluoroethene (HCFO-Z-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122). Preferably, the amount of 1,2-difluoroethane (HFC-152) is selected from one of <100 ppm, <50 ppm, <10 ppm, <5 ppm, or <1 ppm.

[0029] In certain embodiments of HFO-E-1132, HFO-Z-1132, or HFO-Z / E-1132 product mixtures, the amounts of fluoroethylene (HFO-1141), vinyl chloride (HCO-1140), acetylene, and fluoroacetylene are <2000 ppm, <1000 ppm, <500 ppm, <400 ppm, <300 ppm, <200 ppm, <100 ppm, <50 ppm, <10 The value is selected from one of the following values ​​and ranges: ppm, <5 ppm, ≥0.00001 ppm to <500 ppm, ≥0.0001 ppm to <500 ppm, ≥0.00001 ppm to <100 ppm, ≥0.0001 ppm to <100 ppm, ≥1 ppm to less than approximately 2000 ppm, ≥1 ppm to less than approximately 1000 ppm, or ≥0 to <100 ppm, as well as approximately 0.00001 ppm to 2000 ppm.

[0030] In certain embodiments, the HFO-E-1132, HFO-Z-1132, or HFO-Z / E-1132 product mixture comprises one of HFO-Z-1132 or HFO-E-1132 and acetylene, fluoroacetylene, difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), E-1-chloro-1,2-difluoroethylene (HCFO- E-1122a), Z-1-chloro-1,2-difluoroethylene (HCFO-Z-1122a), 1,1,2-trifluoroethylene (CFO-1123), fluoroethylene (HFO-1141), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), 1,1-dichloro-2,2,2-trifluoro It contains one of roethane (HCFC-123), 1,2-difluoroethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene, 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (HCO-1140), 1-chloro-1-fluoroethene (HCFO-1131a), E-1-chloro-2-fluoroethene (HCFO-E-1131), Z-1-chloro-2-fluoroethene (HCFO-Z-1131), vinylidene fluoride (HFO-1132a), and 1-chloro-2,2-difluoroethylene (HCFO-1122), plus at least two additional members selected from these. Preferably, the amount of 1,2-difluoroethane (HFC-152) is selected from one of <100 ppm, 50 ppm, 10 ppm, 5 ppm, or 1 ppm.

[0031] Embodiments disclosed herein relate to a process for converting PCE to CFC-113 (chlorfluorinating) (e.g., producing or generating CFC-113) in a liquid phase catalyzed by a metal halide at a temperature of 80°C to 120°C in the presence of HF and Cl2, or in a gas phase at a temperature of 250°C to 400°C in the presence of a partially fluorinated metal catalyst (including Group 6 metals of the periodic table). In one embodiment disclosed herein, the PCE composition comprises tetrachloroethylene and at least one compound selected from CCl4, CHCl3, bromotrichloromethane, bromodichloroethylene isomers, bromotrichloroethylene, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane.

[0032] Certain embodiments disclosed herein relate to tetrachloroethylene (PCE) compositions comprising, based on the total amount of the composition, >99% by weight of PCE and one or more additional compounds selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromodichloroethylene isomers, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3-trichloro-1-propene, and 1,1,1,3-tetrachloropropane. In one embodiment disclosed herein, the PCE composition comprises tetrachloroethylene and one or more compounds selected from CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane, wherein the amount of the compound is less than 1% by weight of the total composition.

[0033] In another embodiment disclosed herein, the PCE composition is converted into a CFC-113 composition comprising two or more, three or more, or four or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, and PCE.

[0034] Certain embodiments disclosed herein relate to a process of reaction (2) comprising contacting a CFC-113 composition with a reducing metal, including zinc, magnesium, or cadmium, in a liquid phase to dechlorinate CFC-113 and produce CFO-1113.

[0035] In one embodiment, the CFC-113 composition comprises, essentially consists of, or consists of, CFC-113 and two or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, and PCE in an amount of less than 1% by weight of the total composition of the additional compounds.

[0036] In another embodiment disclosed herein, the product mixture containing CFO-1113 comprises, essentially consists of, or comprises at least one compound selected from HCFC-123a, HCFC-133a, HCFC-133b, HCFC-133, and CFC-113.

[0037] Certain embodiments disclosed herein relate to a composition comprising, essentially consisting of, or consisting of, >99% by weight of CFC-113 and three or more additional compounds selected from CFC-113a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114a, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, and PCE, wherein the total amount of such additional compounds is less than 1% by weight of the whole composition.

[0038] In certain embodiments disclosed herein, the second product mixture comprises CFO-1113 in an amount of >99% by weight based on the total amount of the composition, and the composition also comprises one or more additional compounds selected from CFC-113a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFC-114a, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, HFO-1123, HCFC-133, HCFC-133a, HCFC-133b, and PCE, the total amount of such additional compounds being less than 1% by weight of the total composition.

[0039] In certain embodiments disclosed herein, the second product mixture comprises CFO-1113 in an amount of >99% by weight based on the total amount of the composition, and the composition also comprises two or more additional compounds selected from CFC-113a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFC-114a, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, HFO-1123, HCFC-133, HCFC-133a, HCFC-133b, and PCE, the total amount of such additional compounds being less than 1% by weight of the total composition.

[0040] Certain embodiments disclosed herein relate to a process of reaction (3) comprising contacting a second product mixture of CFO-1113 with hydrogen in the gas phase, optionally in the presence of a catalyst, to produce a third product mixture containing HFC-143 (e.g., producing or generating HFC-143).

[0041] In one embodiment disclosed herein, the HFC-143 composition comprises HFC-143 and one or more additional compounds selected from HFO-1123, CFO-1113, HCFC-133, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140, wherein the amount of the additional compounds is greater than 0% by weight and less than 1% by weight, based on the total amount of the HFC-143 composition.

[0042] Certain embodiments disclosed herein relate to a process comprising contacting CFO-1113 with hydrogen at a temperature of about 50°C to about 150°C.

[0043] Certain embodiments disclosed herein relate to a process comprising contacting CFO-1113 with hydrogen at a temperature of about 50°C to about 150°C in the presence of a hydrogenation catalyst comprising a catalyst metal selected from the group of Re, Ni, Pd, Pt, Ru, Rh, and Ir. The catalyst metal is preferably supported on carbon, aluminum oxide, alumina fluoride, or aluminum fluoride, for example, as disclosed in U.S. Patent No. 5,068,473 (the disclosure of which is incorporated herein by reference in its entirety).

[0044] Certain embodiments disclosed herein relate to a process integrating steps (2) and (3) above, wherein CFC-113 is contacted with hydrogen in the gas phase within a reaction zone to provide a mixture containing HFC-143 at a temperature of about 150°C to about 350°C, the reaction zone containing a catalyst metal selected from Pd, Pt, or a mixture thereof, preferably supported on Al2O3, alumina fluoride, AlF3, or chromium oxide, as disclosed in U.S. Patent Application Publications 20080207962 and 20080207963 (each of which is incorporated herein by reference in whole).

[0045] In certain embodiments disclosed herein, the product mixture of reaction (3), the third product mixture mainly comprises HFC-143 and one or more of the following compounds: HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-123a, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113. In certain embodiments disclosed herein, the dehydrofluoridation (4) of HFC-143 is carried out in the gas phase or the liquid phase.

[0046] In certain embodiments disclosed herein, the dehydrofluoridation reaction (4) is carried out in the gas phase.

[0047] In certain embodiments disclosed herein, the dehydrofluoridation reaction (4) is carried out in the liquid phase.

[0048] In certain embodiments disclosed herein, the dehydrofluoride reaction (4) is carried out in the gas phase at a temperature of 150°C to 400°C.

[0049] In certain embodiments disclosed herein, the dehydrofluoride reaction (4) is carried out in the liquid phase at a temperature of -20°C to 150°C.

[0050] In certain embodiments disclosed herein, reaction (4) is carried out at a temperature of 150°C to 400°C in the gas phase in the presence of a catalyst selected from the group consisting of aluminum fluoride, alumina fluoride, a metal supported on a trivalent aluminum compound containing a fluoride anion (e.g., aluminum fluoride and / or alumina fluoride), lanthanum fluoride, lanthanum fluoride oxide, a metal supported on a trivalent lanthanum compound containing a fluoride anion (e.g., lanthanum fluoride and / or lanthanum fluoride oxide), and a trivalent chromium compound (e.g., Cr2O3), wherein the metal is selected from the group consisting of one or more of chromium, manganese, iron, cobalt, nickel, magnesium, and zinc. Other suitable catalysts include cobalt-substituted or nickel-substituted chromium oxide catalysts prepared as disclosed in U.S. Patent No. 7,217,678 (the disclosure of which is incorporated herein by reference in whole).

[0051] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 150°C in the presence of a strong base, a polar solvent, and optionally a phase transfer catalyst.

[0052] Certain embodiments disclosed herein relate to a reaction (4) comprising an HFC-143 composition containing at least two compounds selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HCFO-E-1122a, HCFO-Z-1122a, HFO-1140, HCFC-133, HCFC-133b, HCFC-123a, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113 as starting materials.

[0053] Certain embodiments disclosed herein relate to a reaction (4) in which the starting material comprises an HFC-143 composition containing at least two compounds selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-133b, HCFC-133, HCFC-123a, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113, and the reaction is carried out in the liquid phase at a temperature of -20°C to 150°C in water or a polar solvent containing an alkali metal hydroxide including but not limited to LiOH, NaOH, or KOH, and optionally a phase transfer catalyst.

[0054] In certain embodiments disclosed herein, reaction (4) is carried out in the liquid phase at a temperature of -20°C to 150°C in the presence of a strong base, a polar solvent, and an interphase transfer catalyst comprising optionally selected from quaternary ammonium salts of formula [NR1R2R3R4]X and phosphonium salts of formula [PR1R2R3R4]X (wherein X = F, Cl, Br, I, OH, HCO3, CO3, HSO4, or SO4, and R1, R2, R3, and R4 are independently selected from the group consisting of alkyl groups, aryl groups, or aralkyl groups). Specific examples include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, and triphenylmethylphosphonium chloride.

[0055] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C, in the presence of a strong base, and in or without a catalyst.

[0056] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of a strong base, a solvent, and in or without a catalyst.

[0057] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of an alkali metal or alkaline earth metal alkoxide, an alkali metal or alkaline earth metal hydride, an organometallic lithium compound, or an alkali metal or alkaline earth metal amide, and a solvent.

[0058] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an organic solvent containing an acyclic or cyclic ether.

[0059] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an organic solvent containing an acyclic or cyclic ether, in the presence or absence of a catalyst.

[0060] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C, in the presence of (i) an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, (ii) an organic solvent containing an acyclic or cyclic ether, and (iii) a catalyst containing a crown ether or cryptand.

[0061] Certain embodiments disclosed herein relate to reaction (4), carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an organic solvent containing an acyclic or cyclic ether, and in the presence or absence of a catalyst containing a crown ether or cryptand, wherein the alkali metal is a Group 1A metal of the periodic table excluding hydrogen, and the alkaline earth metal is a Group 2A metal of the periodic table excluding beryllium.

[0062] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an organic solvent containing an acyclic or cyclic ether, and in the presence or absence of a catalyst containing a crown ether or cryptand, wherein the alkali metal or alkaline earth metal alkoxide comprises one of lithium methoxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, sodium isopropoxide, or magnesium ethoxide; the alkali metal or alkaline earth metal hydride comprises lithium hydride, sodium hydride, potassium hydride, or calcium hydride; the organometallic lithium compound comprises n-butyllithium, methyllithium, or isopropyllithium; and the alkali metal or alkaline earth metal amide comprises lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, or magnesium bis(diisopropylamide).

[0063] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an organic solvent containing an acyclic or cyclic ether, and in the presence or absence of a catalyst containing a crown ether or cryptand, wherein the alkali metal or alkaline earth metal alkoxide comprises one of lithium methoxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, sodium isopropoxide, or magnesium ethoxide; the alkali metal or alkaline earth metal hydride comprises lithium hydride, sodium hydride, potassium hydride, or calcium hydride; the organometallic lithium compound comprises n-butyllithium, methyllithium, or isopropyllithium; and the alkali metal or alkaline earth metal amide comprises lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, or magnesium bis(diisopropylamide).

[0064] Certain embodiments disclosed herein relate to reaction (4), carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an organic solvent containing an acyclic or cyclic ether, in the presence or absence of a catalyst, wherein the organic solvent contains one of diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, or dioxane.

[0065] Certain embodiments disclosed herein are carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an organic solvent containing an acyclic or cyclic ether, in the presence or absence of a catalyst, wherein the organic solvent is diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether The present invention relates to reaction (4), wherein the catalyst comprises one of tyl ether, tetrahydrofuran, or dioxane, and the catalyst comprises a crown ether selected from one of 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5) and 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6), or a cryptand comprising 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-(8.8.8)hexacosane (also known as 2,2,2-cryptand).

[0066] One embodiment disclosed herein relates to a process comprising reaction (5) and heating a mixture of HFO-Z-1132 and HFO-E-1132 at a temperature of ≥600°C to isomerize at least a portion of HFO-Z-1132 to HFO-E-1132.

[0067] One embodiment disclosed herein relates to a process comprising reaction (5) and catalytic isomerization of HFO-Z-1132 to HFO-E-1132 at a temperature of about 250°C to about 500°C.

[0068] One embodiment disclosed herein relates to a process comprising reaction (5) and catalytically converting a portion of HFO-Z-1132 to HFO-E-1132 at a temperature of about 300°C to about 450°C, wherein the catalyst is selected from Cr2O3, fluorinated Cr2O3, Al2O3, fluorinated Al2O3, or AlF3, alumina, fluorinated alumina, or chromium supported on AlF3, or cobalt-substituted or nickel-substituted chromium oxide as disclosed in U.S. Patent No. 7,217,678 (the disclosure of which is incorporated herein by reference in whole).

[0069] One embodiment disclosed herein relates to a composition comprising PCE and at least two compounds / components selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromodichloroethylene isomers, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3-trichloro-1-propene, and 1,1,1,3-tetrachloropropane.

[0070] One embodiment disclosed herein relates to a composition comprising PCE and at least two compounds / components selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, bromodichloroethylene isomers, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3-trichloro-1-propene, and 1,1,1,3-tetrachloropropane, wherein the amount of PCE is >99% by weight based on the total amount of the composition, and the amounts of the other components are less than 1% by weight of the total composition.

