Method for preparing 1, 2-difluoroethylene from tetrachloroethylene and composition thereof

Abstract

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

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application 63 / 541,333, filed September 29, 2023, the disclosure of which is incorporated herein by reference in its entirety. Background Technology

[0003] For many years, hydrofluoroolefins (HFOs) with low ozone depletion potential (ODP) and low global warming potential (GWP) have replaced saturated CFCs (chlorofluorocarbons), HCFCs (hydrochlorofluorocarbons), and HFCs (hydrofluorocarbons) in various applications because saturated halogenated hydrocarbons tend to have high GWP values. For example, HFC-32 (CH2F2), HFC-125 (C2HF5), and HFC-134a (CH2FCF3) have GWP values ​​of 675, 3500, and 1430, respectively. Therefore, the use of low ODP and GWP materials as refrigerants, solvents, foam expanders, cleaning agents, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle working fluids continues to attract attention.

[0004] The regulatory environment is constantly evolving, and the properties being considered are no longer limited to ODP and GWP. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potential, but also exhibit low or no flammability, provide excellent performance in a wide range of applications, and meet evolving regulatory standards.

[0005] There is a need in the art for novel refrigerants that meet evolving regulations and provide heat transfer and refrigerant properties that meet or exceed the efficiency of conventional refrigerants.

[0006] To meet these growing demands, existing and novel halogenated olefins continue to be developed, evaluated, and produced using more efficient methods. One such candidate is the E-isomer and / or Z-isomer of 1,2-difluoroethylene (HFO-1132), which is suitable as a blending component due to its environmentally friendly decomposition characteristics in the atmosphere. Current processes typically favor the production of the Z-isomer, which requires the isomerization of significant quantities of the Z-isomer to the E-isomer. Therefore, new methods for producing these novel refrigerant candidates remain needed. Summary of the Invention

[0007] The present invention relates to methods for producing E- and Z-isomers (HFO-E-1132 and HFO-Z-1132) of 1,2-difluoroethylene via intermediates, compositions thereof, and methods for using these isomers.

[0008] Certain embodiments disclosed herein relate to an integrated process for the production of the E-isomer and Z-isomer of HFO-1132 using tetrachloroethylene (CC1 2=CC1 2, PCE) as a starting material according to the following reactions.

[0009] (1): tetrachloroethylene (PCE) + 3HF + Cl2→ 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) + 3HCl

[0010] (2): CFC-113 + Zn→ chlorotrifluoroethylene (CFO-1113) + ZnCl2

[0011] (3): CFO-1113 + 2H2→ 1,1,2-trifluoroethane (HFC-143) + HCl

[0012] (4): HFC-143→ HFO-E-1132 + HFO-Z-1132 + HF

[0013] Certain embodiments disclosed herein relate to an integrated process involving a sequence of a first chemical reaction, a second chemical reaction, a third chemical reaction, and a fourth chemical reaction, which chemical reactions result in the conversion of PCE to a mixture of HFO-E-1132 and HFO-Z-1132.

[0014] Certain embodiments disclosed herein relate to an integrated process for the production of the E-isomer and Z-isomer of HFO-1132 using PCE as a starting material according to the above reactions (1), (2), (3), and (4) and the following isomerization reaction:

[0015] (5): HFO-Z-1132→ HFO-E-1132 (E)

[0016] In certain embodiments disclosed herein, reactions (1), (2), (3), and (4) produce a first product mixture composition, a second product mixture composition, a third product mixture composition, and a fourth product mixture composition, respectively, which product mixture compositions form the reactant feed for subsequent reactions (2), (3), (4), and (5), respectively.

[0017] In certain embodiments disclosed herein, reactions (1), (2), (3), and (4) are part of an integrated process, and each reaction is conducted in a separate and distinct reactor, respectively.

[0018] In some embodiments disclosed herein, reactions (2) and (3) are carried out in separate reactor / reactor systems adjacent to each other, because CFO-1113 is highly unstable in the absence or presence of air. CFO-1113 should be handled like tetrafluoroethylene, therefore it is desirable that the system for producing CFO-1113 be located adjacent to the system for hydrogenating CFO-1113. This can be achieved by integrating the two methods in the same location, either by directly linking the two process steps together or by constructing the hydrogenation process system at the location where CFO-1113 is produced (optionally at a public plant facility) to minimize transport.

[0019] In some embodiments disclosed herein, reactions (2) and (3) are combined in the same reactor, and CFC-113 is directly converted to HFC-143 in a single process step.

[0020] In some implementations, reactions (1), (2), (3), (4) and (5) are part of an integrated approach, and each reaction is carried out in a separate and independent reactor (optionally at a shared plant facility).

[0021] In some implementations, reactions (1), (2), (3), (4) and (5) are part of an integrated method, and reactions (1), (4) and (5) are carried out in separate and independent reactors (optionally at a common plant facility), while reactions (2) and (3) are combined in the same reactor, and CFC-113 is directly converted to HFC-143 in a single method step.

[0022] In some reaction embodiments, for reactions (1), (2), (3), and (4), the feed composition comprises:

[0023] a. A PCE feed composition, which preferably comprises PCE and one or more additional compounds selected from CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropylene, ethylene, and 1,1,1,3-tetrachloropropane (HCC-250fb).

[0024] b. A CFC-113 feed 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;

[0025] c. A CFO-1113 feed 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

[0026] d. 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.

[0027] In some reaction embodiments, for reactions (1), (2), (3), and (4), the feed composition comprises:

[0028] a. A PCE feed composition, which preferably comprises PCE and one or more additional compounds selected from CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropylene, ethylene, and 1,1,1,3-tetrachloropropane (HCC-250fb).

[0029] b. A CFC-113 feed 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;

[0030] c. A CFO-1113 feed 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

[0031] d. An HFC-143 feed 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.

[0032] The respective feed compositions of a), b), c) and d) are present independently in amounts selected from one of the following: >95% by weight, >96% by weight, >97% by weight, >98% by weight or >99% by weight based on the total weight of the compositions, and the corresponding balances include, for example, the total amount of additional compounds of a), b), c) and d) after purification by distillation.

[0033] In some reaction embodiments, for reactions (1), (2), (3), and (4), the feed compositions respectively contain PCE, CFC-113, CFO-1113, or HFC-143 components, which are present independently in amounts selected from: >50% by weight, >60% by weight, >70% by weight, >80% by weight, or >90% by weight before purification, for example by distillation, and about <95% by weight based on the total weight of the composition, and the corresponding balances include the total amounts of additional compounds after purification, for example by distillation, a), b), c), and d).

[0034] In some reaction embodiments, for reactions (1), (2), (3), and (4), the feed composition comprises a PCE, CFC-113, CFO-1113, or HFC-143 component and an additional compound, wherein the amount of each PCE, CFC-113, CFO-1113, or HFC-143 component and the corresponding additional compound is independently selected from one of the following:

[0035] • Based on the total weight of the composition, >95% by weight of the components and <5% by weight of the additional compounds,

[0036] • Based on the total weight of the composition, >96% by weight of the components and <4% by weight of the additional compounds,

[0037] • Based on the total weight of the composition, >97% by weight of the components and <3% by weight of the additional compounds,

[0038] • >98% by weight of components and <2% by weight of additional compounds, and

[0039] • >99% by weight of components and <1% by weight of additional compounds.

[0040] In some embodiments, the CFC-113 feed 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.

[0041] In some embodiments, the relative molar ratio of hydrogen to CFC-113 in reaction (3) is about 1:1 to about 3:1.

[0042] In some embodiments, the relative molar amounts of hydrogen and CFC-113 in reaction (3) are contacted at a temperature of about 80°C to about 250°C.

[0043] In some embodiments, CFC-113 is contacted with hydrogen in the gas phase in the presence of a catalyst to form an HFC-143 composition.

[0044] In some embodiments, 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 mixtures thereof, preferably supported on Al2O3, fluorinated alumina, AlF3, or chromium oxide, as disclosed in U.S. Patent Applications 20080207962 and 20080207963, the disclosure of each of which is incorporated herein by reference.

[0045] In some embodiments, CFC-113 is contacted with hydrogen in the gas phase in the presence of a catalyst, wherein the amount of catalytic metal on the support is about 0.5% to about 10% by weight of the catalyst composition.

[0046] In some 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.

[0047] In certain embodiments involving reaction (5), the HFO-1132 composition comprises at least one of HFO-E-1132 or HFO-Z-1132, and one or more additional compounds selected from 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), vinyl fluoride (HFO-1141), 1-chloro-1,2,2-trifluoroethane (HCFC-133), and 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), dichlorofluoromethane (HCFC-22), ethylene, 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (1140), 1-chloro-1-fluoroethylene (HCFO-1131a), E-1-chloro-2-fluoroethylene (HCFO-E-1131), Z-1-chloro-1-fluoroethylene (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 the following: <100ppm, <50ppm, <10ppm, <5ppm or <1ppm.

[0048] In certain embodiments of HFO-E-1132, HFO-Z-1132, or HFO-Z / E-1132 product mixtures, the amounts of vinyl fluoride (HFO-1141), vinyl chloride (HCO-1140), acetylene, and fluoroacetylene are selected from one of the following: <2000ppm, <1000ppm, <500ppm, <400ppm, <300ppm, <200ppm, <100ppm, <50ppm, <10ppm. m, <5ppm, ≥0.00001ppm to <500ppm, ≥0.0001ppm to <500ppm, ≥0.00001ppm to <100ppm, ≥0.0001ppm to <100ppm, ≥1ppm to less than about 2000ppm, ≥1ppm to less than about 1000ppm, or ≥0ppm and <100ppm, and all values ​​and ranges from about 0.00001ppm to 2000ppm.

[0049] In some embodiments, HFO-E-1132, HFO-Z-1132, or the HFO-Z / E-1132 product mixture contains at least two additional members selected from: one of HFO-Z-1132 or HFO-E-1132, and at least one of: 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), vinyl fluoride (HFO-1141), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethylene (HCFO-1123), fluoroethylene (HFO-1141), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1,2,2-trifluoroethylene (HCFO-1123a ... Fluoroethane (HCFC-133), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2-difluoroethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), dichlorofluoromethane (HCFC-22), ethylene, 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (HCO-1140), 1-chloro-1-fluoroethylene (HCFO-1131a), E-1-chloro-2-fluoroethylene (HCFO-E-1131), Z-1-chloro-2-fluoroethylene (HCFO-Z-1131), vinylidene fluoride (HFO-1132a), and 1-chloro-2,2-difluoroethylene (HCFO-1122). Preferably, the amount of 1,2-difluoroethane (HFC-152) is selected from one of the following: <100ppm, 50ppm, 10ppm, 5ppm or 1ppm.

[0050] The embodiments disclosed herein relate to a method for converting (chlorofluorinating) PCE to CFC-113 (e.g., preparing or producing CFC-113) under the following conditions: (1) a liquid phase catalyzed by a metal halide in the presence of HF and Cl2 at a temperature of 80°C to 120°C, or (2) a gas phase in the presence of a partially fluorinated metal catalyst at a temperature of 250°C to 400°C, wherein the metal includes Group 6 metals of the periodic table. In one embodiment disclosed herein, the PCE composition comprises tetrachloroethylene and at least one or more compounds selected from CCl4, CHCl3, trichlorobromomethane, dichloroethylene bromide isomer, trichlorobromoethylene, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane.

[0051] Some embodiments disclosed herein relate to a tetrachloroethylene (PCE) composition containing >99% by weight of PCE based on the total composition, and one or more additional compounds selected from chloroform, carbon tetrachloride, trichlorobromomethane, dichloroethylene bromide isomer, trichlorobromoethylene, 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 said compound is less than 1% by weight of the total composition.

[0052] 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.

[0053] Some embodiments disclosed herein relate to a method of reaction (2) comprising contacting a CFC-113 composition with a reducing metal (including zinc, magnesium or cadmium) in a liquid phase to dechlorinate the CFC-113 and produce CFO-1113.

[0054] In one embodiment, the CFC-113 composition comprises CFC-113 and less than about 1% by weight of two or more additional compounds, substantially composed of them, or composed of them, wherein the two or more additional compounds are 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, wherein the total amount of said additional compounds is less than 1% by weight of the total composition.

[0055] In another embodiment disclosed herein, the product mixture containing CFO-1113 comprises, is substantially composed of, or is composed of, at least one or more compounds selected from HCFC-123a, HCFC-133a, HCFC-133b, HCFC-133, and CFC-113.

[0056] Some embodiments disclosed herein relate to a composition comprising >99% by weight of CFC-113 based on the total amount of the composition, and three or more additional compounds, substantially consisting of or consisting of them, wherein the three or more additional compounds are 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 said additional compounds is less than 1% by weight of the total composition.