[0071] One embodiment disclosed herein relates to a composition comprising CFO-1113 and at least one or two compounds / components selected from HFO-1123, 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1-chloro-1,2,2-trifluoroethane (HCFC-133).

[0072] One embodiment disclosed herein relates to a composition comprising HFC-143 and at least two compounds / components selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-123a, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

[0073] One embodiment disclosed herein relates to a composition comprising HFC-143 and at least three compounds / components selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-123a, HCFC-133, HCFC-133b, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

[0074] One embodiment disclosed herein relates to a composition comprising HFC-143 and at least four compounds / components selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-123a, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

[0075] One embodiment disclosed herein relates to a composition comprising HFC-143 and at least five compounds / components selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-123a, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

[0076] In one embodiment disclosed herein, HFO-E-1132 and / or HFO-Z-1132 are blended with other HFC compounds, HFO compounds (e.g., HFO-E / Z-1234, HFO-1234yf, HFO-1336), and HCFO compounds for use as refrigerants, solvents, foaming agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle working fluids.

[0077] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in which the present invention pertains. In the event of any conflict, including definitions, this specification shall prevail. Similar or equivalent methods and materials to those described herein may be used in carrying out or testing embodiments of the present invention, but preferred methods and materials are described below. Furthermore, the materials, methods, and examples are illustrative and not intended to limit the scope. [Brief explanation of the drawing]

[0078] [Figure 1] This diagram schematically shows a system for implementing an integration process according to one embodiment of the present invention. [Figure 2] This schematic flow diagram illustrates the use of a distillation column and an optional recirculation flow to obtain compositions having a low Z:E ratio of HFO-1132 according to some embodiments of the present invention. [Modes for carrying out the invention]

[0079] The present invention relates to a process for producing E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132) according to the following reaction: (1): Tetrachloroethylene (PCE) + 3HF + Cl2 → 1,1,2-Trichloro-1,2,2-Trifluoroethane (CFC-113) + 3HCl (2): CFC-113 + Zn → Chlorotrifluoroethylene (CFO-1113) + ZnCl2 (3): CFO-1113 + 2H2 → 1,1,2-trifluoroethane (HFC-143) + HCl (4): HFC-143 → E-1,2-difluoroethylene (HFO-E-1132) + Z-1,2-difluoroethylene (HFO-Z-1132) + HF (5) (Optional): HFO-Z-1132 → HFO-E-1132 In some embodiments, the present invention relates to compositions from steps (1), (2), (3), and / or (4), and optionally from (5).

[0080] Referring to Figure 1, the present invention also relates to a system comprising a series of reactors 10, 20, 30, and 40 for carrying out reactions (1), (2), (3), and (4), respectively. Optionally, in one embodiment, the reactors 10, 20, 30, and 40 are integrated such that each reactor 10, 20, 30, and 40 is in fluid communication with an immediately preceding / upstream reactor and / or immediately following / downstream reactor. The reactors 10, 20, 30, and 40 are preferably configured as liquid-phase or gas-phase reactors, with or without catalysts or reactive metals, as required for each individual reaction step discussed herein, to produce an intermediate mixture and an HFO-E / Z-1132 mixture from starting feeds of tetrachloroethylene (PCE or R-1110), HF, and chlorine. The first, second, and third reactors 10, 20, and 30 generate intermediate product streams containing CFC-113, CFO-1113, and HFC-143, respectively.

[0081] Referring more specifically to Figure 1, the starting feed composition containing PCE, along with HF and Cl2, is introduced into the first reactor 10 to synthesize CFC-113. In this way, the first reactor 10 produces a first intermediate product mixture containing CFC-113, which is withdrawn from the first reactor 10 through line 12 and supplied to the second reactor 20. Optionally, in one embodiment, CFC-113 is separated from the first intermediate stream using a conventional separation device (not shown), and the purified CFC-113 stream is then introduced into a liquid-phase reactor 20 containing a zinc suspension to synthesize CFO-1113. In this way, the second reactor 20 produces a second intermediate product mixture containing CFO-1113, which is withdrawn from the second reactor through line 14 and supplied to the third reactor 30. Optionally, in one embodiment, CFO-1113 is separated from the second intermediate stream using a conventional separation device (not shown), and the purified CFO-1113 is then introduced into a third reactor 30. Hydrogen is also supplied to the third reactor 30 along with CFO-1113, and the components react to form HFC-143.

[0082] In another embodiment, CFC-113 produced in the first reactor 10 and optionally purified as described above can be supplied directly to the third reactor 30 via line 17.

[0083] In this manner, the third reactor 30 produces a third intermediate product mixture containing HFC-143, which is withdrawn from the third reactor 30 through line 16 and supplied to the fourth reactor 40. Optionally, in one embodiment, HFC-143 is separated from the third intermediate mixture using a conventional separation device (not shown), and the purified HFC-143 is then introduced into the fourth reactor 40 for conversion into a fourth product mixture containing HFO-E-1132 + HFO-Z-1132.

[0084] For example, in one embodiment, the fourth product mixture may have an HFO-Z-1132 to HFO-E-1132 ratio of about 5:1 to about 100:1. In such cases (when the Z:E ratio is relatively high), it may be desirable to distill the product mixture to produce a low-boiling fraction rich in HFO-E-1132 and a high-boiling fraction rich in HFO-Z-1132.

[0085] More specifically, as shown in Figure 2, in one embodiment, the fourth product mixture has a relatively high Z:E ratio of HFO-1132, is taken out of the fourth reactor 40, and supplied to a separation system such as a distillation column 50 via line 18. Thus, in one embodiment, the present invention relates to a system of optionally integrated reactors 10, 20, 30, and 40, further including a further transfer line 18 and a distillation column 50, along with transfer lines 12, 14, 16, and 17, as described above with respect to Figure 1.

[0086] For example, a separation system that may include one or more distillation columns 50 is configured to separate the fourth product mixture into a top stream 22 containing a low-boiling fraction rich in HFO-E-1132 and a bottom stream 24 containing a high-boiling fraction rich in HFO-Z-1132.

[0087] In a particular embodiment, the top flow 22 of the column comprises (i) HFO-E-1132, (ii) HFO-Z-1132, and (iii) at least one additional compound selected from acetylene, fluoroacetylene, HFC-32, HFC-125, HCFO-E-1122a, HCFO-Z-1122a, CFO-1123, HFO-1141, HCFC-133b, HCFC-133, HCFC-123, HFC-152, HFC-143, HFC-41, HCFC-22, ethylene, HCFC-142a, HFO-1132a, HCO-1140, HCFO-1131a, HCFO-E-1131, HCFO-Z-1131, HFO-1132a, and HCFO-1122.

[0088] In one embodiment, the top flow 22 has HFO-1132 isomers with a relatively low Z:E ratio (e.g., a Z:E ratio of about 0.01:1 to about 0.1:1), while the bottom flow 24 has HFO-1132 isomers with a relatively higher Z:E ratio (e.g., a Z:E ratio of about 10:1 or higher). In one embodiment, either or both of flows 22, 24 can be transported to an isomerization reactor (not shown) for the isomerization of HFO-Z-1132 to HFO-E-1132. The flow can be subjected to the isomerization reaction to increase the content of the E isomer.

[0089] Additionally, or alternatively, in one embodiment, as shown in Figure 2, the bottom flow 24 may be recycled to the first reactor 10 for use in the synthesis of CFC-113. More specifically, in one embodiment, the high-boiling fraction 24, mainly consisting of HFO-Z-1132, may be returned to the first reactor 10, where it undergoes chlorfluorination by a series of subsequent reactions to produce CFC-113. 1.HFO-Z-1132+Cl2→CHClFCHClF(HCFC-132) 2.HCFC-132+Cl2→HCl+CHClFCCl2F(HCFC-122a) 3.HCFC-122a+Cl2→HCl+CCl2FCCl2F(CFC-112) 4.CFC-112+HF→HCl+Cl2FCClF2(CFC-113)

[0090] Before referring to the details of the embodiments described herein, some terms are defined or clarified as follows:

[0091] As used herein, the term “compound” means all stereoisomers, geometric isomers, tautomers, and isotopes of the structure shown. Unless otherwise specified, a compound identified by name or structure as a particular tautomer is intended to include other tautomers.

[0092] As used herein, the term "hydrohaloalkane" means a molecule containing hydrogen, carbon, fluorine (HFC), and / or chlorine (HCFC), and / or bromine, and / or iodine, and which does not have a carbon-carbon double bond (halo = fluoro, chloro, bromo, iod). Examples are described throughout this specification.

[0093] The term "hydrohaloalkene" is intended to mean a compound selected from the classes of hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO), which contain a double bond between adjacent carbon atoms and may contain 1 to 8 carbon atoms.

[0094] As used herein, the term “isomerization process” refers to a process for changing the shape of a molecule, for example, in an olefin, from cis orientation to trans orientation. As is well known in the art, cis and trans isomers are more precisely referred to as Z or E isomers, depending on the exact substitution pattern in the olefin. In the isomerization process, the relative ratio of Z isomers to E isomers changes.

[0095] The term "scrubbing" refers to the selective removal of specific components using a solid or liquid medium to achieve a desired production quality.

[0096] As used herein, the term “chlorofluorination” means a liquid-phase or gas-phase process that increases the fluorine content of a suitable substrate (e.g., PCE) by contacting it with a mixture of hydrogen fluoride (HF) and chlorine (Cl2) in a reaction zone. In addition to the reactors disclosed herein, heat exchangers, discharge lines, units related to mass transfer, contact vessels (premixers), distillation columns, and feed and material transfer lines related to the reactors, heat exchangers, vessels, columns, and units used in the processes of the embodiments disclosed herein must be constructed of corrosion-resistant materials. Preferably, the reactors and components are made of acid-resistant alloys, such as nickel, nickel-based alloys (e.g., Hastelloy®, available from Special Metals Corp.), nickel-chromium alloys commercially available under the trade name Inconel® (hereinafter, “Inconel®”), or nickel-copper alloys commercially available under the trade name Monel®. Alternatively, containers, piping, or reactors made from metals with low corrosion resistance, such as stainless steel or carbon steel, may be lined with a fluoropolymer such as poly(tetrafluoroethylene). In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed lines and discharge lines, units related to mass transfer, contact vessels (premixers), distillation columns, and valves related to reactors, heat exchangers, vessels, columns, and units used in the processes of the various embodiments disclosed herein must be constructed from corrosion-resistant materials.

[0097] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a process, method, article, or apparatus containing a list of elements is not necessarily limited to those elements alone, and may also include other elements not expressly listed for or specific to such process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, “or” means an inclusive “or” and not an exclusive “or.” For example, condition A or B satisfies one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0098] The transitional phrase "consisting of" excludes any unspecified elements, steps, or components. In the context of claims, such a phrase would close off the claim to materials other than those listed, excluding impurities normally associated with the materials. If the phrase "consists of" appears within a clause in the body of the claim rather than immediately following the preamble, it is limited to the elements described within that clause only, and other elements are not excluded from the claim as a whole.

[0099] The transitional phrase "consisting essentially of" is used to define compositions and methods that include materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, components, or elements do not substantially affect the fundamental and novel characteristics of the claimed invention, in particular the mechanism of operation for achieving any desired result of any of the processes of the invention. The term "consisting essentially of" has an intermediate meaning between "including" and "consisting of".

[0100] If applicants define an invention or part thereof using non-limiting terms such as "includes," it should be readily understood that (unless otherwise specified) such descriptions should be interpreted to include inventions that essentially consist of or comprise the same term.

[0101] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning.

[0102] Where numerical ranges are listed herein, unless otherwise specified, these ranges are intended to encompass their endpoints and include all integers and fractions within them. It is not intended to limit the scope of the invention to any specific value described when defining a range. Furthermore, all ranges described herein are intended to include not only the specific ranges described but also any combination of values ​​within them, including the listed minimum and maximum values.

[0103] Where a quantity, concentration, or other value or parameter is given as a range, a preferred range, or a list of preferred upper and / or preferred lower values, these shall be understood to specifically disclose all ranges formed by any pair of any upper or preferred upper range values ​​and any lower or preferred lower range values, regardless of whether the ranges are disclosed separately. Where numerical ranges are enumerated herein, unless otherwise indicated, these ranges are intended to encompass their endpoints and include all integers and fractions within that range.

[0104] When used herein, GC / FID peak area correlates with the amount of compound present as a percentage of the total area of ​​all detected peaks. The FID area % can be converted to mole % using a calculated or measured response coefficient.

[0105] As used herein, the term “substantially absent” means present in amounts less than approximately 0.0001 weight percent (1 ppm).

[0106] As used herein, the term “about” in certain embodiments may be quantified to mean ±1%, ±2%, ±3%, and ±10% or less of the described value, as well as all integers and fractions between them.

[0107] Table of Compounds Examples of compounds include the following:

[0108] [Table 1-1]

[0109] [Table 1-2]

[0110] Some of the compounds present in the compositions of the present invention specified in Table 1 may exist as different stereoisomers or stereoisomers. The present invention is intended to include all single stereoisomers, single stereoisomers, or any combination or mixture thereof. For example, 1,2-difluoroethylene (HFO-1132) means that it represents the cis isomer (Z), the trans isomer (E), or any combination or mixture of both isomers in any ratio. Similarly, 1-chloro-1,2-difluoroethylene (HFO-1122a) exists as the Z isomer, the E isomer, or any combination or mixture of both isomers in any ratio. Single isomers or multiple isomers of the same compound may be used in any proportion.

[0111] One embodiment disclosed herein relates to an integrated process for producing the E and Z isomers of 1,2-difluoroethylene using PCE as a starting material, according to the following reaction steps. (1): Tetrachloroethylene (PCE) + 3HF + Cl2 → 1,1,2-Trichloro-1,2,2-Trifluoroethane (CFC-113) + 3HCl (2): CFC-113 + Zn → Chlorotrifluoroethylene (CFO-1113) + ZnCl2 (3): CFO-1113 + 2H2 → 1,1,2-trifluoroethane (HFC-143) + HCl (4): HFC-143 → E-1,2-difluoroethylene (HFO-E-1132) + Z-1,2-difluoroethylene (HFO-Z-1132) + HF

[0112] Another embodiment disclosed herein involves the following reaction steps (1), (2), (3), (4), and (5): Regarding the integration process including HFO-Z-1132 → HFO-E-1132.

[0113] One embodiment disclosed herein relates to a process for converting a mixture containing tetrachloroethylene (PCE), hydrogen fluoride, and chlorine in the liquid phase at a temperature of 80°C to 120°C in the presence of a metal halide catalyst into a mixture containing CFC-113.

[0114] In certain embodiments involving liquid-phase chlorofluorination of PCE using a metal halide, the metal halide catalyst includes, but is not limited to, SbCl5, SbCl3, SbF5, SnCl4, TiCl4, FeCl3, TaCl5, and combinations of two or more. The conversion rate of PCE to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is 20-100%, and the selectivity to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is greater than 90%. Preferably, the catalyst is SbCl5, and the conversion takes place at a temperature of about 80°C to about 120°C (including, but not limited to, all values ​​and ranges of 80°C, 90°C, 100°C, 110°C, or 120°C, and 80°C to about 120°C).

[0115] Another embodiment disclosed herein relates to a process for catalytically converting a mixture containing tetrachloroethylene (PCE), hydrogen fluoride, and chlorine to a mixture containing CFC-113 in the gas phase at a temperature of 250°C to 400°C.

[0116] In certain embodiments involving gas phase conversion of PCE, the catalyst includes a chromium-based fluorination catalyst selected from chromium oxide (Cr2O3), fluorinated chromium oxide, chromium fluoride, chromium chloride, or chromium oxide, chromium chloride, or chromium fluoride supported on carbon or alumina, fluorinated alumina, or AlF3. Of particular note are chromium oxide-based catalysts containing about 1 to 10 mol% of a transition metal selected from the group Mn, Fe, Co, Ni, Zn, Pd, and Ag. The catalyst can be prepared by coprecipitation of a mixture of chromium and a transition metal salt from an aqueous solution at a pH greater than about 8, followed by evaporation of the mixture and calcination at a temperature of about 300°C to 900°C.

[0117] In certain embodiments disclosed herein, the gas-phase catalytic conversion of PCE is carried out at temperatures of about 250°C to about 400°C (including, but not limited to, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, or 400°C), and all values ​​and ranges of 250°C to 400°C (including, but not limited to, 250°C to 375°C, 250°C to 350°C, 250°C to 325°C, 250°C to 300°C, 275°C to 375°C, 275°C to 350°C, 275°C to 325°C, 275°C to 300°C, 300°C to 400°C, and 300°C to 375°C).

[0118] In certain embodiments disclosed herein, the PCE converted to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) comprises >99 percent PCE and one or more compounds selected from CCl4, CHCl3, trichloroethylene, bromotrichloromethane, bromodichloroethylene isomers, bromotrichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane, with the total amount of other compounds being less than 1% by weight of the total composition.

[0119] In certain embodiments disclosed herein, the conversion of tetrachloroethylene (PCE) is to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 1,1,1,2-tetrachloro-2,2-difluoroethane (CFC-112a), and 1,1,2,2-tetrachloro-1,2-difluoroethane. A composition is produced comprising one or more additional compounds including (CFC-112), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), and 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124).

[0120] In certain embodiments disclosed herein, the CFC-113 supply composition preferably comprises CFC-113 and one or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, and PCE. In one embodiment disclosed herein, chlorotrifluoroethylene (CFO-1113) is produced by contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) or a first product mixture with a reducing metal in the liquid phase. The liquid-phase conversion rate of CFC-113 is 50-100%, and the selectivity for CFO-1113 is over 90%.

[0121] In certain embodiments disclosed herein, the liquid phase conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is carried out at a temperature of about 20°C to about 120°C, in the presence of optionally polar aprotic solvents such as dimethyl sulfoxide, N,N-dimethylformamide, or N-methylpyrrolidinone, or etheric solvents such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate.

[0122] In certain embodiments disclosed herein, the liquid-phase conversion of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is carried out at a temperature of about 20°C to about 120°C, in the presence of a solvent optionally selected from dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidinone, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate, and in the presence of a reducing metal optionally selected from magnesium, zinc, or cadmium. Optionally, the reducing metal may be promoted with a metal chloride such as ZnCl2, MgCl2, or CdCl2. The reducing metal is preferably activated. This activation of the reducing metal may be carried out by washing the reducing metal with an aqueous hydrochloric acid solution having a concentration of 1 M to about 5 M, followed by washing with water and acetone, and then vacuum drying. Other activators suitable for the process of the present invention include bromine (Br2), iodine (I2), bromoalkanes (e.g., bromoethane), iodoalkanes (e.g., iodomethane), vicinal dibromoalkanes (e.g., 1,2-dibromoethane), vicinal diiodoalkanes (e.g., 1,2-diiodoethane), or vicinal dibromochlorocarbons (e.g., 1,2-dibromotetrachloroethane). The reducing metal can be produced by the reaction of a metal chloride with an alkali metal such as sodium or potassium, as is generally described in RDRieke in Topics in Current Chemistry, Volume 59, pages 1-31 (1975), in which its teaching is incorporated by reference.

[0123] In certain embodiments disclosed herein, the amount of CFO-1113 is >99% by weight and comprises one or more compounds selected from the following components CFO-1112, CFO-1112a, HCFC-123a, HCFC-133, HCFC-133a, and HCFC-133b, as well as one of them, with the total amount of the other compounds being less than 1% by weight of the total composition.

[0124] In one embodiment disclosed herein, the HFC-143 composition produced in reaction (3) and converted in reaction (4) comprises (>99% by weight of HFC-143) and one of the following components: HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-123a, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113, with the total amount of other compounds being less than 1% by weight of the total composition.

[0125] In certain embodiments disclosed herein, the reaction (4) involving the dehydrofluoridation of HFC-143 is carried out in the gas phase or the liquid phase.

[0126] In certain embodiments disclosed herein, reaction (4) is carried out in the gas phase.

[0127] In certain embodiments disclosed herein, reaction (4) is carried out in a liquid phase.

[0128] In certain embodiments disclosed herein, reaction (4) occurs in the gas phase at 150°C to 400°C (150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 39 The process is carried out at temperatures including, but not limited to, 0°C or 400°C, or in the range of 250°C to 400°C (including, but not limited to, 250°C to 375°C, 250°C to 350°C, 250°C to 325°C, 250°C to 300°C, 275°C to 375°C, 275°C to 350°C, 275°C to 325°C, 275°C to 300°C, 300°C to 400°C, and 300°C to 375°C).

[0129] In certain embodiments disclosed herein, the reaction (4) is carried out in the liquid phase at temperatures ranging from -20°C to -150°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C) and the entire range from -20°C to 150°C.

[0130] In certain embodiments disclosed herein, reaction (4) is carried out in the gas phase at a temperature of 150°C to 400°C, including but not limited to 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, or 400°C, using aluminum fluoride, alumina fluoride, and ani fluoride. The process is carried out in the presence of a catalyst selected from the group consisting of a metal supported on a trivalent aluminum compound containing anion (e.g., aluminum fluoride and / or alumina fluoride), lanthanum fluoride, lanthanum fluoride oxide, a metal supported on a trivalent lanthanum compound containing a fluoride anion (e.g., lanthanum fluoride and / or lanthanum fluoride oxide), and a trivalent chromium compound (e.g., Cr2O3), wherein the metal is selected from the group consisting of one or more of chromium, manganese, iron, cobalt, nickel, magnesium, and zinc.

[0131] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 150°C in the presence of a strong base, a polar solvent, and optionally a phase transfer catalyst.

[0132] Certain embodiments disclosed herein relate to a reaction (4) comprising an HFC-143 composition in which the starting material contains at least two compounds selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-123a, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

[0133] Certain embodiments disclosed herein relate to a reaction (4) in which the starting material comprises an HFC-143 composition containing at least two compounds selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-123a, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113, and the reaction is carried out in the liquid phase at a temperature of -20°C to 150°C in the presence of a strong base, a polar solvent, and optionally a phase transfer catalyst. The strong base comprises one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide, and the polar solvent comprises one or more of water, dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, formamide, N,N-dimethylacetamide, N-methylpyrrolidinone, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate.

[0134] Certain embodiments disclosed herein involve a liquid phase at temperatures ranging from -20°C to -150°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C) or the entire range of -20°C to 150°C, with a strong base, a polar solvent, and optionally a formula The present invention relates to a reaction (4) carried out in the presence of a phase transfer catalyst comprising a material selected from the quaternary ammonium salt of formula [NR1R2R3R4]X and the phosphonium salt of formula [PR1R2R3R4]X (wherein X = F, Cl, Br, I, OH, HCO3, CO3, HSO4, or SO4, and R1, R2, R3, and R4 are independently selected from the group consisting of alkyl groups, aryl groups, or aralkyl groups). Specific examples include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium bisulfate, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, and triphenylmethylphosphonium chloride.

[0135] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of a strong base in an aprotic solvent, in the presence or absence of a catalyst.

[0136] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at temperatures ranging from -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) or in all ranges between these temperatures, in the presence or absence of a strong base in an aprotic solvent, in the presence or absence of a catalyst.

[0137] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at temperatures ranging from -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) or in the range between these temperatures, in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an aprotic solvent.

[0138] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at temperatures ranging from -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) or all in between, in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an acyclic or cyclic ether-containing aprotic solvent.

[0139] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at temperatures ranging from -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) or all in between, in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an aprotic solvent containing an acyclic or cyclic ether, in the presence or absence of a catalyst.

[0140] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at temperatures ranging from -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) or in all ranges between therein, in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an aprotic solvent containing an acyclic or cyclic ether, and in the presence or absence of a catalyst containing a crown ether or cryptand.

[0141] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at a temperature of -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an aprotic solvent containing an acyclic or cyclic ether, in the presence or absence of a catalyst containing a crown ether or cryptand, wherein the alkali metal or alkaline earth metal is a Group 1A metal of the periodic table excluding hydrogen, and the alkaline earth metal is a Group 2A metal of the periodic table excluding beryllium.

[0142] Certain embodiments disclosed herein are carried out in the liquid phase at temperatures ranging from -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) or in the range between these temperatures, in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an aprotic solvent containing an acyclic or cyclic ether, in the presence or absence of a catalyst containing a crown ether or cryptand, wherein the alkali metal or alkaline earth metal alkoxide is The present invention relates to reaction (4), comprising one of lithium methoxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, sodium isopropoxide, or magnesium ethoxide; an alkali metal or alkaline earth metal hydride comprising lithium hydride, sodium hydride, potassium hydride, or calcium hydride; an organometallic lithium compound comprising n-butyllithium, methyllithium, or isopropyllithium; and an alkali metal or alkaline earth metal amide comprising lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, or magnesium bis(diisopropylamide).

[0143] Certain embodiments disclosed herein are carried out in the liquid phase at temperatures ranging from -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) or all in the range between therein, in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an aprotic solvent containing an acyclic or cyclic ether, in the presence or absence of a catalyst containing a crown ether or cryptand, wherein the alkali metal or alkaline earth metal alkoxide The present invention relates to reaction (4), which comprises one of lithium methoxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, sodium isopropoxide, and magnesium ethoxide, and the alkali metal or alkaline earth metal hydride comprises lithium hydride, sodium hydride, potassium hydride, or calcium hydride, and the organometallic lithium compound comprises n-butyllithium, methyllithium, or isopropyllithium, and the alkali metal or alkaline earth metal amide comprises lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, or magnesium bis(diisopropylamide).

[0144] Certain embodiments disclosed herein relate to a reaction (4) carried out in the liquid phase at temperatures ranging from -20°C to 100°C (including, but not limited to, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C) or in the range between therein, in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an aprotic solvent containing an acyclic or cyclic ether, and in the presence or absence of a catalyst containing a crown ether or cryptand, wherein the aprotic solvent comprises one of diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, or dioxane.

[0145] Certain embodiments disclosed herein are carried out in the liquid phase at temperatures ranging from -20°C to 100°C or any range therein, in the presence of an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide, in the presence of an aprotic solvent including an acyclic or cyclic ether, in the presence or absence of a catalyst, wherein the aprotic solvent is diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyl ether, etc. The present invention relates to reaction (4), wherein the catalyst comprises one of ethylene glycol dimethyl ether, tetrahydrofuran, or dioxane, and the catalyst comprises a crown ether selected from one of 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5) and 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6), or a cryptand comprising 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-(8.8.8)hexacosane (also known as 2,2,2-cryptand).

[0146] In certain embodiments disclosed herein, the dehydrofluoridation is performed with HFC-143 present in an amount of at least 99% by weight and at least two compounds selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HFO-1141, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113, wherein the total amount of the other compounds is less than 1% by weight of the total composition. The process is carried out in the gas phase at a temperature of 150°C to 400°C in the presence of a catalyst selected from the group consisting of aluminum fluoride, alumina fluoride, a metal supported on a trivalent aluminum compound containing a fluoride anion (e.g., aluminum fluoride and / or alumina fluoride), lanthanum fluoride, lanthanum fluoride oxide, a metal supported on a trivalent lanthanum compound containing a fluoride anion (e.g., lanthanum fluoride and / or lanthanum fluoride oxide), and a trivalent chromium compound (e.g., Cr2O3), wherein the metal is selected from the group consisting of one or more of chromium, manganese, iron, cobalt, nickel, magnesium, and zinc.

[0147] In certain embodiments disclosed herein, the liquid phase contains HFC-143 and a compound selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HFO-1141, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113. The conversion with at least two of the above is carried out at a temperature of -20°C to 150°C in the presence of a strong base in a polar solvent and an interphase transfer catalyst optionally selected from quaternary ammonium salts of formula [NR1R2R3R4]X and phosphonium salts of formula [PR1R2R3R4]X (wherein X = F, Cl, Br, I, OH, HCO3, CO3, HSO4, or SO4, and R1, R2, R3, and R4 are independently selected from the group consisting of alkyl groups, aryl groups, or aralkyl groups). Specific examples include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium bisulfate, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, and triphenylmethylphosphonium chloride.