[0057] In some embodiments disclosed herein, the second product mixture comprises >99% by weight of CFO-1113 based on the total amount of the composition, and the composition further 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, wherein the total amount of said additional compounds is less than 1% by weight of the total composition.

[0058] In some embodiments disclosed herein, the second product mixture comprises >99% by weight of CFO-1113 based on the total amount of the composition, and the composition further 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, wherein the total amount of said additional compounds is less than 1% by weight of the total composition.

[0059] Some embodiments disclosed herein relate to a method of reaction (3) comprising contacting a CFO-1113 second product mixture with hydrogen in the gas phase, optionally in the presence of a catalyst, to produce a third product mixture containing HFC-143, for example, the preparation or production of HFC-143.

[0060] 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, and 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.

[0061] Some embodiments disclosed herein relate to a method that involves contacting CFO-1113 with hydrogen at a temperature of about 50°C to about 150°C.

[0062] Some embodiments disclosed herein relate to a method comprising contacting CFO-1113 with hydrogen at a temperature of about 50°C to about 150°C and 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. The catalytic metal is preferably supported on carbon, alumina, fluorinated alumina, or aluminum fluoride, as disclosed, for example, in US 5,068,473, the entire disclosure of which is incorporated herein by reference.

[0063] Certain embodiments disclosed herein relate to a method integrating steps (2) and (3) above, wherein CFC-113 is contacted with hydrogen in a reaction zone in the gas phase at a temperature of about 150°C to about 350°C to provide a mixture comprising HFC-143, wherein the reaction zone contains a catalytic metal selected from Pd, Pt, or mixtures thereof, preferably supported on Al2O3, fluorinated alumina, AlF3, or chromium oxide, as disclosed in U.S. Patent Applications 20080207962 and 20080207963, the entire disclosure of each of which is incorporated herein by reference.

[0064] In some embodiments disclosed herein, the product mixture of reaction (3), i.e., the third product mixture, primarily 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 some embodiments disclosed herein, the defluorination (4) of HFC-143 is carried out in the gas or liquid phase.

[0065] In some embodiments disclosed herein, the defluorination reaction (4) is carried out in the gas phase.

[0066] In some embodiments disclosed herein, the defluorination reaction (4) is carried out in the liquid phase.

[0067] In some embodiments disclosed herein, the defluorination reaction (4) is carried out in the gas phase at a temperature of 150°C to 400°C.

[0068] In some embodiments disclosed herein, the defluorination reaction (4) is carried out in the liquid phase at a temperature of -20°C to 150°C.

[0069] In some embodiments disclosed herein, reaction (4) is carried out in the gas phase at a temperature of 150°C to 400°C and 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, a metal supported on a trivalent lanthanum compound containing a fluoride anion (e.g., lanthanum fluoride and / or lanthanum fluoride), and a trivalent chromium compound (e.g., Cr₂O₃), wherein the metal is selected from one or more of the group consisting of: chromium, manganese, iron, cobalt, nickel, magnesium, and zinc. Other suitable catalysts include cobalt- or nickel-substituted chromium oxide catalysts prepared as disclosed in US 7,217,678, the entire disclosure of which is incorporated herein by reference.

[0070] Some embodiments disclosed herein involve reaction (4), which 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 optional phase-transfer catalyst.

[0071] Some embodiments disclosed herein relate to reaction (4), wherein the starting material comprises an HFC-143 composition containing at least two of the following compounds: 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.

[0072] Some embodiments disclosed herein relate to reaction (4), wherein the starting material comprises an HFC-143 composition containing at least two of the following compounds: 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 in water or a polar solvent at a temperature of -20°C to 150°C in the presence of an alkali metal hydroxide (including but not limited to LiOH, NaOH, or KOH) and optionally in the presence of a phase transfer catalyst.

[0073] In some embodiments disclosed herein, reaction (4) is carried out in the liquid phase at a temperature from -20°C to 150°C in the presence of a strong base, a polar solvent, and an optional phase-transfer catalyst comprising materials 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, aryl, or aralkyl. 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.

[0074] Some embodiments disclosed herein involve reaction (4), which is carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of a strong base and with or without a catalyst.

[0075] Some embodiments disclosed herein involve reaction (4), which is carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of a strong base and solvent, and with or without a catalyst.

[0076] Some embodiments disclosed herein involve reaction (4), which is 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 alkali metal amide, and a solvent.

[0077] Some embodiments disclosed herein involve reaction (4), which is carried out in the liquid phase at a temperature from -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, in the presence of an organic solvent containing an acyclic or cyclic ether.

[0078] Some embodiments disclosed herein involve reaction (4), which is carried out in the liquid phase at a temperature of -20°C to 100°C in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of an organic solvent containing acyclic or cyclic ethers, with or without a catalyst.

[0079] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase at a temperature from -20°C to 100°C in the presence of (i) 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, (ii) an organic solvent containing an acyclic or cyclic ether, and (iii) in the presence or absence of a catalyst containing a crown ether or a crypt ether.

[0080] Some embodiments disclosed herein relate to reaction (4), which is 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, in the presence of an organic solvent containing an acyclic ether or a cyclic ether, with or without a catalyst containing a crown ether or a crypt ether, 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).

[0081] Some embodiments disclosed herein involve reaction (4), which is 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, in the presence of an organic solvent containing an acyclic ether or a cyclic ether, with or without a catalyst containing a crown ether or a crypt ether, wherein the alkali metal or alkaline earth metal alkoxide includes 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 includes lithium hydride, sodium hydride, potassium hydride, or calcium hydride; the organometallic lithium compound includes n-butyllithium, methyllithium, or isopropyllithium; and the alkali metal or alkaline earth metal amide includes lithium dimethylamino, lithium diethylamino, lithium diisopropylamino, or bis(diisopropylamino)magnesium.

[0082] Some embodiments disclosed herein involve reaction (4), which is 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, in the presence of an organic solvent containing an acyclic ether or a cyclic ether, with or without a catalyst containing a crown ether or a crypt ether, wherein the alkali metal or alkaline earth metal alkoxide includes 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 includes lithium hydride, sodium hydride, potassium hydride, or calcium hydride; the organometallic lithium compound includes n-butyllithium, methyllithium, or isopropyllithium; and the alkali metal or alkaline earth metal amide includes lithium dimethylamino, lithium diethylamino, lithium diisopropylamino, or bis(diisopropylamino)magnesium.

[0083] Some embodiments disclosed herein involve reaction (4), which is carried out in the liquid phase at a temperature from -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, in the presence of an organic solvent containing an acyclic or cyclic ether, with or without a catalyst, and the organic solvent includes one of diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, or dioxane.

[0084] Some embodiments disclosed herein involve reaction (4), which is carried out in the liquid phase at a temperature from -20°C to 100°C in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of an organic solvent containing acyclic or cyclic ethers, with or without a catalyst, and the organic solvent includes diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc. The catalyst comprises a crown ether or a crypt ether, selected from 1,4,7,10,13-pentacyclopentadecane (15-crown-5) and 1,4,7,10,13,16-hexacyclooctadecane (18-crown-6), and the crypt ether comprises 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-(8.8.8)hexacosane (also known as 2,2,2-crypt ether).

[0085] One embodiment disclosed herein relates to a method involving a 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.

[0086] One embodiment disclosed herein relates to a method involving reaction (5) and catalytic isomerization of HFO-Z-1132 to HFO-E-1132 at a temperature of about 250°C to about 500°C.

[0087] One embodiment disclosed herein relates to a method involving a reaction (5) and the catalytic conversion of 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, chromium supported on alumina, fluorinated alumina, or AlF3, or cobalt or nickel-substituted chromium oxide as disclosed in US 7,217,678, the entire disclosure of which is incorporated herein by reference.

[0088] One embodiment disclosed herein relates to a composition comprising PCE and at least two of the following compounds / components: chloroform, carbon tetrachloride, trichlorobromomethane, dichloroethylene bromide isomer, trichloroethylene bromide, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3-trichloro-1-propene, and 1,1,1,3-tetrachloropropane.

[0089] One embodiment disclosed herein relates to a composition comprising PCE and at least two of a compound / component selected from: chloroform, carbon tetrachloride, trichlorobromomethane, trichloroethylene, dichloroethylene bromide isomer, 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 wherein the amount of the other components is less than 1% by weight of the total composition.

[0090] One embodiment disclosed herein relates to a composition comprising CFO-1113 and at least one or both of the following compounds / components: 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).

[0091] One embodiment disclosed herein relates to a composition comprising HFC-143 and at least two of the following compounds / components: 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.

[0092] One embodiment disclosed herein relates to a composition comprising HFC-143 and at least three of the following compounds / components: 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.

[0093] One embodiment disclosed herein relates to a composition comprising HFC-143 and at least four of the following compounds / components: 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.

[0094] One embodiment disclosed herein relates to a composition comprising HFC-143 and at least five or more of the following compounds / components: 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.

[0095] In one embodiment disclosed herein, HFO-E-1132 and / or HFO-Z-1132 are blended with other HFCs, HFOs (e.g., HFO-E / Z1234, HFO-1234yf, HFO-1336) and HCFO compounds for use as refrigerants, solvents, foam expanders, detergents, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle working fluids.

[0096] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In case of any conflict, this specification and its included definitions shall prevail. Although methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting. Attached Figure Description

[0097] Figure 1 A system for performing an integration method according to one embodiment of the present invention is illustrated schematically; and

[0098] Figure 2This is a schematic flow diagram illustrating the use of a distillation column and optional recycle stream according to some embodiments of the invention to obtain a composition of HFO-1132 having a low Z:E ratio. Detailed Implementation

[0099] This invention relates to methods for producing E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132) according to the following reactions:

[0100] (1): Tetrachloroethylene (PCE) + 3HF + Cl2 → 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) + 3HCl

[0101] (2): CFC-113 + Zn → Chlorotrifluoroethylene (CFO-1113) + ZnCl2

[0102] (3): CFO-1113 + 2H2 → 1,1,2-trifluoroethane (HFC-143) + HCl

[0103] (4): HFC-143→E-1,2-difluoroethylene (HFO-E-1132)+Z-1,2-difluoroethylene (HFO-Z-1132)+HF

[0104] (5) (Optional): HFO-Z-1132 → HFO-E-1132

[0105] In some embodiments, the present invention relates to compositions derived from steps (1), (2), (3) and / or (4) and optionally (5).

[0106] refer 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, reactors 10, 20, 30, and 40 are integrated such that each reactor 10, 20, 30, and 40 is in flow communication with an immediately preceding / upstream reactor and / or an immediately following / downstream reactor. Reactors 10, 20, 30, and 40 are suitably configured as liquid-phase reactors or gas-phase reactors, having or not having a catalyst or reactive metal, depending on the needs of each individual reaction step as discussed herein, for producing an intermediate mixture and an HFO-E / Z-1132 mixture from an initial feed of tetrachloroethylene (PCE or R-1110), HF, and chlorine. The first reactor 10, the second reactor 20, and the third reactor 30 respectively produce intermediate product streams comprising CFC-113, CFO-1113, and HFC-143.

[0107] More specifically, see referenceFigure 1 A starting feed composition containing PCE is introduced into a first reactor 10 along with HF and Cl2 to synthesize CFC-113. The first reactor 10 thus produces a first intermediate product mixture containing CFC-113, which is withdrawn from the first reactor 10 via line 12 and fed into a second reactor 20. Optionally, in one embodiment, CFC-113 is separated from the first intermediate stream using conventional separation equipment (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. The second reactor 20 thus produces a second intermediate product mixture containing CFO-1113, which is withdrawn from the second reactor via line 14 and fed into a third reactor 30. Optionally, in one embodiment, CFO-1113 is separated from the second intermediate stream using conventional separation equipment (not shown), and the purified CFO-1113 is then introduced into the third reactor 30. Hydrogen is also fed into the third reactor 30 along with CFO-1113, and the components react to form HFC-143.

[0108] In another embodiment, the CFC-113 generated in the first reactor 10, optionally purified as described above, can be fed directly into the third reactor 30 via line 17.

[0109] The third reactor 30 thus produces a third intermediate product mixture containing HFC-143, which is withdrawn from the third reactor 30 via line 16 and fed into the fourth reactor 40. Optionally, in one embodiment, HFC-143 is separated from the third intermediate stream using conventional separation equipment (not shown), and the purified HFC-143 is then introduced into the fourth reactor 40 to convert it into a fourth product mixture containing HFO-E-1132 + HFO-Z-1132.

[0110] 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.

[0111] More specifically, such as Figure 2As shown, in one embodiment, a fourth product mixture having a relatively high Z:E ratio of HFO-1132 is removed from a fourth reactor 40 and fed via line 18 to a separation system, such as a distillation column 50. Therefore, in one embodiment, the present invention relates to a system of reactors 10, 20, 30, and 40, which optionally relates to the separation system described above. Figure 1 The delivery lines 12, 14, 16 and 17 discussed are integrated together, and also include an additional delivery line 18 and distillation column 50.

[0112] The separation system (which may include, for example, 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.

[0113] In some embodiments, the overhead feed stream 22 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.

[0114] In one embodiment, the overhead stream 22 has a relatively low Z:E ratio of the HFO-1132 isomer, for example, a Z:E ratio of about 0.01:1 to about 0.1:1, while the bottom stream 24 has a relatively high Z:E ratio of the HFO-1132 isomer, for example, a Z:E ratio of about 10:1 or greater. In one embodiment, either or both of streams 22 and 24 may be fed to an isomerization reactor (not shown) to isomerize HFO-Z-1132 to HFO-E-1132. The streams may be allowed to undergo an isomerization reaction to increase the content of the E-isomer.

[0115] Additionally or alternatively, in one implementation scheme, such as Figure 2As shown, the bottom stream 24 can be recycled to the first reactor 10 for the synthesis of CFC-113. More specifically, in one embodiment, the high-boiling fraction 24, which mainly comprises HFO-Z-1132, can be returned to the first reactor 10, where it undergoes chlorofluorination through a series of reactions to produce CFC-113.

[0116] 1.HFO-Z-1132+Cl2→CHClFCCHClF (HCFC-132)

[0117] 2.HCFC-132+Cl2→HCl+CHClFCCl2F (HCFC-122a)

[0118] 3.HCFC-122a+Cl2→HCl+CCl2FCCl2F (CFC-112)

[0119] 4.CFC-112+HF→HCl+Cl2FCClF2 (CFC-113)

[0120] Before addressing the details of the implementation scheme described herein, some terms are defined or clarified below.

[0121] As used herein, the term "compound" means all stereoisomers, geometric isomers, tautomers, and isotopes that include the structure or chemical described. Unless otherwise stated, compounds identified herein by name or structure as a particular tautomer are intended to include other tautomers.

[0122] 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 not containing a carbon-carbon double bond (halogen = fluorine, chlorine, bromine, iodine). Examples are described throughout this specification.

[0123] The term "hydrohaloolefin" is intended to refer to compounds selected from the categories of hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO), which include a double bond between adjacent carbon atoms and may contain 1 to 8 carbon atoms.

[0124] As used herein, the term "isomerization method" refers to a method used to alter the molecular geometry, for example, changing the orientation from cis to trans in an alkene. As is known in the art, cis and trans isomers are more accurately referred to as Z-isomers or E-isomers, depending on the exact substitution pattern in the alkene. In isomerization methods, the relative ratio of Z-isomers to E-isomers is altered.

[0125] The term "washing" refers to the use of solid or liquid media to selectively remove certain components in order to achieve desired production quality.

[0126] As used herein, the term "chlorofluorination" is intended to encompass liquid-phase or gas-phase methods in which a suitable substrate (e.g., PCE) is contacted with a mixture of hydrogen fluoride (HF) and chlorine (Cl2) in a reaction zone to increase the fluorine content of said substrate. In addition to the reactors disclosed herein, heat exchangers, effluent lines, units associated with mass transfer, contact vessels (premixers), distillation columns, and feed and material delivery lines associated with reactors, heat exchangers, vessels, columns, and units used in the methods of the embodiments disclosed herein should be constructed of corrosion-resistant materials. Preferably, reactors and components are made of acid-resistant alloys, such as nickel, nickel-based alloys (e.g., Hastelloy, available from Special Metals Corp.). ® ), under the product name Inconel ® Commercially available nickel-chromium alloys (hereinafter referred to as "Inconel") ® ) or by the product name Monel ® Nickel-copper alloys are available for sale. Alternatively, containers, pipes, or reactors made of less corrosion-resistant metals (such as stainless steel or carbon steel) may be lined with fluoropolymers, such as poly(tetrafluoroethylene). In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed and effluent lines, units related to mass transfer, contact vessels (premixers), distillation columns, and valves associated with reactors, heat exchangers, containers, columns, and units used in the methods of the various embodiments disclosed herein shall be constructed of corrosion-resistant materials.

[0127] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, condition A or B satisfies any of the following conditions: 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).

[0128] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If included in the claims, protection will not be provided for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claims.

[0129] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect the essential and novel features of the invention protected by the claims, particularly the mode of action of any process in carrying out the invention to achieve the desired result. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0130] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0131] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. The description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0132] Wherever a range of values ​​is given herein, that range is intended to include its endpoints, and all integers and fractions within that range, unless otherwise indicated. When a range is defined, it is not intended to limit the disclosed range to the specific value stated. Furthermore, all ranges described herein are intended to include not only the specific range described, but also any combination of values ​​therein, including the stated minimum and maximum values.

[0133] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. Wherever a numerical range is given herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0134] As used herein, the GC / FID peak area is related to the amount of compound present as a proportion of the total area of ​​all detected peaks. The FID area % can be converted to molar % using the calculated or measured response factor.

[0135] As used herein, the term “substantially free” means the presence of less than about 0.0001% by weight (1 ppm).

[0136] As used herein, in some embodiments, the term “about” may be quantified to mean ±1%, ±2%, ±3% up to and including ±10% of the stated value, and all integers and fractions therebetween.

[0137] Compound Table

[0138] As an example, the following compounds are mentioned:

[0139]

[0140]

[0141]

[0142] Some of the compounds identified in Table 1 that are present in the compositions of the present invention can exist as different configurational isomers or stereoisomers. The present invention is intended to include all isomers of a single configuration, a single stereoisomer, or any combination or mixture thereof. For example, 1,2-difluoroethylene (HFO-1132) is intended to represent any combination or mixture of the cis isomer (Z), the trans isomer (E), or any ratio of two isomers. Similarly, 1-chloro-1,2-difluoroethylene (HFO-1122a) exists as the Z-isomer, the E-isomer, or any combination or mixture of two isomers in any ratio. Single or multiple isomers of the same compound can be used in any proportion.

[0143] One embodiment disclosed herein relates to an integrated method for preparing E- and Z-isomers of 1,2-difluoroethylene using PCE as a starting material according to the following reaction steps.

[0144] (1): Tetrachloroethylene (PCE) + 3HF + Cl2 → 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) + 3HCl

[0145] (2): CFC-113 + Zn → Chlorotrifluoroethylene (CFO-1113) + ZnCl2

[0146] (3): CFO-1113 + 2H2 → 1,1,2-trifluoroethane (HFC-143) + HCl

[0147] (4): HFC-143→E-1,2-difluoroethylene (HFO-E-1132)+Z-1,2-difluoroethylene (HFO-Z-1132)+HF

[0148] Another embodiment disclosed herein relates to an integrated method comprising reaction steps (1), (2), (3), (4) and

[0149] (5):HFO-Z-1132→HFO-E-1132

[0150] One embodiment disclosed herein relates to a method for converting a mixture comprising tetrachloroethylene (PCE), hydrogen fluoride, and chlorine into a mixture comprising CFC-113 in the liquid phase at a temperature of 80°C to 120°C in the presence of a metal halide catalyst.

[0151] In some embodiments involving the liquid-phase chlorofluorination of PCE using metal halides, the metal halide catalyst includes, but is not limited to, SbCl5, SbCl3, SbF5, SnCl4, TiCl4, FeCl3, TaCl5, and combinations of two or more thereof. The conversion 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 is carried out at a temperature of about 80°C to about 120°C (including, but not limited to, 80°C, 90°C, 100°C, 110°C, or 120°C, and all values ​​and ranges from 80°C to about 120°C).

[0152] Another embodiment disclosed herein relates to a method for catalytically converting a mixture containing tetrachloroethylene (PCE), hydrogen fluoride, and chlorine into a mixture containing CFC-113 in the gas phase at a temperature of 250°C to 400°C.

[0153] In some embodiments involving PCE gas-phase conversion, the catalyst comprises 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 mol% to 10 mol% of a transition metal selected from Mn, Fe, Co, Ni, Zn, Pd, and Ag. The catalyst can be prepared by co-precipitating 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.

[0154] In some embodiments disclosed herein, the gas-phase catalytic conversion of the PCE is carried out at temperatures from 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 from 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).

[0155] In some embodiments disclosed herein, the PCE to be converted to 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) comprises >99% PCE and one or more compounds selected from CCl4, CHCl3, trichloroethylene, trichlorobromomethane, dichloroethylene bromide isomer, trichlorobromoethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane, wherein the total amount of other compounds is less than 1% by weight of the total composition.

[0156] In some embodiments disclosed herein, the conversion of tetrachloroethylene (PCE) yields a composition comprising 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and one or more additional compounds comprising 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 1,1,1,2-tetrachloro-2,2-difluoroethane (CFC-1... 12a), 1,1,2,2-tetrachloro-1,2-difluoroethane (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).

[0157] In some disclosed embodiments, a CFC-113 feed 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, trichlorofluoroethylene (CFO-1113) is prepared by contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) or a mixture of first products with a reducing metal in the liquid phase. CFC-113 has a liquid phase conversion rate of 50%-100% and a selectivity of more than 90% for CFO-1113.

[0158] In some 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, optionally in the presence of a solvent selected from polar aprotic solvents (such as dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone) or ether solvents (such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate).

[0159] In some 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, optionally in the presence of a solvent and a reducing metal selected from magnesium, zinc, or cadmium, wherein the solvent is selected from dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate. Optionally, the reducing metal may be promoted with a metal chloride (such as ZnCl2, MgCl2, or CdCl2). The reducing metal is preferably activated. The activation of the reducing metal can be carried out by washing the reducing metal with an aqueous solution of hydrochloric acid with a concentration of 1M to about 5M, followed by washing with water and acetone and vacuum drying. Other activators suitable for the methods of the present invention include bromine (Br2), iodine (I2), bromoalkane (e.g., bromoethane), iodoalkane (e.g., iodomethane), o-dibromoalkane (e.g., 1,2-dibromoethane), o-diiodoalkane (e.g., 1,2-diiodoethane), or o-dibromochloroalkane (e.g., 1,2-dibromotetrachloroethane). The reducing metal can be generated by the reaction of a metal chloride with an alkali metal (such as sodium or potassium), as generally described by RD Rieke in Topics in Current Chemistry, Vol. 59, pp. 1-31 (1975).

[0160] In some embodiments disclosed herein, the amount of CFO-1113 is >99% by weight and includes one or more compounds selected from the group consisting of CFO-1112, CFO-1112a, HCFC-123a, HCFC-133, HCFC-133a and HCFC-133b, wherein the total amount of the other compounds is less than 1% by weight of the total composition.

[0161] In one embodiment disclosed herein, the HFC-143 composition generated 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, wherein the total amount of the other compounds is less than 1% by weight of the total composition.

[0162] In some embodiments disclosed herein, the reaction (4) involving the defluorination of HFC-143 is carried out in the gas phase or liquid phase.

[0163] In some embodiments disclosed herein, reaction (4) is carried out in the gas phase.

[0164] In some embodiments disclosed herein, reaction (4) is carried out in the liquid phase.

[0165] In some embodiments disclosed herein, reaction (4) is carried out at temperatures ranging from 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). The temperature ranges from 370°C, 380°C, 390°C, or 400°C, and from 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, are carried out in the gas phase.

[0166] In some embodiments disclosed herein, 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 all ranges from -20°C to 150°C).

[0167] In some embodiments disclosed herein, reaction (4) is carried out at temperatures ranging from 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. The reaction is carried out in the gas phase in the presence of a catalyst selected from the group consisting of: aluminum fluoride, aluminum oxide fluoride, a metal supported on a trivalent aluminum compound containing a fluoride anion (e.g., aluminum fluoride and / or aluminum oxide fluoride), lanthanum fluoride, lanthanum oxide fluoride, a metal supported on a trivalent lanthanum compound containing a fluoride anion (e.g., lanthanum fluoride and / or lanthanum oxide fluoride), 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.

[0168] Some embodiments disclosed herein involve reaction (4), which 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 optional phase-transfer catalyst.

[0169] Some embodiments disclosed herein relate to reaction (4), wherein the starting material comprises an HFC-143 composition containing at least two 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.

[0170] Some embodiments disclosed herein relate to reaction (4), wherein the starting material comprises an HFC-143 composition containing at least two 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-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 includes one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide, and the polar solvent includes one or more of water, dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, formamide, N,N-dimethylacetamide, N-methylpyrrolidone, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate.

[0171] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase at temperatures 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 all ranges from -20°C to 150°C), in the presence of a strong base, a polar solvent, and optionally a phase-transfer catalyst comprising materials 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, aryl, or aralkyl. 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.