[0148] In certain embodiments disclosed herein, HFC-143 is HFC-143 and (1) at least two compounds selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HFO-1141, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113, or (2) 1,1-difluoroethylene (HFO-1132a), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2,2-trifluoroethylene (CFO-1113), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-2,2-difluoroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,(3) At least two compounds selected from 2-difluoroethylene (HCFO-1122a), fluoroethylene (HFO-1141), dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene, or (3) HFC-1123, CFO-1113, HFC-134, HFC-134a, HFCO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a The conversion is performed in the liquid phase using a composition comprising, and at least two compounds selected from HCO-1140, which is performed under anhydrous conditions at a temperature of 20°C to 100°C in the presence of a strong base such as an alkali metal or alkaline earth metal alkoxide, alkali metal or alkaline earth metal hydride, organometallic lithium compound, or alkali metal or alkaline earth metal amide (where the alkali metal is a Group 1A metal of the periodic table excluding hydrogen, and the alkaline earth metal is a Group 2 metal of the periodic table excluding beryllium). The reaction is carried out in an aprotic solvent selected from a group A metal, an alkali metal or alkaline earth metal alkoxide comprising one of lithium methoxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, sodium isopropoxide, or magnesium ethoxide, an alkali metal or alkaline earth metal hydride comprising lithium hydride, sodium hydride, potassium hydride, or calcium hydride, an organometallic lithium compound comprising n-butyllithium, methyllithium, or isopropyllithium, and an alkali metal or alkaline earth metal amide comprising lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, or magnesium bis(diisopropylamide), ethers (e.g., diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether) or cyclic ethers (e.g., tetrahydrofuran, dioxane). The reaction with a strong base can be carried out with or without a catalyst such as a crown ether or cryptand. Specific examples of crown ethers include 1, 4, 7, 10.Examples include 13-pentaoxacyclopentadecane (15-crown-5) and 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6). A well-known example of a cryptand is 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-(8.8.8)hexacosan (also known as 2,2,2-cryptand).

[0149] Certain embodiments disclosed herein include HFC-143 and 1,1-difluoroethylene (HFO-1132a), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2,2-trifluoroethylene (1113), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-2,2-difluoroethylene (HCFC-143a), 1-chloro-2,2-difluoroethylene (HCFC-1131a), 1,2-difluoroethane (HCFC-1521,2,2-trifluoroethylene (HCFC-1113a), 1-chloro-1,2,2-trifluoroethylene (HCFC-1131a), 1,2-difluoroethane (HCFC-152), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123a), 1,1-dichloro-1,2,2-trifluoroethylene (HCFC-1133a), The present invention relates to a composition comprising, essentially consisting of, or comprising one or more compounds selected from chloroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), fluoroethylene (HFO-1141), dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene.

[0150] Certain embodiments disclosed herein include HFC-143 and 1,1-difluoroethylene (HFO-1132a), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2,2-trifluoroethylene (1113), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-2,2-difluoroethane The present invention relates to an HFC-143 supply composition comprising, essentially consisting of, or comprising one or more compounds selected from tan (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), fluoroethylene (HFO-1141), dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene.

[0151] Certain embodiments disclosed herein include HFC-143 and 1,1-difluoroethylene (HFO-1132a), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2,2-trifluoroethylene (1113), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-2,2-difluoroethylene (HCFC-143a), 1-chloro-2,2-difluoroethylene (HCFC-1131a), 1,2-difluoroethane (HCFC-1521,2,2-trifluoroethylene (HCFC-1113a), 1-chloro-1,2,2-trifluoroethylene (HCFC-1131a), 1,2-difluoroethane (HCFC-152), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123a), 1,1-dichloro-1,2,2-trifluoroethylene (HCFC-1133a), The present invention relates to a composition comprising, essentially consisting of, or comprising two or more compounds selected from chloroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), fluoroethylene (HFO-1141), dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene.

[0152] Certain embodiments disclosed herein include HFC-143 and 1,1-difluoroethylene (HFO-1132a), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2,2-trifluoroethylene (1113), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-2,2-difluoroethane The present invention relates to an HFC-143 supply composition comprising, essentially consisting of, or comprising two or more compounds selected from tan (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), fluoroethylene (HFO-1141), dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene.

[0153] Certain embodiments disclosed herein relate to a process comprising contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the gas phase in the presence of a catalyst to form 1,1,2-trifluoroethane (HFC-143).

[0154] Certain embodiments disclosed herein relate to a process comprising contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the gas phase in the presence of a catalyst to form 1,1,2-trifluoroethane (HFC-143), wherein the relative molar amounts of hydrogen to CFC-113 are about 1:1 to about 3:1.

[0155] Certain embodiments disclosed herein relate to a process comprising contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the gas phase in the presence of a catalyst to form 1,1,2-trifluoroethane (HFC-143), wherein the contact is carried out at a temperature of about 80°C to about 250°C.

[0156] Certain embodiments disclosed herein relate to a process that involves contacting CFC-113 with hydrogen in the gas phase, preferably in the presence of a catalyst containing a catalytic metal selected from Pd, Pt, or a mixture thereof, supported on Al2O3, alumina fluoride, AlF3, or chromium oxide, as disclosed in U.S. Patent Application Publications 20080207962 and 20080207963.

[0157] Certain embodiments disclosed herein relate to a process comprising contacting CFC-113 with hydrogen in the gas phase in the presence of a catalyst to form an HFC-143 composition, wherein the amount of catalyst metal on the support constitutes about 0.5% to about 10% by weight of the catalyst composition.

[0158] In certain embodiments, the content of HFO-E-1132 in the mixture of HFO-Z-1132 and HFO-E-1132 increases in step (5) by isomerization in the presence or absence of the catalyst. In certain embodiments disclosed herein, isomerization occurs at a temperature of 600°C to 800°C (from any one of 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C to any one of 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C, or 800°C). The process is carried out at temperatures within all values ​​and ranges between those ranges (including 600°C to 690°C, 610°C to 690°C, 600°C to 680°C, 600°C to 670°C, 600°C to 660°C, 700°C to 800°C, 710°C to 790°C or 800°C, 720°C to 780°C, 790°C or 800°C, or 730°C to 750°C, 760°C, 770°C, 780°C, 790°C, or 800°C).

[0159] In certain embodiments disclosed herein, isomerization is carried out at temperatures of 600°C to 800°C (including, but not limited to, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C, 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C, or 800°C).

[0160] In certain embodiments disclosed herein, the molar ratio of HFO-E-1132 to HFO-Z-1132 is increased in step (5) by isomerization in the gas phase at a temperature of about 300°C to about 450°C in the presence of a catalyst selected from Cr2O3, fluorinated Cr2O3, Al2O3, fluorinated Al2O3, or AlF3, alumina, fluorinated alumina, or chromium supported on AlF3, or cobalt-substituted or nickel-substituted chromium oxide.

[0161] Certain embodiments disclosed herein include, or are essentially composed of, (i) HFO-E-1132 and at least one of HFO-1141, HFO-1123, acetylene, HFO-Z-1132, HCFO-E-1131, HCFO-Z-1131, HFC-125, HFC-32, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140, or (ii) relating to compositions comprising the same, or compositions comprising (ii) HFO-Z-1132 and at least one of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-Z-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140.

[0162] In certain embodiments disclosed herein, (i) HFO-E-1132 and at least two of HFO-1141, HFO-1123, acetylene, HFO-Z-1132, HCFO-E-1131, HCFO-Z-1131, HFC-125, HFC-32, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140, or (i) including, essentially comprising, or The present invention relates to a composition comprising the same, or (ii) a composition comprising, essentially comprising, or consisting of HFO-Z-1132 and at least two of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-Z-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140.

[0163] In certain embodiments disclosed herein, (i) HFO-E-1132 and at least three of HFO-1141, HFO-1123, acetylene, HFO-Z-1132, HCFO-E-1131, HCFO-Z-1131, HFC-125, HFC-32, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140, or (i) including, essentially consisting of, or (ii) relating to compositions comprising the same, or compositions comprising (ii) HFO-Z-1132 and at least three of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-Z-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140.

[0164] In certain embodiments disclosed herein, (i) HFO-E-1132 and at least four of HFO-1141, HFO-1123, acetylene, HFO-Z-1132, HCFO-E-1131, HFC-125, HFC-32, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140, comprising, essentially comprising, or comprising (ii) relating to a composition comprising, essentially comprising, or consisting of HFO-Z-1132 and at least four of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-Z-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140. [Examples]

[0165] Example 1 - Preparation of a 98% chromium / 2% palladium catalyst A solution of 760.28 g of Cr(NO3)3[9(H2O)] (1.90 mol) and 10.1 g of Pd(NO3)2[2(H2O)] (0.038 mol) is prepared in 2000 mL of deionized water. The pH of the solution is adjusted to 8.5 by treatment with a 7.4 M aqueous ammonium hydroxide solution. The resulting slurry is stirred overnight at room temperature, and then dried in air at 110-120°C for 48 hours. The dried solid is pulverized into a powder and calcined in air at 400°C for 24 hours. The calcined powder is pressed into a disc shape, pulverized, and sieved to obtain fractions of 10-+20 mesh (1.68-0.84 mm), which are used for catalyst evaluation.

[0166] Preparation of a 97% chromium / 3% iron catalyst A beaker containing 500 mL of 2 M Cr(NO3)3[9(H2O)] aqueous solution (1.00 mol) was treated with a solution of 7.64 g of Fe(NO3)3(H2O)9 (0.0189 mol) dissolved in 500 mL of deionized water. The pH of the solution was adjusted to 8.50 by treatment with a 7.4 M ammonium hydroxide aqueous solution. The resulting slurry was stirred overnight at room temperature and then dried in air at 110-120°C for 48 hours. The dried solid was pulverized into a powder and calcined in air at 400°C for 24 hours. The calcined powder was pressed into a disc shape, pulverized, and sieved to obtain fractions of -12 to +20 mesh (1.68 to 0.84 mm), which were used for catalyst evaluation.

[0167] Preparation of a 98% chromium / 2% silver catalyst A solution of 784.30 g of Cr(NO3)3[9(H2O)] (1.96 mol) and 6.79 g of AgNO3 (0.04 mol) is prepared in 2000 mL of deionized water. The pH of the solution is adjusted to 8.50 by treatment with a 7.4 M aqueous ammonium hydroxide solution. The resulting slurry is stirred overnight at room temperature, and then dried in air at 110-120°C for 48 hours. The dried solid is pulverized into a powder and calcined in air at 900°C for 24 hours. The calcined powder is pressed into a disc shape, pulverized, and sieved to obtain fractions of -12 to +20 mesh (1.68 to 0.84 mm), which are used for catalyst evaluation.

[0168] Chlorofluorination of tetrachloroethene over Cr / Ag(98 / 2) A pelletized Cr / Ag(98 / 2) catalyst (15 mL, 31.64 g) is placed in a 5 / 8 inch (1.58 cm) diameter Inconel™ nickel alloy reaction tube heated in a fluidized sand bath. The tube is heated from 67°C to 174°C over about 0.5 hours under a nitrogen flow (50 cc / min; 8.3(10) -7 m 3 / s). Then HF is introduced into the reactor at a flow rate of 50 cc / min (8.3(10) -7 m 3 / s). After about 10 minutes, the nitrogen flow is reduced to 20 cc / min (3.3(10) -7 m 3 / s), the HF flow is increased to 80 cc / min (1.3(10) -6 m 3 / s), and this flow rate is maintained for about 0.5 hours. Subsequently, the temperature of the reactor is gradually raised to 400°C over 3 hours. The nitrogen flow is reduced to 10 cc / min (1.7(10) -7 m 3 / s), and the fluorination is continued at 400°C for 2 hours. At the end of this period, the HF flow is stopped, and the reactor is cooled under a nitrogen flow of 20 sccm (3.3(10) -7 m 3 / s). Then a mixture of HF, C2Cl4, and Cl2 is passed over the catalyst at various ratios and temperatures of 325 to 400°C. At 350°C, with an HF / C2Cl4 / Cl2 ratio of 5 / 1 / 1 and a contact time of 15 seconds, the reactor effluent is mainly CCl3CClF2 (56.6%) and CClF2CCl2F (37.2%) (containing small amounts of CClF2CClF2 (0.29%), CF3CCl2F (0.99%), CCl2=CF2 (0.37%), CHCl2CClF2 (0.12%), CCl2=CClF (0.73%), and CCl3CCl2F (1.9%)). The conversion rate is 100%.

[0169] Chlorofluorination of tetrachloroethene over Cr / Fe(97 / 3) Place the pelletized Cr / Fe(97 / 3) catalyst (20 mL, 28.8 g) into an Inconel® nickel alloy reaction tube (5 / 8 inch diameter, 1.58 cm) heated in a fluidized sand bath. The tube is then subjected to a nitrogen stream (50 cc / min; 8.3 (10) -7 m 3 Heat overnight in a medium (8.3 / second) from 67°C to 176°C. Then, add HF at 50cc / min (8.3(10) -7 m 3 The HF flow is supplied to the reactor at a flow rate of 1.3 cc / min (1.3(10)) for approximately 45 minutes. Then, the temperature is raised from 175°C to 402°C over approximately 5.5 hours while the HF flow is increased to 80 cc / min (1.3(10) -6 m 3 Increase the nitrogen flow rate to 20 cc / min (3.3(10) / second) -7 m 3 Reduce the flow rate to 20 sccm (3.3 (10)). Stop the HF flow and reduce the reactor to 20 sccm (3.3 (10) -7 m 3 Cooled under a nitrogen stream ( / second). Then, a mixture of HF, C2Cl4, and Cl2 is passed over the catalyst in various ratios and at temperatures of 250-375°C. At 350°C, with an HF / C2Cl4 / Cl2 ratio of 6 / 1 / 1 and a contact time of 15 seconds, the reactor effluent mainly consists of C2Cl4F2 isomers (4.9%), CClF2CCl2F (81.5%), CClF2CClF2 (7.2%), and CF3CCl2F (4.6%) (including small amounts of CF3CCl3 (0.94%), CClF2CF3 (0.07%), C2HClF4 isomers (0.03%), CHCl2CClF2 (0.01%), CHCl=CClF (0.02%), CCl2=CClF (0.06%), CCl2=CF2 (0.6%), and CCl3CCl2F (0.02%)). The conversion rate is 100%.

[0170] Chlorfluorination of PCE Gas phase: An Inconel® tube (0.5-inch outer diameter, 15-inch length, 0.34-inch wall thickness) is packed with 12 cc (6.45 g) of carbon-supported 15% chromium chloride catalyst. The catalyst is activated at 300°C with anhydrous HF. The reactor is heated to 300°C in a Lindbergh furnace, and tetrachloroethylene and one additional compound selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3-trichloro-1-propene, and 1,1,1,3-tetrachloropropane are supplied at a rate of 4 mL / hour through a vaporizer controlled at 150°C, with HF gas at 22.2 sccm (standard cubic centimeters per minute) and Cl2 gas at 5.4 sccm. All experiments were performed at 1–2 psig. The reactor effluent was analyzed online using an Agilent® 6890 GC / 5973 MS and a Restek® PC2618 5% Krytox® CBK-D / 60 / 80 (6 m x 2 mm inner diameter, 1 / 8 inch outer diameter) packed column purged with 30 sccm of helium. The reaction had a conversion rate of 55% and a selectivity of 90%.