[0172] Some embodiments disclosed herein involve reaction (4), which is 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, with or without a catalyst.

[0173] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase in the presence of a strong base in the presence of a strong base in an aprotic solvent, with or without a catalyst, at a temperature 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 ranges thereof) at a temperature from -20°C to 100°C.

[0174] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase at a temperature 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 ranges thereof), 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.

[0175] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase at temperatures 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 ranges thereof), in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of an aprotic solvent containing acyclic or cyclic ethers.

[0176] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase at a temperature 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 ranges thereof), in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of a non-protic solvent containing acyclic or cyclic ethers, with or without a catalyst.

[0177] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase at a temperature 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 ranges thereof), in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of a non-protic solvent containing acyclic or cyclic ethers, with or without a catalyst containing crown ethers or crypt ethers.

[0178] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase at a temperature 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), in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of a non-protic solvent containing acyclic or cyclic ethers, with or without a catalyst containing crown ethers or crypt ethers, 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).

[0179] Some embodiments disclosed herein involve reaction (4), which is carried out at temperatures 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 ranges thereof), in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of a non-protic solvent containing acyclic or cyclic ethers, in the presence of... The process is carried out in the liquid phase, with or without a catalyst containing crown ethers or crypt ethers, wherein the alkali metal or alkaline earth metal alkoxide includes 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 includes lithium hydride, sodium hydride, potassium hydride, or calcium hydride; the organometallic lithium compound includes n-butyllithium, methyllithium, or isopropyllithium; and the alkali metal or alkaline earth metal amide includes lithium dimethylamino, lithium diethylamino, lithium diisopropylamino, or bis(diisopropylamino)magnesium.

[0180] Some embodiments disclosed herein involve reaction (4), which is carried out at temperatures 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 ranges thereof), in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of a non-protic solvent containing acyclic or cyclic ethers, in the presence of... The process is carried out in the liquid phase, with or without a catalyst containing crown ethers or crypt ethers, wherein the alkali metal or alkaline earth metal alkoxide includes one of lithium methoxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, sodium isopropoxide, and magnesium ethoxide; the alkali metal or alkaline earth metal hydride includes lithium hydride, sodium hydride, potassium hydride, or calcium hydride; the organometallic lithium compound includes n-butyllithium, methyllithium, or isopropyllithium; and the alkali metal or alkaline earth metal amide includes lithium dimethylamino, lithium diethylamino, lithium diisopropylamino, or bis(diisopropylamino)magnesium.

[0181] Some embodiments disclosed herein relate to reaction (4), which is carried out in the liquid phase at a temperature 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 ranges thereof), in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of a non-protic solvent containing acyclic or cyclic ethers, with or without a catalyst, and the non-protic solvent includes one of diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, or dioxane.

[0182] Some embodiments disclosed herein involve reaction (4), which is carried out in the liquid phase at a temperature of -20°C to 100°C (or all ranges therebetween), in the presence of alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides, in the presence of an aprotic solvent containing acyclic or cyclic ethers, with or without a catalyst, and the aprotic solvent includes diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. The catalyst comprises one of dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, or dioxane, and the crown ether or crypt ether comprises one of 1,4,7,10,13-pentacyclopentadecane (15-crown-5) and 1,4,7,10,13,16-hexacyclooctadecane (18-crown-6), and the crypt ether comprises 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-(8.8.8)hexacosane (also known as 2,2,2-crypt ether).

[0183] In certain embodiments disclosed herein, the defluorination of hydrogen fluoride from HFC-143, present in an amount of at least 99% by weight, and from at least two or more compounds, is carried out in the gas phase at a temperature of 150°C to 400°C in the presence of a catalyst, wherein the at least two or more compounds are 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, and HCFO-Z-1131. HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113, wherein the total amount of other compounds is less than 1% by weight of the total composition, and the catalyst is selected from the group consisting of: aluminum fluoride, aluminum oxide fluoride, metal supported on a trivalent aluminum compound containing a fluoride anion (e.g., aluminum fluoride and / or aluminum oxide fluoride), lanthanum fluoride, lanthanum oxide fluoride, metal supported on a trivalent lanthanum compound containing a fluoride anion (e.g., lanthanum fluoride and / or lanthanum oxide fluoride), and trivalent chromium compound (e.g., Cr2O3), wherein the metal is selected from one or more of the group consisting of: chromium, manganese, iron, cobalt, nickel, magnesium, and zinc.

[0184] In some embodiments disclosed herein, HFC-143 and HFC-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- The transformation of at least two of the compounds in 113 in the liquid phase is carried out at a temperature from -20°C to 150°C, in the presence of a strong base, in a polar solvent, and optionally in the presence of a phase-transfer catalyst 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, aryl, 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.

[0185] In some embodiments disclosed herein, a composition is used to convert HFC-143 in a liquid phase, the composition comprising HFC-143 and (1) at least two of a compound 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, HFO-1141, HCFC-133b, HCFC-133, HCFO-Z-1131, HCFO-E-1131, HCFC-151a, HCC-160, and CFC-113, or (2) at least two or more of a compound selected from the group consisting of: HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1132, HCFC-151a, HCC-160, and CFC-113, or (2) at least two or more of a compound selected from the group consisting of: HFO-1123, HFC-134a, HFC-152a, HFC-236fa, HFO-Z-1132, HFO-E-1131, HCFC-151a, HCC-160, and CFC-113, or (2) a compound selected from the group consisting of: HFO-1123, HFC-134a, HFC-152a, HFC-151 ... : 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-1,2-Difluoroethylene (HCFO-1122a), fluoroethylene (HFO-1141), dichlorofluoromethane (HCFC-21), dichlorofluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene and acetylene, or (3) at least two of the following compounds: HFC-1123, CFO-1113, HFC-134, HFC-134a, HFCO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a and HCO-1140, wherein the conversion is carried out under anhydrous conditions at a temperature of 20°C to 100°C in a strong base (such as alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal hydrides, organometallic lithium compounds, or alkali metal or alkaline earth metal amides). The reaction is carried out in the presence of an aprotic solvent selected from ethers (e.g., diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether) or cyclic ethers (e.g., tetrahydrofuran, dioxane), 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), and wherein the alkali metal or alkaline earth metal alkoxide includes 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 includes lithium hydride, sodium hydride, potassium hydride, or calcium hydride; the organometallic lithium compound includes n-butyllithium, methyllithium, or isopropyllithium; and the alkali metal or alkaline earth metal amide includes lithium dimethylamino, lithium diethylamino, lithium diisopropylamino, or bis(diisopropylamino)magnesium. The reaction with a strong base can be carried out with or without a catalyst (such as crown ethers or cryptanes). Specific examples of crown ethers include 1,4,7,10,13-pentaoxetane (15-crown-5) and 1,4,7,10,13,16-hexaoxetane (18-crown-6). A known example of a cryptether is 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-(8.8.8)hexacosane (also known as 2,2,2-cryptether).

[0186] Some embodiments disclosed herein relate to a composition comprising HFC-143 and one or more compounds, substantially consisting of, or consisting of, those compounds selected from 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 (HFC-152), fluoroethane (HFC-161), 1,2-dichloro-1-fluoroethane (HFC-161), etc. 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 (HFO-1141), dichlorofluoromethane (HCFC-21), dichlorofluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene.

[0187] Some embodiments disclosed herein relate to an HFC-143 feed composition comprising, substantially comprising, or comprising of, HFC-143 and one or more compounds selected from 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 (HFO-1141), dichlorofluoromethane (HCFC-21), dichlorofluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene.

[0188] Some embodiments disclosed herein relate to a composition comprising HFC-143 and two or more compounds, substantially consisting of, or consisting of, those compounds selected from 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), and 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 (HFO-1141), dichlorofluoromethane (HCFC-21), dichlorofluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene.

[0189] Some embodiments disclosed herein relate to an HFC-143 feed composition comprising HFC-143 and two or more compounds, substantially consisting of, or consisting of, them selected from 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 (HFO-1141), dichlorofluoromethane (HCFC-21), dichlorofluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene, and acetylene.

[0190] Some embodiments disclosed herein relate to a method 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).

[0191] Some embodiments disclosed herein relate to a method 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 ratio of hydrogen to CFC-113 is about 1:1 to about 3:1.

[0192] Some embodiments disclosed herein relate to a method 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.

[0193] Some embodiments disclosed herein relate to a method comprising contacting CFC-113 with hydrogen in the gas phase in the presence of a catalyst comprising a catalytic metal selected from Pd, Pt, or mixtures thereof, preferably supported on Al2O3, fluorinated alumina, AlF3, or chromium oxide, as disclosed in U.S. Patent Applications 20080207962 and 20080207963.

[0194] Some embodiments disclosed herein relate to a method 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 the catalytic metal on the support is from about 0.5% to about 10% by weight of the catalyst composition.

[0195] In some embodiments, in step (5), the content of HFO-E-1132 in the mixture of HFO-Z-1132 and HFO-E-1132 is increased by isomerization in the presence or absence of a catalyst. In some embodiments disclosed herein, the isomerization is carried out at a temperature of 600°C to 800°C (from one of 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C to 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, to... And all values ​​and ranges therein, including 600℃ to 690℃, 610℃ to 690℃, 600℃ to 680℃, 600℃ to 670℃, 600℃ to 660℃, 700℃ to 800℃, 710℃ to 790℃ or 800℃, 720℃ to 780℃, 790℃ or 800℃, or 730℃ to 750℃, 760℃, 770℃, 780℃, 790℃ or 800℃.

[0196] In some embodiments disclosed herein, isomerization is performed at temperatures ranging from 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).

[0197] In some embodiments disclosed herein, in step (5), the molar ratio of HFO-E-1132 to HFO-Z-1132 is increased 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, chromium supported on alumina, fluorinated alumina, or AlF3, or chromium oxide substituted with cobalt or nickel.

[0198] Some embodiments disclosed herein relate to a composition comprising, substantially comprising, or comprising: (i) HFO-E-1132, and 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, At least one of HCFO-1122 and HCO-1140, or (ii) HFO-Z-1132, and at least one of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-Z-1131, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122 and HCO-1140.

[0199] Some embodiments disclosed herein relate to a composition comprising, substantially comprising, or comprising: (i) HFO-E-1132, and 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, At least two of HCFO-1122 and HCO-1140, or (ii) HFO-Z-1132, and at least two of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-Z-1131, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122 and HCO-1140.

[0200] Some embodiments disclosed herein relate to a composition comprising, substantially comprising, or comprising: (i) HFO-E-1132, and 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, At least three of HCFO-1122 and HCO-1140, or (ii) HFO-Z-1132, and at least three of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-Z-1131, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122 and HCO-1140.

[0201] Some embodiments disclosed herein relate to a composition comprising, substantially comprising, or comprising: (i) HFO-E-1132, and HFO-1141, HFO-1123, acetylene, HFO-Z-1132, HCFO-E-1131, HFC-125, HFC-32, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-112 2 and four or more of HCO-1140, or (ii) HFO-Z-1132, and four or more of HFO-1141, HFO-1123, acetylene, HFC-134, HFO-E-1132, HCFO-E-1131, HCFO-Z-1131, HCFO-1131a, HCFO-Z-1122a, HCFO-E-1122a, HCFO-1122 and HCO-1140.

[0202] Example

[0203] Example 1 - Preparation of 98% Chromium / 2% Palladium Catalyst

[0204] A solution of 760.28 g Cr(NO3)3[9(H2O)] (1.90 mol) and 10.1 g Pd(NO3)2[2(H2O)] (0.038 mol) was prepared in 2000 mL of deionized water. The pH of the solution was adjusted to 8.5 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 powder and calcined in air at 400 °C for 24 hours. The calcined powder was pressed into discs, crushed, and sieved to provide a 10 to +20 mesh (1.68 mm to 0.84 mm) fraction for catalyst evaluation.

[0205] Preparation of 97% Chromium / 3% Iron Catalyst

[0206] A beaker containing 500 mL of 2M Cr(NO3)3[9(H2O)] (1.00 mol) aqueous solution was treated with a solution of 7.64 g 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 7.4M 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 powder and calcined in air at 400 °C for 24 hours. The calcined powder was pressed into discs, crushed, and sieved to provide a -12 to +20 mesh (1.68 mm to 0.84 mm) fraction for catalyst evaluation.

[0207] Preparation of 98% Chromium / 2% Silver Catalyst

[0208] A solution of 784.30 g Cr(NO3)3[9(H2O)] (1.96 mol) and 6.79 g AgNO3 (0.04 mol) was prepared in 2000 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 h. The dried solid was pulverized into powder and calcined in air at 900 °C for 24 h. The calcined powder was pressed into discs, crushed, and sieved to provide a -12 to +20 mesh (1.68 mm to 0.84 mm) fraction for catalyst evaluation.

[0209] Chlorofluorination of Tetrachloroethylene over Cr / Ag (98 / 2)

[0210] Granular Cr / Ag (98 / 2) catalyst (15 mL, 31.64 g) was placed in an Inconel container with a diameter of 5 / 8 inch (1.58 cm) heated in a fluidized sand bath. ™ In a nickel alloy reactor tube. Under a nitrogen flow rate of 50 cc / min; 8.3(10) -7 m 3 The tube was heated from 67°C to 174°C over approximately 0.5 hours at a rate of 50 cc / min. Then, HF was introduced into the reactor at a flow rate of 50 cc / min (8.3(10)). -7 m 3 / sec). After about 10 minutes, the nitrogen flow rate was reduced to 20 cc / min (3.3(10)). -7 m 3 / sec), and the HF flow rate increased to 80cc / min (1.3(10)). -6 m 3 / sec); maintain this flow rate for approximately 0.5 hours. Then gradually increase the reactor temperature to 400°C over 3 hours. Reduce the nitrogen flow rate to 10 cc / min (1.7(10)). -7 m 3 / sec), and continued fluorination at 400°C for 2 hours. At the end of this period, the HF flow was stopped, and the reactor was kept at 20 sccm (3.3(10)). -7 m 3Cooled under a nitrogen stream ( / sec). Then, at temperatures ranging from 325°C to 400°C, a mixture of HF, C2Cl4, and Cl2 was passed through the catalyst in various ratios. At 350°C, with an HF / C2Cl4 / Cl2 ratio of 5 / 1 / 1 and a contact time of 15 seconds, the reactor effluent consisted primarily of CCl3CClF2 (56.6%) and CClF2CCl2F (37.2%) (along with minor 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 was 100%.

[0211] Chlorofluorination of Tetrachloroethylene over Cr / Fe (97 / 3)

[0212] Granular Cr / Fe (97 / 3) catalyst (20 mL, 28.8 g) was placed in an Inconel container with a diameter of 5 / 8 inch (1.58 cm) heated in a fluidized sand bath. ™ In a nickel alloy reactor tube. Under a nitrogen flow rate of 50 cc / min; 8.3(10) -7 m 3 The tube was heated from 67°C to 176°C and held overnight at 8.3 cc / min. Then HF was applied at 50 cc / min (8.3 (10)). -7 m 3 The feed was introduced into the reactor at a flow rate of 1.3 cc / min for approximately 45 minutes. Then, as the temperature increased from 175°C to 402°C over approximately 5.5 hours, the HF flow rate was increased to 80 cc / min (1.3 cc / min). -6 m 3 / sec), and the nitrogen flow rate was reduced to 20cc / min (3.3(10)). -7 m 3 / sec). Stop the HF flow and keep the reactor at 20 sccm (3.3(10)). -7 m 3Cooled under a nitrogen flow of ( / sec). Then, a mixture of HF, C2Cl4, and Cl2 was passed through the catalyst at various ratios at temperatures ranging from 250°C to 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 consisted mainly of C2Cl4F2 isomers (4.9%), CClF2CCl2F (81.5%), CClF2CClF2 (7.2%), and CF3CCl2F (4.6%), along with trace 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 was 100%.

[0213] Chlorofluorination of PCE

[0214] Gas phase: Inconel was filled with 12 cc (6.45 g) of 15% carbon-supported chromium chloride catalyst. ® Tube (OD 0.5 inch, length 15 inches, wall thickness 0.34). The catalyst was activated with anhydrous HF at 300°C. The reactor was heated to 300°C in a Lindberg furnace and fed tetrachloroethylene and one or more additional compounds selected from chloroform, carbon tetrachloride, trichlorobromomethane, trichlorobromoethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3-trichloro-1-propene, and 1,1,1,3-tetrachloropropane at 4 ml / h, with HF gas fed at 22.2 sccm (standard cubic centimeters / min) and Cl2 gas fed at 5.4 sccm, controlled by a vaporizer at 150°C. All experiments were conducted at 1–2 psig. Agilent was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® A CBK-D / 60 / 80 6m × 2mm ID1 / 8'' OD packed column was used, purged with helium at 30 sccm, for online analysis of the reactor effluent. The reaction exhibited 55% conversion and 90% I13 selectivity.

[0215] In one embodiment, the chlorofluorination of PCE produces a CFC-113 composition, which, after purification, comprises about 99% by weight of CFC-113 based on the total amount of the composition, 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, wherein the total amount of the additional compounds is less than 1% by weight of the total composition.

[0216] Liquid phase: SbCl5 (10.5 g) was added to a 210 mL Hastelloy C reactor, followed by HF (49 g) and Cl2 (42 g). The reaction mixture was heated at 100 °C for 1 hour and then cooled to 0 °C. Tetrachloroethylene (19 g) and one or more additional compounds selected from chloroform, carbon tetrachloride, trichlorobromomethane, trichlorobromoethylene, 1,2-dichloroethane, ethylene, trichloroethylene, 1,1,3-trichloro-1-propene, and 1,1,1,3-tetrachloropropane were added to the reactor, and the reaction mixture was heated to 100 °C. The reaction rate was indicated by pressure increase and pressure stabilization (indicating completion of the reaction). Similar reactions were also carried out using TaCl5 or NbCl5 as catalysts. The reaction achieved 100% conversion and 95% selectivity.

[0217] Step 2: CFC-113 + Zn → CFO-1113 + ZnCl2

[0218] Dechlorination of CFC-113

[0219] A 500 mL three-necked round-bottom flask was equipped with a large stir bar, thermocouple sheath, feeding funnel, and condenser connected in series with two traps placed in a dry ice / acetone bath, followed by a nitrogen bubbler. Each trap contained 100 mg of d-limonene as a polymerization inhibitor. Magnesium powder (9.0 g, 0.37 mol) and tetrahydrofuran (222.2 g) were 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) was added to the feeding funnel. The 1,1,2-trichloro-1,2,2-trifluoroethane was first added dropwise to the magnesium / THF mixture at room temperature. As the temperature increased, the exothermic reaction was controlled to 40-50°C using an ice-water bath. The volatile reaction products were collected in a gas cylinder. Gas chromatography analysis of the products showed that they consisted of trichlorofluoroethylene. Other low-content impurities are 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-difluoroethylene. In one embodiment, the isolated chlorotrifluoroethylene (CFO-1113) comprises 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-difluoroethylene.

[0220] Hydrodechlorination of CFC-113

[0221] 15 mL (19 g) of granulated Cr / Pd (98 / 2) catalyst was placed in an Inconel container with a diameter of 5 / 8'' (1.58 cm) heated in a fluidized sand bath. ™In a nickel alloy reactor tube, the catalyst was dried under a nitrogen flow (20 cc / min) over a 1.5-hour process, as the temperature increased from 34 °C to 150 °C. The nitrogen flow was then replaced with hydrogen (20 cc). The catalyst was reduced at 150 °C for 3 hours and then at 200 °C for 3 hours. The performance of the catalyst for the hydrodechlorination of CFC-113 was then tested at various ratios of H2 to CClF2CCl2F from 87 °C to 156 °C. At an H2 / CClF2CCl2F ratio of 2:1, a reaction temperature of 95 °C, and a contact time of 15 seconds, the reactor effluent consisted mainly of CHF2CH2F (84.5%) and CClF2CH2F (6.8%), with trace amounts of C2H6 (0.2%), CH3CF3 (0.2%), CH2FCF3 (0.2%), and CH3CHF2 (0.5%), as determined by GC-MS. The conversion rate was 100%.

[0222] Step 3: CFO-1113 + H2→ HFC-143 + HCl

[0223] A Hastelloy tubular reactor (80'' length, OD (outer diameter) 1'', wall thickness 0.074'') was packed with 30 g of 0.5% carbon-supported Pd catalyst. The catalyst was conditioned at 200 °C for one hour with a nitrogen (1000 sccm) and a hydrogen (1000 sccm) stream. A mixture of CFO-1113, hydrogen, and N2 was then introduced into the reactor at a back pressure of 10 psig. The reaction was operated at 50% conversion with 90% HFC-143 selectivity.

[0224] In one embodiment, the contact of trichlorotrifluoroethylene (CFO-1113) with hydrogen is carried out under one of the following conditions: (i) at a temperature of about 50°C to 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), in the presence of a hydrogenation catalyst comprising a catalytic metal selected from the group consisting of Re, N i. Pd, Pt, Ru, Rh and Ir, or (ii) at temperatures from 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, 350°C).

[0225] Step 4: HFC-143 → HFO-Z-1132 + HFO-E-1132 + HF

[0226] Gas Phase :

[0227] Inconel was filled with 2cc of chromium oxide catalyst. ® Tube (OD 0.5 inch, length 10 inches, wall thickness 0.35). The reactor is heated to 375°C, optionally with oxygen-containing gas. The HFC-143 generated in step (3) comprises HFC-143 and at least one or more compounds selected from (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, HCF O-E-1131, HCFC-151a, HCC-160, and CFC-113, or (ii) at least one or more compounds selected from 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), vinyl fluoride (HFO-1141), dichlorofluoromethane (HCFC-21), dichlorodifluoromethane (HCFC- 22) trifluoromethane (HFC-23), ethylene, and acetylene, or (iii) at least one or more compounds selected from HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a, and HCO-1140, fed via an ISCO pump at 4.23 mL / hr through a vaporizer controlled at 20 °C. The reaction pressure varied between 0 psig and 50 psig. Agilent was used. ® The reactor effluent was analyzed online using a 7890 GC / 5971 MS. The HFC-143 conversion was 53%, with 90% selectivity for HFO-1132. The molar ratio of Z-1132 to E-1132 was approximately 4:1.

[0228] Liquid Phase :

[0229] HFC-143 (84 g, 1 mol) and (i) one or more 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-11 31. HCFC-151a, HCC-160 and CFC-113, 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-di... 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), vinyl fluoride (HFO-1141), dichlorofluoromethane (HCFC-21), dichlorofluoromethane (HCFC-22), trifluoromethane (HFC-23), ethylene A mixture of alkene and acetylene, or (iii) at least two compounds selected from the following: HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a and HCO-1140, and a solution of t-BuOK (80 g, 1 mmol) in anhydrous DMF (200 mL) was stirred in a 400 mL autoclave at 0 °C. The reaction was monitored by gas chromatography. After 3 hours, the product was collected in a dry ice trap connected to the autoclave. The formation of HFO-1132 had about 70% HFC-143 conversion and 96% selectivity. The molar ratio of HFO-Z-1132 to HFO-E-1132 was about 9:1.

[0230] Step 5: HFO-Z-1132 → HFO-E-1132

[0231] In some embodiments, the content of HFO-E-1132 in the mixture of HFO-Z-1132 and HFO-E-1132 is increased in step (5) by isomerization with or without a catalyst. In the absence of a catalyst, isomerization is carried out at a temperature of 600°C to 800°C (and all values ​​and ranges therebetween).

[0232] In some 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, chromium supported on alumina, fluorinated alumina or AlF3, or cobalt or nickel-substituted chromium oxide.

[0233] In some embodiments, the content of HFO-Z-1132 in HFO-E / Z- can be increased by isomerizing HFO-E-1132 in the gas phase with or without a catalyst.

[0234] The E to Z molar ratio of a mixture of HFO-Z-1132 and HFO-E-1132 was increased by thermal isomerization at 600°C to 800°C for a contact time of approximately 0.1 to 60 seconds.

[0235] Some embodiments disclosed herein relate to a system and method comprising a series of reactors including a first reactor, a second reactor, and a third reactor respectively configured for synthesizing a first CFC-113 intermediate mixture, a second CFO-1113 intermediate mixture, and a third HFC-143 intermediate mixture; and a fourth reactor configured for synthesizing a mixture of HFO-E-1132 and HFO-Z-1132 isomers. The system further includes a conversion system in fluid communication with the fourth reactor for altering the HFO-1132 E / Z ratio, wherein the conversion system comprises one of a distillation column, a catalyst-free thermal converter, or a catalytic reactor suitable for altering the HFO-E-1132 to HFO-Z-1132 ratio.

[0236] Some embodiments disclosed herein relate to a method that provides a starting feed and contacts the starting feed with tetrachloroethylene (PCE), HF, and chlorine to synthesize 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feed, wherein the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) as part of a product mixture is contacted with a reducing metal in the liquid phase to form chlorotrifluoroethylene (CFO-1113), wherein the product is... A portion of the mixture of chlorotrifluoroethylene (CFO-1113) is contacted with hydrogen in either the gas or liquid phase to form 1,1,2-trifluoroethane (HFC-143), which is then converted in either the liquid or gas phase as part of the product mixture from step (d) to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0237] Some embodiments disclosed herein relate to a method that provides a starting feed and contacts the starting feed with tetrachloroethylene (PCE), HF, and chlorine to synthesize 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the starting feed. The 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), as part of a product mixture, is contacted with hydrogen in either a gaseous or liquid phase to form 1,1,2-trifluoroethane (HFC-143). The 1,1,2-trifluoroethane (HFC-143), as part of a product mixture from step (d), is then converted in a liquid or gaseous phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0238] Some embodiments disclosed herein relate to a method that further includes steps (a), (b), (c), (d), and (e) in separate and independent reactors.