[0171] In one embodiment, chlorination of PCE produces a CFC-113 composition. After purification, this composition comprises, based on the total amount of the composition, about 99% by weight of CFC-113 and two or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, CFO-1112a, and PCE, with the total amount of the additional compounds being less than 1% by weight of the total composition.

[0172] Liquid phase: Add SbCl5 (10.5 g) to a 210 mL Hastelloy C reactor, followed by the addition of HF (49 g) and Cl2 (42 g). Heat the reaction mixture at 100°C for 1 hour, then cool to 0°C. Add tetrachloroethylene (19 g) and one or more additional compounds selected from chloroform, carbon tetrachloride, bromotrichloromethane, bromotrichloroethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3-trichloro-1-propene, and 1,1,1,3-tetrachloropropane to the reactor, and heat the reaction mixture to 100°C. The reaction rate is indicated by an increase in pressure, and stabilization of pressure indicates completion of the reaction. The same reaction can also be carried out using a TaCl5 catalyst or an NbCl5 catalyst. The reaction has a 100% conversion rate and a 95% selectivity.

[0173] Step 2: CFC-113 + Zn → CFO-1113 + ZnCl2 Dechlorination of CFC-113 A 500 mL three-necked round-bottom flask is equipped with a large stirring rod, a thermocouple well, a dropping funnel, and a condenser connected in series to two traps placed in a dry ice / acetone bath, followed by a nitrogen bubbler. Each trap contains 100 mg of d-limonene as a polymerization inhibitor. Magnesium powder (9.0 g, 0.37 mol) and tetrahydrofuran (222.2 g) are added to the flask, followed by iodine crystals as a magnesium activator. 1,1,2-trichloro-1,2,2-trifluoroethane (58.0 g, 0.31 mol) is added to the dropping funnel. 1,1,2-trichloro-1,2,2-trifluoroethane is added dropwise to the magnesium / THF mixture, initially at room temperature. As the temperature rises, an ice bath is used to adjust the exothermic reaction to 40-50°C. The volatile reaction products are collected in a cylinder. Gas chromatography analysis of the product indicates that it consists of chlorotrifluoroethene. Other low-level impurities include 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), 1-chloro-2,2,2-trifluoroethane (HCFC-133a), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), 1,1-dichloro-2,2-difluoroethylene, and E / Z-1,2-dichloro-1,2-difluoroethene. In one embodiment, isolated chlorotrifluoroethylene (CFO-1113) includes 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), 1-chloro-2,2,2-trifluoroethane (HCFC-133a), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133), 1,1-dichloro-2,2-difluoroethylene, and E / Z-1,2-dichloro-1,2-difluoroethene.

[0174] Hydrogen dechlorination of CFC-113 A 15 mL portion (19 g) of granular Cr / Pd(98 / 2) catalyst is placed in a 5 / 8 inch (1.58 cm) diameter Inconel® nickel alloy reaction tube heated in a fluidized sand bath. The catalyst is dried in a nitrogen stream (20 cc / min) for 1.5 hours while increasing the temperature from 34°C to 150°C. The nitrogen stream is then replaced with hydrogen (20 cc). The catalyst is reduced at 150°C for 3 hours and then at 200°C for 3 hours. The catalyst performance for the hydrogeno-dechlorination of CFC-113 is then tested at various ratios of H2 to CClF2CCl2F at 87°C to 156°C. With an H2 / CClF2CCl2F ratio of 2 / 1, a reaction temperature of 95°C, and a contact time of 15 seconds, the reactor effluent, as determined by GC-MS, is mainly CHF2CH2F (84.5%) and CClF2CH2F (6.8%) (containing small amounts of C2H6 (0.2%), CH3CF3 (0.2%), CH2FCF3 (0.2%), and CH3CHF2 (0.5%)). The conversion rate is 100%.

[0175] Step 3: CFO-1113 + H2 → HFC-143 + HCl A Hastelloy tube reactor (80 inches long, 1 inch OD (outer diameter), and 0.074 inches wall thickness) is packed with 30 g of carbon-supported 0.5% Pd. The catalyst is conditioned at 200°C for 1 hour using a nitrogen stream (1000 sccm) and a hydrogen stream (1000 sccm). A mixture of CFO-1113, hydrogen, and N2 is then introduced into the reactor under a back pressure of 10 psig. The reaction is carried out with a conversion rate of 50% and a HFC-143 selectivity of 90%.

[0176] In one embodiment, contact of chlorotrifluoroethylene (CFO-1113) with hydrogen is performed by (i) a catalyst gold selected from the group consisting of Re, Ni, Pd, Pt, Ru, Rh, and Ir at a temperature of 50°C to about 150°C (including, but not limited to, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C). The process is carried out in the presence of a hydrogenation catalyst containing the genus, or (ii) at a temperature of 150°C to about 350°C (including, but not limited to, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, and 350°C).

[0177] Step 4: HFC-143 → HFO-Z-1132 + HFO-E-1132 + HF gas phase: 2 cc of chromium oxide catalyst is packed into an Inconel® pipe (0.5 inch outer diameter, 10 inch length, 0.35 inch wall thickness). The reactor is heated to 375°C with an optionally oxygen-containing gas. The HFC-143 produced in step (3) is combined with at least (i) HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HFO-1141, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113. One or more compounds, or (ii) 1,1-difluoroethylene (HFO-1132a), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2,2-trifluoroethylene (1113), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro-2,2,2-trifluoroethylene Oloethane (HCFC-123), 1-chloro-2,2-difluoroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), fluoroethylene (HFO-1141), dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), trifluoromethane (HF (iii) at least one compound selected from C-23), ethylene, and acetylene, or at least one compound selected from HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140, supplied at 4.23 mL / hour by an ISCO pump via a vaporizer controlled at 20°C. The reaction pressure is varied from 0 to 50 psig.The reactor effluent was analyzed online using an Agilent® 7890 GC / 5971 MS. The conversion rate for HFC-143 was 53%, and the selectivity for HFO-1132 was 90%. The molar ratio of Z-1132 to E-1132 was approximately 4:1.

[0178] Liquid phase: In anhydrous DMF (200 mL), HFC-143 (84 g, 1 mol) and (i) selected from HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HFO-1141, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113... (ii) at least one compound that is, or (ii) 1,1-difluoroethylene (HFO-1132a), 1,1,1-trifluoroethane (HFC-143a), 1-chloro-1,2,2-trifluoroethylene (1113), 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HCFC-141), 1,1-dichloro -2,2,2-trifluoroethane (HCFC-123), 1-chloro-2,2-difluoroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), fluoroethylene (HCFO-1141), dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-2 2) A mixture of trifluoromethane (HFC-23), ethylene, and acetylene, or (iii) at least two compounds selected from HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140, with t-BuOK (80 g, 1 mmol) is stirred in a 400 mL autoclave at 0°C. The reaction is monitored using gas chromatography. After 3 hours, the product is collected in a dry eye trap connected to the autoclave. HFO-1132 is formed with a conversion rate of approximately 70% of HFC-143 and a selectivity of 96%. The molar ratio of HFO-Z-1132 to HFO-E-1132 is approximately 9:1.

[0179] Step 5: HFO-Z-1132 → HFO-E-1132 In a particular embodiment, the content of HFO-E-1132 in the mixture of HFO-Z-1132 and HFO-E-1132 is increased in step (5) by isomerization in or out of the presence of a catalyst. In the absence of a catalyst, isomerization is carried out at temperatures of 600°C to 800°C and all values ​​and ranges in between.

[0180] In certain embodiments disclosed herein, the isomerization reaction (5) is carried out in the gas phase at a temperature of about 300°C to about 450°C in the presence of a catalyst selected from Cr2O3, fluorinated Cr2O3, Al2O3, fluorinated Al2O3, or AlF3, alumina, fluorinated alumina, or chromium supported on AlF3, or cobalt-substituted or nickel-substituted chromium oxide.

[0181] In certain embodiments, the content of HFO-Z-1132 in HFO-E / Z- can be increased by isomerizing HFO-E-1132 in the gas phase, either in the presence or absence of a catalyst.

[0182] The E:Z molar ratio of a mixture of HFO-Z-1132 and HFO-E-1132 increases with contact time of approximately 0.1 to 60 seconds and thermal isomerization at 600°C to 800°C.

[0183] Certain embodiments disclosed herein relate to a system and process comprising a series of reactors, the system including first, second, and third reactors configured to synthesize a first CFC-113 intermediate product mixture, a second CFO-1113 intermediate product mixture, and a third HFC-143 intermediate product mixture, respectively, and a fourth reactor configured to synthesize a mixture of the isomers HFO-E-1132 and HFO-Z-1132, the system further comprising a conversion system in fluid communication with the fourth reactor to change the E / Z ratio of HFO-1132, the conversion system comprising one of a distillation column, a non-catalytic thermal converter, or a catalytic reactor suitable for changing the HFO-E-1132:HFO-Z-1132 ratio.

[0184] Certain embodiments disclosed herein are processes comprising providing and contacting starting feeds tetrachloroethylene (PCE), HF, and chlorine to synthesize 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feeds, and contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) as part of a product mixture with a reducing metal in the liquid phase to form chlorotrifluoroethylene (CFO-1113), and one of the product mixtures The present invention relates to a process comprising contacting chlorotrifluoroethylene (CFO-1113) as a part with hydrogen in either the gas or liquid phase to form 1,1,2-trifluoroethane (HFC-143), and then converting 1,1,2-trifluoroethane (HFC-143) as part of the product mixture from step (d) in either the liquid or gas phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0185] Certain embodiments disclosed herein relate to a process comprising supplying and contacting starting feed tetrachloroethylene (PCE), HF, and chlorine to synthesize 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feed, contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) as part of a product mixture with hydrogen in either the gas or liquid phase to form 1,1,2-trifluoroethane (HFC-143), and then converting 1,1,2-trifluoroethane (HFC-143) as part of a product mixture from step (d) in either the liquid or gas phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0186] Certain embodiments disclosed herein relate to a process further comprising performing steps (a), (b), (c), (d), and (e) in separate and individual reactors.

[0187] Certain embodiments disclosed herein relate to a process that further comprises purifying one of CFC-113, CFO-113, or HFC-143 and first separating it from the product mixture before the next step.

[0188] A system comprising a refrigerant charging source, an evaporator, a compressor, a condenser, a charging valve, and a refrigerant circuit including a charging line for temporarily connecting the charging source and the charging valve, wherein the charging source contains a refrigerant comprising at least (E)-1,2-difluoroethylene (HFO-E-1132) and (Z)-1,2-difluoroethylene (HFO-Z-1132).

[0189] A system comprising a refrigerant charging source and a refrigerant circuit including an evaporator, a compressor, a condenser, a charging valve, and a charging line for temporarily connecting the charging source and the charging valve, wherein the charging source contains a refrigerant comprising at least (E)-1,2-difluoroethylene (HFO-E-1132) and (Z)-1,2-difluoroethylene (HFO-Z-1132), and the system is part of a heat transfer system selected from one of a refrigeration system, a refrigerator, an air conditioning system, a heat pump, a chiller, and a mobile air conditioning system.

[0190] Embodiment of the Claim Embodiment 1. A process, (a) Contacting tetrachloroethylene (PCE) with HF and chlorine to form 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), (b) In the liquid phase, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is brought into contact with a reducing metal to form chlorotrifluoroethylene (CFO-1113), (c) In either the gas phase or the liquid phase, chlorotrifluoroethylene (CFO-1113) is brought into contact with hydrogen to form 1,1,2-trifluoroethane (HFC-143), (d) A process comprising converting 1,1,2-trifluoroethane (HFC-143) in the liquid or gas phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0191] Embodiment 2.(e) The process according to Embodiment 1, further comprising isomerizing a portion of Z-1,2-difluoroethylene (HFO-Z-1132) in a mixture of E-1,2-difluoroethylene and Z-1,2-difluoroethylene to E-1,2-difluoroethylene (HFO-E-1132).

[0192] Embodiment 3. The process according to Embodiment 1, wherein (a), (b), and (c) are part of an integrated process, and each reaction is carried out in a separate and individual reactor.

[0193] Embodiment 4. The process according to Embodiment 1, wherein (a), (b), (c), and (d) are part of an integrated process, and each reaction is carried out in a separate and individual reactor.

[0194] Embodiment 5. The process according to Embodiment 2, wherein (a), (b), (c), (d), and (e) are part of an integrated process, and each reaction is carried out in a separate and individual reactor.

[0195] Embodiment 6. The process according to Embodiment 1 or 2, wherein (a) comprises chlorfluorination, (b) comprises dechlorination, (c) comprises hydrogenation, and (d) comprises dehydrofluorination.

[0196] Embodiment 7. The process according to Embodiment 6, wherein chlorination of PCE produces a first product mixture, dechlorination of CFC-113 produces a second product mixture, hydrogenation of CFO-1113 produces a third product mixture, and dehydrofluorination of HFC-143 produces a fourth product mixture.

[0197] Embodiment 8. The process according to Embodiment 1 or 2, wherein the PCE conversion is carried out in the presence of hydrogen fluoride and chlorine, in one of the following: (1) a liquid phase catalyzed by a metal halide catalyst at a temperature of 80 to 120°C, or (2) a gas phase in the presence of a chromium-based fluorination catalyst at a temperature of 250 to 400°C.

[0198] Embodiment 9. The process according to Embodiment 1 or 2, wherein the PCE is a supply composition comprising, based on the total amount of the composition, >99% by weight of PCE and one or more additional compounds selected from the group consisting of 1,1,1-trichloroethane, carbon tetrachloride, dichloromethane, and trichloroethylene.

[0199] Embodiment 10. The process according to Embodiment 9, wherein the amount of the additional compound is greater than 0% by weight and less than 1% by weight, based on the total amount of the supplied composition.

[0200] Embodiment 11. The process according to Embodiment 1 or 2, wherein the PCE conversion produces a first product mixture comprising 1,1,2-trichloro-1,2,2-trifluoroethane (CFO-113) and one or more additional compounds selected from the group consisting of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), CFC-113a, CFC-114, CFC-114a, HCFC-124, and HCFC-123, and PCE.

[0201] Embodiment 12. The process according to Embodiment 11, wherein the amount of CFC-113 in the first product mixture is >95% by weight, based on the total weight of the composition.