[0239] Some embodiments disclosed herein relate to a method that further includes purifying one of CFC-113, CFO-113, or HFC-143 from its product mixture prior to the next step.

[0240] A system comprising a refrigerant containment source, a refrigerant circuit including an evaporator, a compressor, a condenser, a charging valve, and a charging line for temporarily connecting the containment source and the charging valve, wherein the containment source comprises a refrigerant comprising at least (E)-1,2-difluoroethylene (HFO-E-1132) and (Z)-1,2-difluoroethylene (HFO-Z-1132).

[0241] A system comprising a refrigerant containment source, a refrigerant circuit including an evaporator, a compressor, a condenser, a charging valve, and a charging line for temporarily connecting the containment source and the charging valve, wherein the containment source comprises a refrigerant comprising at least (E)-1,2-difluoroethylene (HFO-E-1132) and (Z)-1,2-difluoroethylene (HFO-Z-1132), wherein the system is part of a heat transfer system selected from refrigeration systems, refrigerators, air conditioning systems, heat pumps, coolers, and portable air conditioning systems.

[0242] CLAIM EMBODIMENTS

[0243] Implementation Scheme 1. A method, the method comprising:

[0244] (a) Tetrachloroethylene (PCE) is contacted with HF and chlorine to form 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113).

[0245] (b) 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is brought into contact with a reducing metal in the liquid phase to form chlorotrifluoroethylene (CFO-1113).

[0246] (c) Contacting trichlorotrifluoroethylene (CFO-1113) with hydrogen in either the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143), and

[0247] (d) Converting 1,1,2-trifluoroethane (HFC-143) in the liquid phase or the gas phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0248] Implementation Scheme 2. The method according to Implementation Scheme 1, the method further comprising (e) 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).

[0249] Implementation Scheme 3. The method according to Implementation Scheme 1, wherein (a), (b) and (c) are part of an integrated method, and each reaction is carried out in a separate and independent reactor.

[0250] Implementation Scheme 4. The method according to Implementation Scheme 1, wherein (a), (b), (c) and (d) are part of an integrated method, and each reaction is carried out in a separate and independent reactor.

[0251] Implementation Scheme 5. The method according to Implementation Scheme 2, wherein (a), (b), (c), (d) and (e) are part of an integrated method, and each reaction is carried out in a separate and independent reactor.

[0252] Implementation Scheme 6. The method according to any one of Implementation Scheme 1 or 2, wherein (a) includes chlorofluorination, (b) includes dechlorination, (c) includes hydrogenation, and (d) includes dehydrofluorination.

[0253] Implementation Scheme 7. The method according to Implementation Scheme 6, wherein the chlorofluorination of PCE produces a first product mixture, wherein the dechlorination of CFC-113 produces a second product mixture, wherein the hydrogenation of CFO-1113 produces a third product mixture, and wherein the dehydrofluorination of HFC-143 produces a fourth product mixture.

[0254] Implementation Scheme 8. The method according to any one of Implementation Scheme 1 or 2, wherein the PCE conversion is carried out in the presence of hydrogen fluoride and chlorine in one of: (1) the liquid phase catalyzed by a metal halide catalyst at a temperature of 80°C to 120°C, or (2) the gas phase in the presence of a chromium-based fluorination catalyst at a temperature of 250°C to 400°C.

[0255] Implementation Scheme 9. The method according to any one of Implementation Scheme 1 or 2, wherein the PCE is a feed composition comprising >99% by weight of PCE based on the total amount of the composition, and one or more additional compounds selected from the group consisting of: 1,1,1-trichloroethane, carbon tetrachloride, dichloromethane, and trichloroethylene.

[0256] Implementation Scheme 10. The method according to Implementation Scheme 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 feed composition.

[0257] Implementation Scheme 11. The method according to any one of Implementation Scheme 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.

[0258] Implementation Scheme 12. The method according to Implementation Scheme 11, wherein the amount of CFC-113 in the first product mixture is >95% by weight based on the total weight of the composition.

[0259] Implementation Scheme 13. The method according to Implementation Scheme 12, wherein the amount of the additional compound in the first product composition is greater than 0% by weight and less than 1% by weight, based on the total amount of the first product composition.

[0260] Implementation Scheme 14. The method according to Implementation Scheme 11, wherein the 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) comprises a portion of the first product mixture.

[0261] Implementation Scheme 15. The method according to 14, wherein the first product mixture is used to prepare the second product mixture.

[0262] Implementation Scheme 16. The method according to any one of Implementation Scheme 1 or 2, wherein the reducing metal comprises zinc, magnesium or cadmium in the solvent of the liquid phase.

[0263] Implementation Scheme 17. The method according to any one of Implementation Scheme 1 or 2, wherein the solvent comprises a polar aprotic solvent.

[0264] Implementation Scheme 18. The method according to 15, wherein contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with the reducing metal in the liquid phase is carried out at a temperature of about 20°C to about 120°C.

[0265] Implementation Scheme 19. The method according to any one of Implementation Scheme 1 or 2, wherein the contact of chlorotrifluoroethylene (CFO-1113) with hydrogen is carried out under one of the following conditions: (i) at a temperature of about 50°C to about 150°C, and 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 about 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.

[0266] Implementation Scheme 20. The method according to any one of Implementation Scheme 1 or 2, wherein the contact of trichlorofluoroethylene (CFO-1113) with hydrogen is carried out in the presence of a hydrogenation catalyst selected from the group consisting of Pd and Pt.

[0267] Implementation Scheme 21. The method according to Implementation Scheme 11, wherein the hydrogenation of chlorotrifluoroethylene (CFO-1113) produces the third product mixture, the third product mixture mainly comprising 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.

[0268] Implementation Scheme 22. According to the method of Implementation Scheme 11, wherein the third product mixture is converted in the gas phase or the liquid phase into a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0269] Implementation Scheme 23. The method according to Implementation Scheme 20, wherein the conversion is carried out in the gas phase at a temperature of 150°C to 400°C.

[0270] Implementation Scheme 24. The method according to Implementation Scheme 20, wherein the conversion is carried out in the liquid phase at a temperature of -20°C to 150°C.

[0271] Implementation Scheme 25. A composition comprising one of the following:

[0272] (a) Tetrachloroethylene (PCE) and at least one additional compound, said at least one additional compound being selected from the group consisting of: CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene or 1,1,1,3-tetrachloropropane;

[0273] (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;

[0274] (c) Chlorotrifluoroethylene (CFO-1113) and at least one additional compound, said at least one additional compound being selected from the group consisting of: HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b and CFC-113;

[0275] (d) 1,1,2-trifluoroethane (HFC-143) and at least one additional compound selected from the group consisting of: HFO-1123, CFO-1113, HFC-134, HFC-134a, HCFO-1131a, HCFC-142, HCFC-142a, HCFO-1122, HCFO-1122a and HCO-1140;

[0276] (e) E-1,2-difluoroethylene (HFO-E-1132) and at least one additional compound, said at least one additional compound being 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

[0277] (f) 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.

[0278] Implementation Scheme 26. A composition comprising at least one of the following:

[0279] (a) HFO-E-1132 and at least one additional compound, said additional compound being selected from the group consisting of: HFO-1141, HCFO-1140, acetylene, and fluoroacetylene, in an amount <500 ppm.

[0280] (b) HFO-Z-1132 and at least one additional compound, said additional compound being selected from the group consisting of: HFO-1141, HCFO-1140, acetylene, and fluoroacetylene, in an amount <500 ppm.

[0281] (c) At least one of HFO-E-1132 and HFO-Z-1132, and at least two additional compounds selected from the group consisting of: 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), vinyl fluoride (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), dichlorofluoromethane (HCFC-22), ethylene (HCO-1150), 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (1140), 1-chloro-1-fluoroethylene (HCFO-E-1131a), E-1-chloro-2-fluoroethylene (HCFO-E-1131), Z-1-chloro-2-fluoroethylene (HCFO-Z-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122).

[0282] Implementation Scheme 27. A composition comprising at least one of HFO-E-1132 and HFO-Z-1132, and at least two additional compounds selected from the group consisting of: 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), and 1,1,2-trifluoroethylene (HFO-1123). Vinyl fluoride (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), dichlorofluoromethane (HFC-22), ethylene, 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a) Vinyl chloride (1140), 1-chloro-1-fluoroethylene (HCFO-E-1131a), E-1-chloro-2-fluoroethylene (HCFO-E-1131), Z-1-chloro-2-fluoroethylene (HCFO-Z-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122), wherein the total amount of HFO-1141, HCFO-1140, acetylene, and fluoroacetylene is selected from one of the following: <2000ppm, <1000ppm, <500ppm, <2000ppm, <1000ppm, <500ppm, 400ppm pm, <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 about 2000ppm, ≥1ppm to less than about 1000ppm, or ≥0ppm and <100ppm, and all values ​​and ranges from about 0.00001ppm to 2000ppm.

[0283] Implementation Scheme 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).

[0284] Implementation Scheme 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).

[0285] Implementation Scheme 30. The composition according to Implementation Scheme 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.

[0286] Implementation Scheme 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.

[0287] Implementation Scheme 32. The composition according to Implementation Scheme 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.

[0288] Implementation Scheme 33. The composition according to Implementation Scheme 31, wherein the total amount of the additional compound is greater than 0% by weight and less than 1% by weight based on the total amount of the composition.

[0289] Implementation Scheme 34. A method comprising blending HFO-E-1132 and / or HFO-Z-1132 formed according to any one of Implementation Scheme 1 or 2 with one or more other compounds selected from the group consisting of:

[0290] (i) one or more HFC compounds, said one or more HFC compounds being selected from the group consisting of: HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea and HFC-1123; and

[0291] (ii) One or more HFO compounds, said one or more HFO compounds being selected from the group consisting of: HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd and HFO-E-1336mzz.

[0292] Implementation Scheme 35. A blend composition comprising HFO-E-1132 and / or HFO-Z-1132, and one or more HFC and / or HFO compounds, said one or more HFC and / or HFO compounds being selected from at least one of the following:

[0293] (i) one or more HFC compounds, said one or more HFC compounds being selected from the group consisting of: HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea and HFC-1123; and

[0294] (ii) One or more HFO compounds, said one or more HFO compounds being selected from the group consisting of: HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd and HFO-E-1336mzz.

[0295] Implementation Scheme 36. A method of using the blend composition according to Implementation Scheme 35 as a refrigerant, solvent, foam expander, detergent, aerosol propellant, dielectric, fire extinguishing agent or power cycle working fluid.

[0296] Implementation Scheme 37. A method, the method comprising:

[0297] (a) Contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with a reducing metal in the liquid phase to dechlorinate the CFC-113 and form chlorotrifluoroethylene (CFO-1113), and

[0298] (b) Contact the CFO-1113 with hydrogen in either the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143).

[0299] Implementation Scheme 38. The method according to Implementation Scheme 38 further includes converting the HFC-143 in the liquid phase or the gas phase to form a mixture of E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0300] Implementation Scheme 39. The method according to Implementation Scheme 38, the method 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.

[0301] Implementation Scheme 40. The method according to Implementation Scheme 37, wherein steps (a) and (b) are carried out in a separate reactor or in one of the same reactors.

[0302] Implementation Scheme 41. The method according to Implementation Scheme 1, the method further includes isomerizing the HFO-E-1132 into HFO-Z-1132.

[0303] Implementation Scheme 42. A method 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).

[0304] Implementation Scheme 43. The method according to Implementation Scheme 42, wherein the relative molar ratio of hydrogen to CFC-113 is about 1:1 to about 3:1.

[0305] Implementation Scheme 44. The method according to Implementation Scheme 42 or 43, wherein the contact is performed at a temperature of about 80°C to about 250°C.

[0306] Implementation Scheme 45. A method comprising contacting PCE with hydrogen in the gas phase in the presence of a catalyst to form an HFC-143 composition.

[0307] Implementation Scheme 46. The method according to Implementation Scheme 45, wherein the PCE is contacted with hydrogen in the gas phase in the presence of a catalyst comprising a catalytic metal selected from the group consisting of Pd, Pt and mixtures thereof, preferably supported on Al2O3, fluorinated alumina, AlF3 or chromium oxide.

[0308] Implementation Scheme 47. The method according to Implementation Scheme 46, wherein the amount of catalytic metal on the support is about 0.5% by weight to about 10% by weight of the catalyst composition.

[0309] Implementation Scheme 48. The method according to Implementation Scheme 1, the method further includes isomerizing the HFO-E-1132 into HFO-Z-1132.

[0310] Implementation Scheme 49. A system comprising:

[0311] A first reactor is configured to synthesize a first mixture comprising 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from a feed 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;

[0312] A second reactor is configured to convert the CFC-113 in the first mixture into a second mixture containing chlorotrifluoroethylene (CFO-1113);

[0313] A third reactor, configured to convert the CFO-1113 of the second mixture into a third mixture containing 1,1,2-trifluoroethane (HFC-143); and

[0314] A fourth reactor is configured to convert the HFC-143 of the third mixture into a fourth mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0315] Implementation Scheme 50. The system according to Implementation Scheme 49, wherein the first reactor, the second reactor, the third reactor and the fourth reactor are in flow communication with each other.

[0316] Implementation Scheme 51. The system according to Implementation Scheme 50, wherein the system is an integrated system comprising the first reactor, the second reactor, the third reactor, and the fourth reactor.

[0317] Implementation Scheme 52. The system according to any one of Implementation Schemes 49 to 51, the system further comprising a conversion system in fluid communication with the fourth reactor, the conversion system being configured to adjust the HFO-1132E / Z ratio of the fourth mixture.

[0318] Implementation Scheme 53. The system according to Implementation Scheme 52, wherein the conversion system is selected from the group consisting of: distillation column, catalyst-free thermal converter and catalytic reactor.

[0319] Implementation Scheme 54. A method, the method comprising:

[0320] (a) Provide an initial feed consisting of tetrachloroethylene (PCE), HF and chlorine.

[0321] (b) Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the said starting feed as part of the first product mixture.

[0322] (c) The CFC-113 is contacted with a reducing metal in the liquid phase to form chlorotrifluoroethylene (CFO-1113) as part of the second product mixture.

[0323] (d) Contacting the CFO-1113 with hydrogen in the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143) as part of a third product mixture, and

[0324] (e) In the liquid phase or the gas phase, the HFC-143 is converted into a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0325] Implementation Scheme 55. The method according to Implementation Scheme 54, wherein, prior to the next step, at least one of CFC-113, CFO-1113 or HFC-143 is first separated from the respective product mixture.

[0326] Implementation Scheme 56. The method according to Implementation Scheme 54 or Implementation Scheme 55, the method 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.

[0327] Implementation Scheme 57. The method according to Implementation Scheme 56, wherein the processing includes distilling the fourth product mixture to form a first stream and a second stream, the first stream comprising the composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the fourth product mixture, and the second stream having an HFO-Z-1132:HFO-E-1132 ratio higher than that of the first stream.

[0328] Implementation Scheme 58. The method according to Implementation Scheme 57, the method further comprising recycling the second feed stream to step (b).

[0329] Implementation Scheme 59. A method, the method comprising:

[0330] (a) Provide an initial feed consisting of tetrachloroethylene (PCE), HF and chlorine.

[0331] (b) Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the said starting feed as part of the first product mixture.

[0332] (c) Contacting the CFC-113 with hydrogen in the gas or liquid phase to form 1,1,2-trifluoroethane (HFC-143) as part of a second product mixture, and

[0333] (d) In the liquid phase or the gas phase, the HFC-143 is converted into a third product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0334] Implementation Scheme 60. The method according to Implementation Scheme 59, wherein, prior to the next step, at least one of CFC-113 or HFC-143 is separated from its respective product mixture.

[0335] Implementation Scheme 61. The method according to Implementation Scheme 59 or Implementation Scheme 60, the method further comprising processing the third product mixture to form a composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the third product mixture.

[0336] Implementation Scheme 62. The method according to Implementation Scheme 61, wherein the processing includes distilling the third product mixture to form a first stream and a second stream, the first stream comprising the composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the third product mixture, and the second stream having an HFO-Z-1132:HFO-E-1132 ratio higher than that of the first stream.

[0337] Implementation Scheme 63. The method according to Implementation Scheme 62, the method further comprising recycling the second feed stream to step (b).

[0338] OTHER EMBODIMENTS

[0339] OE1. A PCE feed mixture comprising one or more additional compounds selected from PCE, CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane.

[0340] 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.

[0341] OE3. A CFC-113 product mixture comprising one or more additional compounds selected from CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123, and PCE.

[0342] OE4. A CFO-1113 product mixture comprising one or more additional compounds selected from HCFC-123a, HCFC-133b, HCFC-133a, HCFC-133, and CFC-113.

[0343] OE5. An HFC-143 feed mixture 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 and HCO-1140.

[0344] OE6. 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.

[0345] OE7. A mixture of HFO-E-1132 and / or HFO-Z-1132 products, said HFO-E-1132 and / or HFO-Z-1132 product mixture comprising HFO-1141, HCO-1140 and acetylene, wherein the amounts of said HFO-1141, said HCO-1140 and said acetylene are selected from one of the following: <2000ppm, <1000ppm, <500ppm, <400ppm, <300ppm, <200ppm, <100ppm. ppm, <50ppm, <10ppm, <5ppm, ≥0.00001ppm to <500ppm, ≥0.0001ppm to <500ppm, ≥0.00001ppm to <100ppm, ≥0.0001ppm to <100ppm, ≥1ppm to less than about 2000ppm, ≥1ppm to less than about 1000ppm, or ≥0ppm and <100ppm, and all values ​​and ranges from about 0.00001ppm to 2000ppm.

[0346] OE8. An HFO-E-1132 (or HFO-Z-1132) product mixture, said HFO-E-1132 (or HFO-Z-1132) product mixture comprising HFO-1141, HCO-1140 and acetylene, said HFO-1141, said HCO-1140 and said acetylene being selected from the following amounts: <100ppm, <50ppm, <10ppm, <5ppm.

[0347] OE9. A mixture of HFO-E-1132 and / or HFO-Z-1132 products, said HFO-E-1132 and / or HFO-Z-1132 product mixture comprising HFO-1141, HCO-1140 and acetylene, said HFO-1141, said HCO-1140 and said acetylene being selected from one of the following: <100ppm, <50ppm, <10ppm or <5ppm.

[0348] OE10. In certain embodiments of the HFO-E-1132 and / or HFO-Z-1132 product mixture, the amounts of vinyl fluoride (HFO-1141), vinyl chloride (HCO-1140), acetylene, and fluoroacetylene are selected from one of the following: <2000ppm, <1000ppm, <500ppm, <2000ppm, <1000ppm, <500ppm, <400ppm, <300ppm, <200ppm, <100ppm, <50ppm, <10ppm, <5ppm, ≥0.00001ppm to <500ppm, ≥0.00001ppm to <500ppm, ≥0.00001ppm to <100ppm, ≥0.0001ppm to <100ppm, or ≥0ppm and <100ppm.

[0349] OE11. An embodiment of a mixture of HFO-E-1132 and / or HFO-Z-1132 products, wherein the total amount of vinyl fluoride (HFO-1141), vinyl chloride (HCO-1140), and acetylene and fluoroacetylene is selected from one of the following: <100ppm, <50ppm, <10ppm, <5ppm, ≥0.00001ppm to <100ppm, ≥0.0001ppm to <100ppm, or ≥0ppm and <100ppm.

[0350] OE12. An embodiment of an HFO-E-1132 and / or HFO-Z-1132 product mixture, wherein the HFO-E-1132 and / or HFO-Z-1132 product mixture embodiment optionally contains at least one of vinyl fluoride (HFO-1141), vinyl chloride (HCO-1140), acetylene, and fluoroacetylene, wherein at least one of vinyl fluoride (HFO-1141), vinyl chloride (HCO-1140), acetylene, and fluoroacetylene... The amount of the product is selected from one of the following: <100ppm, <50ppm, <10ppm, <5ppm, ≥0.00001ppm to <100ppm, ≥0.0001ppm to <100ppm, or ≥0ppm and <100ppm. The HFO-E-1132 and / or HFO-Z-1132 product mixture embodiment is preferably free of at least one of vinyl fluoride (HFO-1141) and vinyl chloride (HCO-1140).

[0351] OE13. A mixture of HFO-E-1132 and / or HFO-Z-1132 products, said HFO-E-1132 and / or HFO-Z-1132 product mixture comprising at least two of 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), vinyl fluoride (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), dichlorofluoromethane (HCFC-22), ethylene (HCO-1150), 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (1140), 1-chloro-1-fluoroethylene (HCFO-1131a), E-1-chloro-2-fluoroethylene (HCFO-E-1131), Z-1-chloro-2-fluoroethylene (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.

[0352] OE14. A method for converting a PCE feed mixture into a CFC-113 product mixture, the PCE feed mixture comprising one or more additional compounds selected from PCE, CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane.

[0353] OE15. A method for converting a PCE product mixture (also a CFC-113 feed) comprising one or more additional compounds selected from CFC-113, CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123 and PCE.

[0354] OE16. A method for converting a CFC-113 mixture into a product mixture comprising CFO-1113, said CFC-113 mixture comprising CFC-113 and one or more additional compounds selected from CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123 and PCE.

[0355] OE17. A method for converting a CFO-1113 mixture into a product mixture containing HFC-143, the CFO-1113 mixture containing one or more additional compounds selected from HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b and CFC-113.

[0356] OE18. A method for converting an HFC-143 mixture into a mixture of HFO-E-1132 and HFO-Z-1132 products, wherein the HFC-143 mixture 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.

[0357] OE19. A method for converting an HFC-143 product mixture into an HFO-E-1132 (or HFO-Z-1132) product mixture, wherein the HFC-143 product mixture 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.

[0358] OE20. A method for converting a PCE feed mixture into a CFC-113 product mixture by chlorofluorination, wherein the PCE feed mixture further comprises one or more additional compounds selected from PCE, CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane.

[0359] OE21. A method for converting CFC-113 in a product mixture further comprising one or more additional compounds into a product mixture comprising CFO-1113 by dechlorination, wherein the one or more additional compounds are selected from CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123 and PCE.

[0360] OE22. A method for converting CFO-1113 in a product mixture further comprising one or more additional compounds into a product mixture comprising HFC-143 by hydrogenation, said one or more additional compounds being selected from HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b and CFC-113.

[0361] OE23. A method for converting HFC-143 in a product mixture, which also contains one or more additional compounds, into a product mixture of HFO-E-1132 and HFO-Z-1132 by dehydrofluorination, wherein the one or more additional compounds are 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.

[0362] OE24. A method for converting a PCE feed mixture into a CFC-113 product mixture by chlorofluorination, the PCE feed mixture further comprising one or more additional compounds selected from PCE, CCl4, CHCl3, trichloroethylene, 1,1,3-trichloropropene, ethylene, and 1,1,1,3-tetrachloropropane, wherein the chlorofluorination is carried out at a temperature selected from 80°C-120°C or 250°C-400°C.

[0363] OE25. A method for converting CFC-113 in a product mixture further comprising one or more additional compounds into a product mixture comprising CFO-1113 by dechlorination, said one or more additional compounds being selected from CFC-113a, CFC-114, CFC-114a, HCFC-124, HCFC-123 and PCE, wherein said CFC-113 is hydrodechlorinated or dechlorinated to CFO-1113.

[0364] OE26. A method for converting CFO-1113 in a product mixture further comprising one or more additional compounds into a product mixture comprising HFC-143 by hydrogenation, said one or more additional compounds being selected from HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b and CFC-113.

[0365] OE27. A method for converting HFC-143 in a product mixture further comprising one or more additional compounds into a product mixture of HFO-E-1132 and HFO-Z-1132 by dehydrofluorination, wherein the one or more additional compounds are 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.

[0366] Any one of OE28, OE7 to OE12, wherein the total amount of the additional compound is greater than 0% by weight and less than 1% by weight based on the total amount of the composition.

[0367] Any one of OE29, OE7 to OE12, wherein the total amount of the additional compound is greater than 0% by weight and less than 0.5% by weight based on the total amount of the composition.

[0368] OE30. A method comprising blending any one of the HFO-E-1132 and / or HFO-Z-1132 compositions according to OE7 to OE12 with at least one of the following:

[0369] • One or more HFC compounds, wherein the one or more HFC compounds are selected from HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea, and HFC-1123.

[0370] • One or more HFO compounds, wherein the one or more HFO compounds are selected from HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd and HFO-E-1336mzz.

[0371] OE31. In some 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.

[0372] OE32. A method comprising using a blend of HFO-E-1132 and / or HFO-Z-1132 compositions according to OE7 to OE12 with other HFC, HFO and HCFO compounds as a refrigerant, solvent, foam expander, detergent, aerosol propellant, dielectric, fire extinguishing agent or power cycle working fluid.