[0202] Embodiment 13. The process according to Embodiment 12, wherein the amount of the additional compound in the first product composition constitutes more than 0% by weight and less than 1% by weight, based on the total amount of the first product composition.

[0203] Embodiment 14. The process according to Embodiment 11, wherein 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is included as part of the first product mixture.

[0204] Embodiment 15. The process according to Embodiment 14, wherein the first product mixture is used to prepare the second product mixture.

[0205] Embodiment 16. The process according to Embodiment 1 or 2, wherein the reducing metal comprises zinc, magnesium, or cadmium in the solvent as a liquid phase.

[0206] Embodiment 17. The process according to Embodiment 1 or 2, wherein the solvent comprises a polar aprotic solvent.

[0207] Embodiment 18. The process according to Embodiment 15, wherein in the liquid phase, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is brought into contact with a reducing metal at a temperature of about 20°C to about 120°C.

[0208] Embodiment 19. The process according to Embodiment 1 or 2, wherein contact of chlorotrifluoroethylene (CFO-1113) with hydrogen is carried out (i) at a temperature of 50°C to about 150°C in the presence of a hydrogenation catalyst containing a catalytic metal selected from the group consisting of Re, Ni, Pd, Pt, Ru, Rh, and Ir, or (ii) at a temperature of 150°C to about 350°C in the presence of a hydrogenation catalyst containing a catalytic metal selected from the group consisting of Re, Ni, Pd, Pt, Ru, Rh, and Ir.

[0209] Embodiment 20. The process according to Embodiment 1 or 2, wherein chlorotrifluoroethylene (CFO-1113) is contacted with hydrogen in the presence of a hydrogenation catalyst selected from the group consisting of Pd and Pt.

[0210] Embodiment 21. The process according to Embodiment 11, wherein the hydrogenation of chlorotrifluoroethylene (CFO-1113) produces a third product mixture comprising mainly HFC-143 and one or more additional compounds selected from the group consisting of HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-133b, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

[0211] Embodiment 22. The process according to Embodiment 11, wherein the third product mixture is converted in the gas phase or liquid phase to a fourth product mixture containing E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0212] Embodiment 23. The process according to Embodiment 20, wherein the conversion is carried out in the gas phase at a temperature of 150°C to 400°C.

[0213] Embodiment 24. The process according to Embodiment 20, wherein the conversion is performed in the liquid phase at a temperature of -20°C to 150°C.

[0214] Embodiment 25. A composition, (a) Tetrachloroethylene (PCE), and at least one additional compound selected from the group consisting of CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, or 1,1,1,3-tetrachloropropane. (b) 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), and at least one additional compound selected from the group consisting of CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE, (c) Chlorotrifluoroethylene (CFO-1113), and at least one additional compound selected from the group consisting of HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b, and CFC-113. (d) At least one additional compound selected from the group consisting of 1,1,2-trifluoroethane (HFC-143), HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140, (e) E-1,2-difluoroethylene (HFO-E-1132), and at least one additional compound selected from the group consisting of HFO-1141, HFO-1123, acetylene, HFO-Z-1132, HCFO-E-1131, HFC-125, HFC-32, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140, or (f) A composition comprising Z-1,2-difluoroethylene (HFO-Z-1132), and at least one additional compound selected from the group consisting of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140.

[0215] Embodiment 26. A composition, (a) HFO-E-1132, and at least one additional compound selected from the group consisting of HFO-1141, HCFO-1140, acetylene, and fluoroacetylene in an amount of <500 ppm, (b) HFO-Z-1132, and at least one additional compound selected from the group consisting of HFO-1141, HCFO-1140, acetylene, and fluoroacetylene in an amount of <500 ppm, (c) At least one of HFO-E-1132 and HFO-Z-1132, and acetylene, fluoroacetylene, difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), E-1-chloro-1,2-difluoroethylene (HCFO-E-1122a), Z-1-chloro-1,2-difluoroethylene (HCFO-Z-1122a), 1,1,2-trifluoroethylene (HFO-1123), fluoroethylene (HFO-1141), 1-chloro-1,1,2-trifluoroethane (HCFC-133), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2-difluoro A composition comprising at least one of at least two additional compounds selected from the group consisting of oleethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene (HCO-1150), 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (1140), 1-chloro-1-fluoroethene (HCFO-E-1131a), E-1-chloro-2-fluoroethene (HCFO-E-1131), Z-1-chloro-2-fluoroethene (HCFO-Z-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122).

[0216] Embodiment 27. A composition comprising at least one of HFO-E-1132 and HFO-Z-1132, and acetylene, fluoroacetylene, difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), E-1-chloro-1,2-difluoroethylene (HCFO-E-1122a), Z-1-chloro-1,2-difluoroethylene (HCFO-Z-1122a), 1,1,2-trifluoroethylene (HFO-1123), fluoroethylene (HFO-1141), 1-chloro-1,1 ,2-trifluoroethane (HCFC-133), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2-difluoroethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene, 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride ( A total amount of HFO-1141, HCFO-1140, acetylene, and fluoroacetylene is <2000 ppm, <1000 ppm, <500 ppm, <2000 ppm, <1 A composition selected from one of the following values ​​or ranges: 000ppm, <500ppm, 400ppm, <300ppm, <200ppm, <100ppm, <50ppm, <10ppm, <5ppm, or ≥0.00001ppm to <500ppm, ≥0.0001ppm to <500ppm, ≥0.00001ppm to <100ppm, ≥0.0001ppm to <100ppm, ≥1ppm to less than approximately 2000ppm, ≥1ppm to less than approximately 1000ppm, or ≥0 and <100ppm, and approximately 0.00001ppm to 2000ppm.

[0217] Embodiment 28. A composition comprising tetrachloroethylene (PCE) and at least two additional compounds selected from the group consisting of 1,1,1-trichloroethane, carbon tetrachloride, dichloromethane, and trichloroethylene (TCE).

[0218] Embodiment 29. A composition comprising 1-chloro-1,2,2-trifluoroethylene (CFO-1113) and one or more additional compounds selected from the group consisting of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1-chloro-1,2,2-trifluoroethane (HCFC-133).

[0219] Embodiment 30. The composition according to Embodiment 29, wherein the amount of 1-chloro-2-fluoroethylene (HCFC-1113) is 99% by weight or more based on the total amount of the composition.

[0220] Embodiment 31. A composition comprising 1,1,2-trifluoroethane (HFC-143) and at least two additional members selected from the group consisting of HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-E-1132, HFO-Z-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

[0221] Embodiment 32. The composition according to Embodiment 31, wherein the amount of 1,1,2-trifluoroethane (HFC-143) is 99% by weight or more based on the total amount of the composition.

[0222] Embodiment 33. The composition according to Embodiment 31, wherein the total amount of the additional compound is greater than 0 weight percent and less than 1 weight percent based on the total amount of the composition.

[0223] Embodiment 34. A process comprising HFO-E-1132 and / or HFO-Z-1132 formed in either Embodiment 1 or 2, (i) One or more HFC compounds selected from the group consisting of HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea, and HFC-1123, and (ii) A process comprising blending one or more HFO compounds selected from the group consisting of HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd, and HFO-E-1336mzz with one or more other compounds selected from the group consisting of HFO-E-1336mzz.

[0224] Embodiment 35. A blended composition comprising HFO-E-1132 and / or HFO-Z-1132, (i) One or more HFC compounds selected from the group consisting of HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea, and HFC-1123, and (ii) A blended composition comprising one or more HFC and / or HFO compounds selected from at least one of the HFO compounds selected from the group consisting of HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd, and HFO-E-1336mzz.

[0225] Embodiment 36. A process using the blend composition described in Embodiment 35 as a refrigerant, solvent, foam expander, cleaning agent, aerosol propellant, dielectric, fire extinguishing agent, or power cycle working fluid.

[0226] Embodiment 37. A process, (a) In the liquid phase, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is brought into contact with a reducing metal to dehydrochlorinate CFC-113 and form chlorotrifluoroethylene (CFO-1113), (b) A process comprising contacting CFO-1113 with hydrogen in either the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143).

[0227] Embodiment 38. The process according to Embodiment 38, further comprising converting HFC-143 in the liquid or gas phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0228] Embodiment 39. The process according to Embodiment 38, further comprising isomerizing a portion of HFO-Z-1132 in a mixture of E-1,2-difluoroethylene and Z-1,2-difluoroethylene to HFO-E-1132.

[0229] Embodiment 40. The process according to Embodiment 37, wherein steps (a) and (b) are carried out in separate reactors or in one of the same reactors.

[0230] Embodiment 41. The process according to Embodiment 1, further comprising isomerizing HFO-E-1132 to HFO-Z-1132.

[0231] Embodiment 42. A process comprising contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the gas phase in the presence of a catalyst to form 1,1,2-trifluoroethane (HFC-143).

[0232] Embodiment 43. The process according to Embodiment 42, wherein the relative molar amounts of hydrogen and CFC-113 are approximately 1:1 to approximately 3:1.

[0233] Embodiment 44. The process according to Embodiment 42 or 43, wherein the contact is performed at a temperature of approximately 80°C to approximately 250°C.

[0234] Embodiment 45. A process comprising contacting PCE with hydrogen in the gas phase in the presence of a catalyst to form an HFC-143 composition.

[0235] Embodiment 46. The process according to Embodiment 45, wherein the PCE is contacted with hydrogen in the gas phase in the presence of a catalyst, and the catalyst comprises a catalyst metal selected from the group consisting of Pd, Pt, and mixtures thereof, preferably supported on Al2O3, alumina fluoride, AlF3, or chromium oxide.

[0236] Embodiment 47. The process according to Embodiment 46, wherein the amount of catalyst metal on the carrier constitutes about 0.5% to about 10% by weight of the catalyst composition.

[0237] Embodiment 48. The process according to Embodiment 1, further comprising isomerizing HFO-E-1132 to HFO-Z-1132.

[0238] Embodiment 49. A system, A first reactor is configured to synthesize a first mixture containing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from a supply composition comprising tetrachloroethylene (PCE) and at least one additional compound selected from the group consisting of CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane. A second reactor configured to convert CFC-113 of the first mixture into a second mixture containing chlorotrifluoroethylene (CFO-1113), A third reactor configured to convert CFO-1113 of the second mixture into a third mixture containing 1,1,2-trifluoroethane (HFC-143), A system comprising a fourth reactor configured to convert HFC-143 of a third mixture into a fourth mixture containing E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0239] Embodiment 50. The system according to Embodiment 49, wherein the first, second, third, and fourth reactors are in fluid communication with one another.

[0240] Embodiment 51. The system according to Embodiment 50, wherein the system is an integrated system comprising first, second, third, and fourth reactors.

[0241] Embodiment 52. The system according to any one of Embodiments 49 to 51, further comprising a conversion system in fluid communication with a fourth reactor, wherein the conversion system is configured to adjust the E / Z ratio of HFO-1132 in the fourth mixture.

[0242] Embodiment 53. The system according to Embodiment 52, wherein the conversion system is selected from the group consisting of a distillation column, a non-catalytic heat converter, and a catalytic reactor.

[0243] Embodiment 54. A process, (a) To provide a starting feed containing tetrachloroethylene (PCE), HF, and chlorine, (b) Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feed as part of the first product mixture, (c) In the liquid phase, CFC-113 is brought into contact with a reducing metal to form chlorotrifluoroethylene (CFO-1113) as part of the second product mixture, (d) Contacting CFO-1113 with hydrogen in the gas or liquid phase to form 1,1,2-trifluoroethane (HFC-143) as part of the third product mixture, (e) A process comprising converting HFC-143 in a liquid or gas phase to a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0244] Embodiment 55. The process according to Embodiment 54, wherein at least one of CFC-113, CFO-1113, or HFC-143 is first separated from its respective product mixture before the next step.

[0245] Embodiment 56. The process according to Embodiment 54 or 55, further comprising processing the fourth product mixture to form a composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the fourth product mixture.

[0246] Embodiment 57. The process according to Embodiment 56, wherein the processing comprises distilling the fourth product mixture to form a first stream containing a composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the fourth product mixture, and a second stream having an HFO-Z-1132:HFO-E-1132 ratio higher than that of the first stream.

[0247] Embodiment 58. The process according to Embodiment 57, further comprising the process recirculating the second flow to step (b).

[0248] Embodiment 59. A process, (a) To provide a starting feed containing tetrachloroethylene (PCE), HF, and chlorine, (b) Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feed as part of the first product mixture, (c) In the gas phase or liquid phase, CFC-113 is brought into contact with hydrogen to form 1,1,2-trifluoroethane (HFC-143) as part of the second product mixture, (d) A process comprising converting HFC-143 in a liquid or gas phase to a third product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0249] Embodiment 60. The process of Embodiment 59, wherein at least one of CFC-113 or HFC-143 is separated from its respective product mixture prior to the next step.

[0250] Embodiment 61. The process of Embodiment 59 or 60, further comprising processing the third product mixture to form a composition having a lower HFO-Z-1132:HFO-E-1132 ratio than the HFO-Z-1132:HFO-E-1132 ratio of the third product mixture.

[0251] Embodiment 62. The process of Embodiment 61, wherein the processing comprises distilling the third product mixture to form a first stream comprising a composition having a lower HFO-Z-1132:HFO-E-1132 ratio than the HFO-Z-1132:HFO-E-1132 ratio of the third product mixture, and a second stream having a higher HFO-Z-1132:HFO-E-1132 ratio than the HFO-Z-1132:HFO-E-1132 ratio of the first stream.

[0252] Embodiment 63. The process of Embodiment 62, further comprising recycling the second stream to step (b).

[0253] Other Embodiments (OE) OE1. A PCE feed mixture comprising PCE and one or more additional compounds selected from CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane.

[0254] OE2. A PCE conversion product mixture comprising one or more additional compounds selected from CFC-113, CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE.

[0255] OE3. A CFC-113 product mixture, which comprises one or more additional compounds selected from CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE.

[0256] OE4. A CFO-1113 product mixture, which comprises one or more additional compounds selected from HCFC-123a, HCFC-133b, HCFC-133a, HCFC-133, and CFC-113.

[0257] OE5. A HFC-143 feed mixture, which comprises HFC-143 and one or more additional compounds selected from HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140.

[0258] OE6. A HFC-143 product mixture, which comprises one or more additional compounds selected from HFO-1123, CFO-1113, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140.

[0259] OE7.HFO-E-1132 and / or HFO-Z-1132 product mixture, comprising HFO-1141, HCO-1140, and acetylene in concentrations of <2000 ppm, <1000 ppm, <500 ppm, <400 ppm, <300 ppm, <200 ppm, <100 ppm, <50 ppm, <10 ppm, <5 ppm, ≥0.00001 ppm to <500 ppm, ≥0.0001 ppm) A mixture of HFO-E-1132 and / or HFO-Z-1132 products containing an amount selected from any one of the following values ​​and ranges: ~<500 ppm, ≥0.00001 ppm~<100 ppm, ≥0.0001 ppm~<100 ppm, ≥1 ppm~less than approximately 2000 ppm, ≥1 ppm~less than approximately 1000 ppm, or ≥0~<100 ppm, and approximately 0.00001 ppm~2000 ppm.

[0260] OE8.HFO-E-1132 (or HFO-Z-1132) product mixture comprising HFO-1141, HCO-1140, and acetylene in an amount selected from one of <100 ppm, <50 ppm, <10 ppm, and <5 ppm.

[0261] OE9.HFO-E-1132 and / or HFO-Z-1132 product mixture, comprising HFO-1141, HCO-1140, and acetylene in an amount selected from one of <100 ppm, <50 ppm, <10 ppm, or <5 ppm.

[0262] OE10. In certain embodiments of HFO-E-1132 and / or HFO-Z-1132 product mixtures, the amounts of fluoroethylene (HFO-1141), vinyl chloride (HCO-1140), acetylene, and fluoroacetylene are selected from one of <2000 ppm, <1000 ppm, <500 ppm, <2000 ppm, <1000 ppm, <500 ppm, <400 ppm, <300 ppm, <200 ppm, <100 ppm, <50 ppm, <10 ppm, <5 ppm, ≥0.00001 to <500 ppm, ≥0.0001 to <500 ppm, ≥0.00001 to <100 ppm, ≥0.0001 to <100 ppm, or ≥0 and <100 ppm.

[0263] An embodiment of the HFO-E-1132 and / or HFO-Z-1132 product mixture, wherein the total amount of fluoroethylene (HFO-1141), vinyl chloride (HCO-1140), and acetylene and fluoroacetylene is selected from one of <100 ppm, <50 ppm, <10 ppm, <5 ppm, ≥0.00001 to <100 ppm, ≥0.0001 to <100 ppm, or ≥0 and <100 ppm.

[0264] An embodiment of the HFO-E-1132 and / or HFO-Z-1132 product mixture, which optionally contains at least one of fluoroethylene (HFO-1141), vinyl chloride (HCO-1140), acetylene, and fluoroacetylene, selected from one of <100 ppm, <50 ppm, <10 ppm, <5 ppm, ≥0.00001 to <100 ppm, ≥0.0001 to <100 ppm, or ≥0 and <100 ppm, preferably without at least one of fluoroethylene (HFO-1141) and vinyl chloride (HCO-1140).

[0265] OE13.HFO-E-1132 and / or HFO-Z-1132 product mixture, comprising the following components: HFO-Z-1132 (or HFO-E-1132), acetylene, fluoroacetylene, difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), E-1-chloro-1,2-difluoroethylene (HCFO-E-1122a), Z-1-chloro -1,2-difluoroethylene (HCFO-Z-1122a), 1,1,2-trifluoroethylene (HFO-1123), fluoroethylene (HFO-1141), 1-chloro-1,1,2-trifluoroethane (HCFC-133), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2 -Difluoroethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene (HCO-1150), 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (1140), 1-chloro-1-fluoroethene A mixture of HFO-E-1132 and / or HFO-Z-1132 products comprising at least two of (HCFO-1131a), E-1-chloro-2-fluoroethene (HCFO-E-1131), Z-1-chloro-2-fluoroethene (HCFO-Z-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122), wherein the total amount of other components is less than 1% by weight of the total composition.

[0266] A process to convert a PCE supply mixture containing one or more additional compounds selected from OE14.PCE, CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane into a CFC-113 product mixture.

[0267] A process for converting a PCE product mixture (including a CFC-113 feed) containing one or more additional compounds selected from OE15.CFC-113, CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE.

[0268] A process for converting a CFC-113 mixture, comprising OE16.CFC-113 and one or more additional compounds selected from CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE, into a product mixture containing CFO-1113.

[0269] A process for converting a CFO-1113 mixture containing one or more additional compounds selected from OE17.HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b, and CFC-113 into a product mixture containing HFC-143.

[0270] A process for converting an HFC-143 mixture containing one or more additional compounds selected from OE18.HFC-143, HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140 into an HFO-E-1132 and HFO-Z-1132 product mixture.

[0271] OE19. An HFC-143 product mixture comprising one or more additional compounds selected from HFO-1123, CFO-1113, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140 to an HFO-E-1132 (or HFO-Z-1132) product mixture.

[0272] OE20. A process of converting a PCE feed mixture that also comprises one or more additional compounds selected from PCE, CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane into a CFC-113 product mixture by chlorofluorination.

[0273] OE21. A process of converting CFC-113 in a product mixture that also comprises one or more additional compounds selected from CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE into a product mixture comprising CFO-1113 by dechlorination.

[0274] OE22. A process of converting CFO-1113 in a product mixture that also comprises one or more additional compounds selected from HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b, and CFC-113 into a product mixture comprising HFC-143 by hydrogenation.

[0275] OE23. A process of converting HFC-143 in a product mixture that also comprises one or more additional compounds selected from HFC-143, HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140 into an HFO-E-1132 and HFO-Z-1132 product mixture by dehydrofluorination.

[0276] OE24. A process of converting a PCE feed mixture that also comprises one or more additional compounds selected from PCE, CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane into a CFC-113 product mixture by chlorofluorination, wherein the chlorofluorination is carried out at a temperature selected from 80 to 120°C or 250°C to 400°C.

[0277] A process for converting CFC-113 in a product mixture, which also includes one or more additional compounds selected from OE25.CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE, into a product mixture containing CFO-1113 by dechlorination, wherein CFC-113 is hydrogenodechlorinated or dechlorinated to CFO-1113.

[0278] A process for converting CFO-1113 in a product mixture containing one or more additional compounds selected from HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b, and CFC-113 into a product mixture containing HFC-143 by hydrogenation.

[0279] A process for converting HFC-143 in a product mixture, which also includes one or more additional compounds selected from OE27.HFC-143, HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140, into a product mixture of HFO-E-1132 and HFO-Z-1132 by dehydrofluoridation.

[0280] OE28. Any of OE7 to OE12, where the total amount of additional compounds is greater than 0% by weight and less than 1% by weight, based on the total amount of the composition.

[0281] OE29. Any of OE7 to OE12, where the total amount of additional compounds is greater than 0% by weight and less than 0.5% by weight, based on the total amount of the composition.

[0282] Any of the HFO-E-1132 and / or HFO-Z-1132 compositions described in OE30, OE7 to OE12, • One or more HFC compounds selected from HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea, and HFC-1123. A process comprising blending with at least one of the following HFO compounds selected from HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd, and HFO-E-1336mzz.

[0283] OE31. In certain embodiments disclosed herein, HFO-E-1132 and / or HFO-Z-1132 blends containing one or more HFC and / or HFO compounds are used as refrigerants, solvents, foam expanders, cleaning agents, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle working fluids.

[0284] OE32. A process comprising using a blend of the HFO-E-1132 and / or HFO-Z-1132 compositions described in OE7 to OE12 with other HFC, HFO, and HCFO compounds as a refrigerant, solvent, foam expander, cleaning agent, aerosol propellant, dielectric, fire extinguishing agent, or power cycle working fluid.

[0285] OE33. Process, (a) In the liquid phase, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is brought into contact with a reducing metal to dehydrochlorinate CFC-113 and form chlorotrifluoroethylene (CFO-1113), (b) In either the gas phase or the liquid phase, chlorotrifluoroethylene (CFO-1113) is brought into contact with hydrogen to form 1,1,2-trifluoroethane (HFC-143), (c) A process comprising converting 1,1,2-trifluoroethane (HFC-143) in the liquid or gas phase to form E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0286] OE33 further comprises isomerizing OE34.Z-1,2-difluoroethylene (HFO-Z-1132) to E-1,2-difluoroethylene (HFO-E-1132).

[0287] OE35. The process according to OE32-34, wherein steps "a" and "b" are carried out in separate reactors or in one of the same reactors.

[0288] OE36. The process described in OE32-34, wherein steps "a" and "b" are carried out in the same reactor.

[0289] OE37. The process according to OE32-34, wherein steps "a" and "b" are carried out in separate and different reactors.

[0290] OE38. Embodiments of a process, wherein the CFC-113 supply composition preferably comprises CFC-113 and one or more additional compounds selected from CFC-113a, CFC-114a, HCFC-123, HCFC-123a, CFC-115, CFC-12, HCFC-124, CFC-114, CFO-1317, CFC-216, CFC-318, CFC-316, CFC-215cb, CFC-214cb, HCFC-122, CFC-112, CFC-112a, and CFO-1112a.

[0291] An embodiment of the process described in OE37, wherein CFC-113 is brought into contact with hydrogen, and the relative molar amounts of hydrogen and CFC-113 in the reaction are approximately 1:1 to approximately 3:1.

[0292] OE40. An embodiment of the process described in OE37, wherein contact is performed at a temperature of approximately 80°C to approximately 250°C.

[0293] OE41. An embodiment of a process in which CFC-113 is contacted with hydrogen in the gas phase in the presence of a catalyst to form an HFC-143 composition.

[0294] An embodiment of the process described in OE40, as disclosed in U.S. Patent Application Publications No. 20080207962 and 20080207963, wherein CFC-113 is contacted with hydrogen in the gas phase in the presence of a catalyst comprising a catalytic metal selected from Pd, Pt, or a mixture thereof, preferably supported on Al2O3, alumina fluoride, AlF3, or chromium oxide.

[0295] OE43. An embodiment of the process described in OE41, wherein CFC-113 is brought into contact with hydrogen in the gas phase in the presence of a catalyst, and the amount of catalyst metal on the support constitutes about 0.5% to about 10% by weight of the catalyst composition.

[0296] Embodiments of the compositions described in OE40-OE42, wherein the OE44.HFC-143 product comprises at least one compound selected from HCFC-123a, HCFC-132c, HCFC-133, HCFC-133b, C2H6, HFC-143a, HFC-134a, and HFC-152a.

[0297] The process according to OE32, further comprising isomerizing E-1,2-difluoroethylene (HFO-E-1132) to Z-1,2-difluoroethylene (HFO-Z-1132).

[0298] OE46. In each OE process, one of the feeds from reactions (1) to (4) is independently selected from >50% by weight, >60% by weight, >70% by weight, <80% by weight, or <90% by weight before purification (e.g., by distillation), based on the total weight of the composition, and from approximately >95% by weight or >99% by weight after distillation.

[0299] OE47. System, A first reactor configured to synthesize a first mixture containing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from a supply composition comprising tetrachloroethylene (PCE) and at least one additional compound selected from CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, or 1,1,1,3-tetrachloropropane, A second reactor configured to convert CFC-113 of the first mixture into a second mixture containing chlorotrifluoroethylene (CFO-1113), A third reactor configured to convert CFO-1113 of the second mixture into a third mixture containing 1,1,2-trifluoroethane (HFC-143), A system comprising a fourth reactor configured to convert HFC-143 of a third mixture into a fourth mixture containing E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0300] OE48. The system described in OE47, wherein the first, second, third, and fourth reactors are in fluid communication with one another.

[0301] OE49. The system described in OE48, wherein the system is an integrated system comprising first, second, third, and fourth reactors.

[0302] The system according to any one of OE47 to OE49, wherein the system further comprises a conversion system in fluid communication with a fourth reactor, the conversion system being configured to adjust the E / Z ratio of HFO-1132 in the fourth mixture.

[0303] OE51. The system according to OE50, wherein the conversion system is selected from the group consisting of a distillation column, a non-catalytic heat converter, and a catalytic reactor.

[0304] OE52. Process, a. To provide a starting feed containing tetrachloroethylene (PCE), HF, and chlorine, b. Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feed as part of the first product mixture, c. In the liquid phase, CFC-113 is brought into contact with a reducing metal to form chlorotrifluoroethylene (CFO-1113) as part of the second product mixture, d. In the gas phase or liquid phase, CFO-1113 is brought into contact with hydrogen to form 1,1,2-trifluoroethane (HFC-143) as part of the third product mixture, e. A process comprising converting HFC-143 in the liquid or gas phase to a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0305] The process described in OE52, wherein at least one of CFC-113, CFO-1113, or HFC-143 is first separated from its respective product mixture before the next step.

[0306] The process according to OE52 or OE53, further comprising processing a fourth product mixture to form a composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the fourth product mixture.

[0307] OE55: The process according to OE54, comprising distilling a fourth product mixture to form a first stream containing a composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the fourth product mixture, and a second stream having an HFO-Z-1132:HFO-E-1132 ratio higher than that of the first stream.

[0308] OE56: The process described in OE55, further comprising the process of recirculating the second flow to step (b).

[0309] While certain aspects, embodiments, and principles have been described above, it should be understood that this specification is for illustrative purposes only and does not limit the scope of the present invention or the appended claims. The various aspects, embodiments, and principles described above may be used individually or in combination with each other.

Claims

1. It is a process, (a) Contacting tetrachloroethylene (PCE) with HF and chlorine to form 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), (b) In the liquid phase, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is brought into contact with a reducing metal to form chlorotrifluoroethylene (CFO-1113), (c) In either the gas phase or the liquid phase, chlorotrifluoroethylene (CFO-1113) is brought into contact with hydrogen to form 1,1,2-trifluoroethane (HFC-143), (d) A process comprising converting 1,1,2-trifluoroethane (HFC-143) in the liquid or gas phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

2. (e) The process according to claim 1, further comprising isomerizing a portion of the Z-1,2-difluoroethylene (HFO-Z-1132) in the mixture of E-1,2-difluoroethylene and Z-1,2-difluoroethylene to E-1,2-difluoroethylene (HFO-E-1132).

3. The process according to claim 1, wherein (a), (b), and (c) are part of an integrated process, and each reaction is carried out in a separate and individual reactor.

4. The process according to claim 1, wherein (a), (b), (c), and (d) are part of an integrated process, and each reaction is carried out in a separate and individual reactor.