[0373] OE33. A method, the method comprising:

[0374] (a) 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is contacted with a reducing metal in the liquid phase to dechlorinate CFC-113 and form chlorotrifluoroethylene (CFO-1113).

[0375] (b) Contacting chlorotrifluoroethylene (CFO-1113) with hydrogen in either the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143), and

[0376] (c) Converting 1,1,2-trifluoroethane (HFC-143) in the liquid phase or the gas phase to form E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0377] OE34.OE33, wherein OE33 further includes isomerization of Z-1,2-difluoroethylene (HFO-Z-1132) to E-1,2-difluoroethylene (HFO-E-1132).

[0378] OE35. The method according to OE 32 to OE 34, wherein steps “a” and “b” are carried out in a separate reactor or in one of the same reactor.

[0379] OE36. The method according to OE 32 to OE 34, wherein steps “a” and “b” are carried out in the same reactor.

[0380] OE37. The method according to OE 32 to OE 34, wherein steps “a” and “b” are carried out in separate and different reactors.

[0381] OE38. A method embodiment wherein the CFC-113 feed 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.

[0382] OE39. Method implementation scheme OE37, wherein CFC-113 is contacted with hydrogen, and the relative molar amounts of hydrogen to CFC-113 in the reaction are about 1:1 to about 3:1.

[0383] OE40. Method implementation scheme OE37, wherein the contact is carried out at a temperature of about 80°C to about 250°C.

[0384] OE41. Method embodiment, wherein CFC-113 is contacted with hydrogen in the gas phase in the presence of a catalyst to form an HFC-143 composition.

[0385] OE42. Method embodiment OE40, 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 mixtures thereof, preferably supported on Al2O3, fluorinated alumina, AlF3, or chromium oxide, as disclosed in U.S. Patent Applications 20080207962 and 20080207963.

[0386] OE43. Method embodiment OE41, wherein CFC-113 is contacted with hydrogen in the gas phase in the presence of a catalyst, wherein the amount of catalytic metal on the support is about 0.5% to about 10% by weight of the catalyst composition.

[0387] OE44. Composition embodiments derived from OE40 to OE-42, wherein 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.

[0388] OE45. The method according to OE32, the method further comprising isomerizing E-1,2-difluoroethylene (HFO-E-1132) to Z-1,2-difluoroethylene (HFO-Z-1132).

[0389] OE46. In each OE method, the feed for any of reactions (1) to (4) is independently selected from one of the following: >50% by weight, >60% by weight, >70% by weight, <80% by weight or <90% by weight before purification, for example by distillation, and about >95% by weight or >99% by weight based on the total weight of the composition after distillation.

[0390] OE47. A system comprising:

[0391] A first reactor configured to synthesize a first mixture comprising 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from a feed 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;

[0392] A second reactor is configured to convert the CFC-113 in the first mixture into a second mixture containing chlorotrifluoroethylene (CFO-1113);

[0393] A third reactor, configured to convert the CFO-1113 of the second mixture into a third mixture containing 1,1,2-trifluoroethane (HFC-143); and

[0394] A fourth reactor is configured to convert the HFC-143 of the third mixture into a fourth mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0395] OE48. The system according to OE47, wherein the first reactor, the second reactor, the third reactor and the fourth reactor are in flow communication with each other.

[0396] OE49. The system according to OE48, wherein the system is an integrated system comprising the first reactor, the second reactor, the third reactor, and the fourth reactor.

[0397] OE50. The system according to any one of OE47 to OE49, the system further comprising a conversion system in fluid communication with the fourth reactor, the conversion system being configured to adjust the HFO-1132 E / Z ratio of the fourth mixture.

[0398] OE51. The system according to OE50, wherein the conversion system is selected from the group consisting of: distillation column, catalyst-free thermal converter and catalytic reactor.

[0399] OE52. A method, the method comprising:

[0400] a. Provide an initial feedstock containing tetrachloroethylene (PCE), HF, and chlorine.

[0401] b. Synthesize 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the said starting feed as part of the first product mixture.

[0402] c. Contact the CFC-113 with a reducing metal in the liquid phase to form chlorotrifluoroethylene (CFO-1113) as part of the second product mixture.

[0403] d. Contacting the CFO-1113 with hydrogen in the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143) as part of a third product mixture, and

[0404] e. Converting the HFC-143 in the liquid phase or the gas phase into a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

[0405] OE53. The method according to OE52, wherein, prior to the next step, at least one of CFC-113, CFO-1113, or HFC-143 is first separated from its respective product mixture.

[0406] OE54. The method according to OE52 or OE53, the method further comprising treating 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.

[0407] OE55: The method according to OE54, wherein the processing includes distilling the fourth product mixture to form a first stream and a second stream, the first stream comprising the composition having an HFO-Z-1132:HFO-E-1132 ratio lower than that of the fourth product mixture, and the second stream having an HFO-Z-1132:HFO-E-1132 ratio higher than that of the first stream.

[0408] OE56: According to the method of OE55, the method further includes recycling the second feed stream to step (b).

[0409] While certain aspects, embodiments, and principles have been described above, it should be understood that this description is exemplary only and not intended to limit the invention or the appended claims. The various aspects, embodiments, and principles described above can be used individually or in combination with each other.

Claims

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

2. The method according to claim 1, further comprising (e) 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 method according to claim 1, wherein (a), (b) and (c) are part of an integrated method, and each reaction is carried out in a separate and independent reactor.

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

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

6. The method according to any one of claims 1 or 2, wherein (a) comprises chlorofluorination, (b) comprises dechlorination, (c) comprises hydrogenation, and (d) comprises dehydrofluorination.

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

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

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

10. The method of 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 feed composition.

11. The method according to any one of claims 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 method of 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 method of claim 12, wherein the amount of the additional compound in the first product composition is greater than 0% by weight and less than 1% by weight, based on the total amount of the first product composition.

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

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

16. The method according to any one of claims 1 or 2, wherein the reducing metal comprises zinc, magnesium or cadmium in the solvent of the liquid phase.

17. The method according to any one of claims 1 or 2, wherein the solvent comprises a polar aprotic solvent.

18. The method according to 15, wherein contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with the reducing metal in the liquid phase is carried out at a temperature of about 20°C to about 120°C.

19. The method according to any one of claims 1 or 2, wherein the contact of trichlorofluoroethylene (CFO-1113) with hydrogen is carried out under one of the following conditions: (i) at a temperature of about 50°C to about 150°C, and 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 about 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 method according to any one of claims 1 or 2, wherein the contact of trichlorofluoroethylene (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 method of claim 11, wherein the hydrogenation of chlorotrifluoroethylene (CFO-1113) produces the third product mixture, the third product mixture comprising primarily 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 method of claim 11, wherein the third product mixture is converted in the gas phase or the liquid phase into a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

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

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

25. A composition comprising one of the following: (a) Tetrachloroethylene (PCE) and at least one additional compound, said at least one additional compound being 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, said at least one additional compound being selected from the group consisting of: HCFC-123a, HCFC-133, HCFC-133a, HCFC-133b and CFC-113; (d) 1,1,2-trifluoroethane (HFC-143) and at least one additional compound selected from the group consisting of: 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, said at least one additional compound being 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) 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 comprising at least one of the following: (a) HFO-E-1132 and at least one additional compound, said additional compound being selected from the group consisting of: HFO-1141, HCFO-1140, acetylene, and fluoroacetylene, in an amount <500 ppm. (b) HFO-Z-1132 and at least one additional compound, said additional compound being selected from the group consisting of: HFO-1141, HCFO-1140, acetylene, and fluoroacetylene, in an amount <500 ppm. (c) At least one of HFO-E-1132 and HFO-Z-1132, and at least two additional compounds selected from the group consisting of: 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), vinyl fluoride (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), dichlorofluoromethane (HCFC-22), ethylene (HCO-1150), 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), vinyl chloride (1140), 1-chloro-1-fluoroethylene (HCFO-E-1131a), E-1-chloro-2-fluoroethylene (HCFO-E-1131), Z-1-chloro-2-fluoroethylene (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 at least two additional compounds selected from the group consisting of: 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), and 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), dichlorofluoromethane (HFC-22), ethylene, 1-chloro-1,2-difluoroethane (HCFC-142a), 1,1-difluoroethylene (HFO-1132a), chlorine Ethylene (1140), 1-chloro-1-fluoroethylene (HCFO-E-1131a), E-1-chloro-2-fluoroethylene (HCFO-E-1131), Z-1-chloro-2-fluoroethylene (HCFO-Z-1131), and 1-chloro-2,2-difluoroethylene (HCFO-1122), wherein the total amounts of HFO-1141, HCFO-1140, acetylene, and fluoroacetylene are selected from one of the following: <2000 ppm, <1000 ppm, <500 ppm, <2000 ppm, <1000 ppm, <500 ppm, 400 ppm m, <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 about 2000ppm, ≥1ppm to less than about 1000ppm, or ≥0ppm and <100ppm, and all values ​​and ranges from about 0.00001ppm to 2000ppm.

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 of 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 of 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 of claim 31, wherein the total amount of the additional compound is greater than 0% by weight and less than 1% by weight based on the total amount of the composition.

34. A method comprising blending HFO-E-1132 and / or HFO-Z-1132 formed according to any one of claims 1 or 2 with one or more other compounds selected from the group consisting of: (i) one or more HFC compounds, said one or more HFC compounds being selected from the group consisting of: HFC-32, HFC-134, HFC-134a, HFC-125, HFC-152a, HFC-227ea and HFC-1123; and (ii) One or more HFO compounds, said one or more HFO compounds being selected from the group consisting of: HFO-E-1234ze, HFO-Z-1234ze, HFO-1234yf, HFO-Z-1224yd and HFO-E-1336mzz.

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

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

37. A method, the method comprising: (a) Contacting 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) with a reducing metal in the liquid phase to dechlorinate the CFC-113 and form chlorotrifluoroethylene (CFO-1113), and (b) Contact the CFO-1113 with hydrogen in either the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143).

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

39. The method of 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 method of claim 37, wherein steps (a) and (b) are carried out in a separate reactor or in one of the same reactor.

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

42. A method 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 method of claim 42, wherein the relative molar ratio of hydrogen to CFC-113 is about 1:1 to about 3:

1.

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

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

46. ​​The method of claim 45, wherein the PCE is contacted with hydrogen in the gas phase in the presence of a catalyst comprising a catalytic metal selected from the group consisting of Pd, Pt, and mixtures thereof, preferably supported on Al2O3, fluorinated alumina, AlF3, or chromium oxide.

47. The method of claim 46, wherein the amount of catalytic metal on the support is from about 0.5% to about 10% by weight of the catalyst composition.

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

49. A system comprising: A first reactor is configured to synthesize a first mixture comprising 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from a feed 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 is configured to convert the CFC-113 in 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); and A fourth reactor is configured to convert the HFC-143 of the third mixture into a fourth mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

50. The system of claim 49, wherein the first reactor, the second reactor, the third reactor, and the fourth reactor are in flow communication with each other.

51. The system of claim 50, wherein the system is an integrated system comprising the first reactor, the second reactor, the third reactor, and the fourth reactor.

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

53. The system of claim 52, wherein the conversion system is selected from the group consisting of: distillation column, catalyst-free thermal converter and catalytic reactor.

54. A method, the method comprising: (a) Provide an initial feed consisting of tetrachloroethylene (PCE), HF and chlorine. (b) Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the said starting feed as part of the first product mixture. (c) The CFC-113 is contacted with a reducing metal in the liquid phase to form chlorotrifluoroethylene (CFO-1113) as part of the second product mixture. (d) Contacting the CFO-1113 with hydrogen in the gas phase or the liquid phase to form 1,1,2-trifluoroethane (HFC-143) as part of a third product mixture, and (e) In the liquid phase or the gas phase, the HFC-143 is converted into a fourth product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

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

56. The method of claim 54 or claim 55, the method 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.

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

58. The method of claim 57, further comprising recycling the second feed stream to step (b).

59. A method, the method comprising: (a) Provide an initial feed consisting of tetrachloroethylene (PCE), HF and chlorine. (b) Synthesizing 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) from the said starting feed as part of the first product mixture. (c) Contacting the CFC-113 with hydrogen in the gas or liquid phase to form 1,1,2-trifluoroethane (HFC-143) as part of a second product mixture, and (d) In the liquid phase or the gas phase, the HFC-143 is converted into a third product mixture comprising E-1,2-difluoroethylene (HFO-E-1132) and Z-1,2-difluoroethylene (HFO-Z-1132).

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

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

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

63. The method of claim 62, further comprising recycling the second feed stream to step (b).

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