5. The process according to claim 2, wherein (a), (b), (c), (d), and (e) are part of an integrated process, and each reaction is carried out in a separate and individual reactor.

6. The process according to claim 1 or 2, wherein (a) comprises chlorofluorination, (b) comprises dechlorination, (c) comprises hydrogenation, and (d) comprises dehydrofluorination.

7. The process according to claim 6, wherein the chlorine fluorination of PCE produces a first product mixture, the dechlorination of CFC-113 produces a second product mixture, the hydrogenation of CFO-1113 produces a third product mixture, and the dehydrofluorination of HFC-143 produces a fourth product mixture.

8. The process according to claim 1 or 2, wherein the PCE conversion is carried out in the presence of hydrogen fluoride and chlorine, in one of the following: (1) a liquid phase catalyzed by a metal halide catalyst at a temperature of 80 to 120°C, or (2) a gas phase in the presence of a chromium-based fluorination catalyst at a temperature of 250 to 400°C.

9. The process according to claim 1 or 2, wherein the PCE is a supply composition comprising, based on the total amount of the composition, >99% by weight of PCE and one or more additional compounds selected from the group consisting of 1,1,1-trichloroethane, carbon tetrachloride, dichloromethane, and trichloroethylene.

10. The process according to claim 9, wherein the amount of the additional compound is greater than 0% by weight and less than 1% by weight, based on the total amount of the supply composition.

11. The process according to claim 1 or 2, wherein the PCE conversion produces a first product mixture comprising 1,1,2-trichloro-1,2,2-trifluoroethane (CFO-113) and one or more additional compounds selected from the group consisting of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), CFC-113a, CFC-114, CFC-114a, HCFC-124, and HCFC-123, and PCE.

12. The process according to claim 11, wherein the amount of CFC-113 in the first product mixture is >95% by weight, based on the total weight of the composition.

13. The process according to claim 12, wherein the amount of the additional compound in the first product composition constitutes more than 0% by weight and less than 1% by weight, based on the total amount of the first product composition.

14. The process according to claim 11, wherein the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) comprises a portion of the first product mixture.

15. The process according to claim 14, wherein the first product mixture is used to prepare the second product mixture.

16. The process according to claim 1 or 2, wherein the reducing metal comprises zinc, magnesium, or cadmium in a solvent as a liquid phase.

17. The process according to claim 1 or 2, wherein the solvent includes a polar aprotic solvent.

18. The process according to claim 15, wherein in the liquid phase, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is brought into contact with the reducing metal at a temperature of about 20°C to about 120°C.

19. The process according to claim 1 or 2, wherein contact of chlorotrifluoroethylene (CFO-1113) with hydrogen is carried out (i) at a temperature of 50°C to about 150°C in the presence of a hydrogenation catalyst comprising a catalytic metal selected from the group consisting of Re, Ni, Pd, Pt, Ru, Rh, and Ir, or (ii) at a temperature of 150°C to about 350°C in the presence of a hydrogenation catalyst comprising a catalytic metal selected from the group consisting of Re, Ni, Pd, Pt, Ru, Rh, and Ir.

20. The process according to claim 1 or 2, wherein contact of chlorotrifluoroethylene (CFO-1113) with hydrogen is carried out in the presence of a hydrogenation catalyst selected from the group consisting of Pd and Pt.

21. The process according to claim 11, wherein the hydrogenation of chlorotrifluoroethylene (CFO-1113) produces the third product mixture comprising mainly HFC-143 and one or more additional compounds selected from the group consisting of HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-133b, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

22. The process according to claim 11, wherein the third product mixture is converted in the gas phase or liquid phase to a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

23. The process according to claim 20, wherein the conversion is carried out in the gas phase at a temperature of 150°C to 400°C.

24. The process according to claim 20, wherein the conversion is carried out in the liquid phase at a temperature of -20°C to 150°C.

25. A composition, (a) Tetrachloroethylene (PCE) and CCl 4 , CHCl 3 , at least one additional compound selected from the group consisting of trichloroethylene, 1,1,3-trichloropropene, ethylene, or 1,1,1,3-tetrachloropropane, (b) 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), and at least one additional compound selected from the group consisting of CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE, (c) Chlorotrifluoroethylene (CFO-1113), and at least one additional compound selected from the group consisting of HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b, and CFC-113. (d) At least one additional compound selected from the group consisting of 1,1,2-trifluoroethane (HFC-143), HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140, (e) E-1,2-difluoroethylene (HFO-E-1132), and at least one additional compound selected from the group consisting of HFO-1141, HFO-1123, acetylene, HFO-Z-1132, HCFO-E-1131, HFC-125, HFC-32, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140, or (f) A composition comprising Z-1,2-difluoroethylene (HFO-Z-1132), and at least one additional compound selected from the group consisting of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122, and HCO-1140.

26. A composition, (a) HFO-E-1132, and at least one additional compound selected from the group consisting of HFO-1141, HCFO-1140, acetylene, and fluoroacetylene in an amount of <500 ppm, (b) HFO-Z-1132, and at least one additional compound selected from the group consisting of HFO-1141, HCFO-1140, acetylene, and fluoroacetylene in an amount of <500 ppm, (c) At least one of HFO-E-1132 and HFO-Z-1132, and acetylene, fluoroacetylene, difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), E-1-chloro-1,2-difluoroethylene (HCFO-E-1122a), Z-1-chloro-1,2-difluoroethylene (HCFO-Z-1122a), 1,1,2-trifluoroethylene (HFO-1123), fluoroethylene (HFO-1141), 1-chloro-1,1,2-trifluoroethane (HCFC-133), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2-difluoro A composition comprising at least one of at least two additional compounds selected from the group consisting of oloethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene (HCO-1150), 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (1140), 1-chloro-1-fluoroethene (HCFO-E-1131a), E-1-chloro-2-fluoroethene (HCFO-E-1131), Z-1-chloro-2-fluoroethene (HCFO-Z-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122).

27. A composition comprising at least one of HFO-E-1132 and HFO-Z-1132, and acetylene, fluoroacetylene, difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), E-1-chloro-1,2-difluoroethylene (HCFO-E-1122a), Z-1-chloro-1,2-difluoroethylene (HCFO-Z-1122a), 1,1,2-trifluoroethylene (HFO-1123), fluoroethylene (HFO-1141), and 1-chloro-1,1,2-tri Fluoroethane (HCFC-133), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2-difluoroethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene, 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (114 0), comprising at least two additional compounds selected from the group consisting of 1-chloro-1-fluoroethene (HCFO-E-1131a), E-1-chloro-2-fluoroethene (HCFO-E-1131), Z-1-chloro-2-fluoroethene (HCFO-Z-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122), wherein the total amount of HFO-1141, HCFO-1140, acetylene, and fluoroacetylene is <2000 ppm, <1000 ppm, <500 ppm, <2000 ppm, <100 A composition selected from one of the following values ​​or ranges: 0 ppm, <500 ppm, 400 ppm, <300 ppm, <200 ppm, <100 ppm, <50 ppm, <10 ppm, <5 ppm, or ≥0.00001 ppm to <500 ppm, ≥0.0001 ppm to <500 ppm, ≥0.00001 ppm to <100 ppm, ≥0.0001 ppm to <100 ppm, ≥1 ppm to less than approximately 2000 ppm, ≥1 ppm to less than approximately 1000 ppm, or ≥0 and <100 ppm, and approximately 0.00001 ppm to 2000 ppm.

28. A composition comprising tetrachloroethylene (PCE) and at least two additional compounds selected from the group consisting of 1,1,1-trichloroethane, carbon tetrachloride, dichloromethane, and trichloroethylene (TCE).

29. A composition comprising 1-chloro-1,2,2-trifluoroethylene (CFO-1113) and one or more additional compounds selected from the group consisting of 1,2-dichloro-1,1,2-trifluoroethane (HCFC-123a), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and 1-chloro-1,2,2-trifluoroethane (HCFC-133).

30. The composition according to claim 29, wherein the amount of 1-chloro-2-fluoroethylene (HCFC-1113) is 99% by weight or more based on the total amount of the composition.

31. A composition comprising 1,1,2-trifluoroethane (HFC-143) and at least two additional members selected from the group consisting of HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-E-1132, HFO-Z-1132, HCFO-E-1122a, HCFO-Z-1122a, HCFO-1140, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113.

32. The composition according to claim 31, wherein the amount of 1,1,2-trifluoroethane (HFC-143) is 99% by weight or more based on the total amount of the composition.

33. The composition according to claim 31, wherein the total amount of the additional compound is greater than 0 weight percent and less than 1 weight percent based on the total amount of the composition.

34. A process comprising: (i) One or more HFC compounds selected from the group consisting of HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea, and HFC-1123, and (ii) A process comprising blending one or more HFO compounds selected from the group consisting of HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd, and HFO-E-1336mzz with one or more other compounds selected from the group consisting of (ii) HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd, and HFO-E-1336mzz.

35. A blended composition comprising HFO-E-1132 and / or HFO-Z-1132, (i) One or more HFC compounds selected from the group consisting of HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea, and HFC-1123, and (ii) A blended composition comprising one or more HFC and / or HFO compounds selected from at least one of the HFO compounds selected from the group consisting of HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd, and HFO-E-1336mzz.

36. A process using the blend composition according to claim 35 as a refrigerant, solvent, foam expander, cleaning agent, aerosol propellant, dielectric, fire extinguishing agent, or power cycle working fluid.

37. It is a process, (a) In the liquid phase, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is brought into contact with a reducing metal to dehydrochlorinate the CFC-113 and form chlorotrifluoroethylene (CFO-1113), (b) A process comprising contacting the CFO-1113 with hydrogen in either the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143).

38. The process according to claim 38, further comprising converting the HFC-143 in the liquid or gas phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

39. The process according to claim 38, further comprising isomerizing a portion of the HFO-Z-1132 in the mixture of E-1,2-difluoroethylene and Z-1,2-difluoroethylene to HFO-E-1132.

40. The process according to claim 37, wherein steps (a) and (b) are carried out in separate reactors or in one of the same reactors.

41. The process according to claim 1, further comprising isomerizing HFO-E-1132 to HFO-Z-1132.

42. A process comprising contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with hydrogen in the gas phase in the presence of a catalyst to form 1,1,2-trifluoroethane (HFC-143).

43. The process according to claim 42, wherein the relative molar amounts of hydrogen and CFC-113 are approximately 1:1 to approximately 3:

1.

44. The process according to claim 42 or 43, wherein the contact is performed at a temperature of about 80°C to about 250°C.

45. A process comprising contacting PCE with hydrogen in the gas phase in the presence of a catalyst to form an HFC-143 composition.

46. The PCE is brought into contact with hydrogen in the gas phase in the presence of a catalyst, and the catalyst is preferably Al 2 O 3 fluorinated alumina, AlF 3 The process according to claim 45, comprising a catalyst metal selected from the group consisting of Pd, Pt, and mixtures thereof, supported on chromium oxide.

47. The process according to claim 46, wherein the amount of catalyst metal on the support constitutes about 0.5% to about 10% by weight of the catalyst composition.

48. The process according to claim 1, further comprising isomerizing HFO-E-1132 to HFO-Z-1132.

49. It is a system, Tetrachloroethylene (PCE) and CCl 4 , CHCl 3 A first reactor is configured to synthesize a first mixture containing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from a supply composition comprising, at least one additional compound selected from the group consisting of trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane, A second reactor configured to convert the CFC-113 of the first mixture into a second mixture containing chlorotrifluoroethylene (CFO-1113), A third reactor configured to convert the CFO-1113 of the second mixture into a third mixture containing 1,1,2-trifluoroethane (HFC-143), A system comprising: a fourth reactor configured to convert the HFC-143 of the third mixture into a fourth mixture containing E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

50. The system according to claim 49, wherein the first, second, third, and fourth reactors are in fluid communication with one another.

51. The system according to claim 50, wherein the system is an integrated system comprising the first, second, third, and fourth reactors.

52. The system according to any one of claims 49 to 51, further comprising a conversion system in fluid communication with the fourth reactor, wherein the conversion system is configured to adjust the E / Z ratio of the HFO-1132 in the fourth mixture.

53. The system according to claim 52, wherein the conversion system is selected from the group consisting of a distillation column, a non-catalytic heat converter, and a catalytic reactor.

54. It is a process, (a) To provide a starting feed containing tetrachloroethylene (PCE), HF, and chlorine, (b) Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feed as part of the first product mixture, (c) In the liquid phase, the CFC-113 is brought into contact with a reducing metal to form chlorotrifluoroethylene (CFO-1113) as part of the second product mixture, (d) Contacting CFO-1113 with hydrogen in the gas phase or liquid phase to form 1,1,2-trifluoroethane (HFC-143) as part of the third product mixture, (e) A process comprising converting the HFC-143 in the liquid or gas phase to a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

55. The process according to claim 54, wherein at least one of CFC-113, CFO-1113, or HFC-143 is first separated from the respective product mixture before the next step.

56. The process according to claim 54 or 55, further comprising processing the fourth product mixture to form a composition having an HFO-Z-1132:HFO-E-1132 ratio lower than the HFO-Z-1132:HFO-E-1132 ratio of the fourth product mixture.

57. The process according to claim 56, wherein the processing comprises distilling the fourth product mixture to form a first stream containing the composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the fourth product mixture, and a second stream having an HFO-Z-1132:HFO-E-1132 ratio higher than that of the first stream.

58. The process according to claim 57, further comprising recirculating the second flow to step (b).

59. It is a process, (a) To provide a starting feed containing tetrachloroethylene (PCE), HF, and chlorine, (b) Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feed as part of the first product mixture, (c) In the gas phase or liquid phase, the CFC-113 is brought into contact with hydrogen to form 1,1,2-trifluoroethane (HFC-143) as part of the second product mixture, (d) A process comprising converting the HFC-143 in the liquid or gas phase to a third product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

60. The process according to claim 59, wherein at least one of CFC-113 or HFC-143 is separated from the respective product mixture before the next step.

61. The process according to claim 59 or 60, further comprising processing the third product mixture to form a composition having an HFO-Z-1132:HFO-E-1132 ratio lower than the HFO-Z-1132:HFO-E-1132 ratio of the third product mixture.

62. The process according to claim 61, wherein the processing comprises distilling the third product mixture to form a first stream containing the composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the third product mixture, and a second stream having an HFO-Z-1132:HFO-E-1132 ratio higher than that of the first stream.

63. The process according to claim 62, further comprising recirculating the second flow to step (b).

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