Process for production of fluoroolefin compositions by catalytic hydrodechlorination of hydrochlorofluorocarbon and compositions thereof

Abstract

Provided herein are methods for the production of fluoroolefins, and more particularly difluoroolefins, such as 1, 1-difluoropropene, particularly HFO-1252zc or E / Z-1, 2-difluoroethylene, by the catalytic hydrodechlorination of a hydrochlorofluorocarbon. Also provided herein are compositions produced by these methods.

Description

Cross-references to related applications

[0001] This application claims the benefit of priority to U.S. Provisional Application 63 / 565,052, filed March 14, 2024, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0002] This invention relates to a method and composition for producing fluoroolefins, and more specifically difluoroolefins, by catalytic hydrodechlorination of hydrochlorofluorocarbons (HCFCs). Background Technology

[0003] For decades, the fluorocarbon industry has been striving to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and HCFCs, which are being phased out due to the Montreal Protocol. Solutions for many applications involve the commercialization of hydrofluorocarbon (HFC) compounds used as refrigerants, solvents, fire extinguishing agents, foaming agents, and propellants. These currently most widely used new compounds, such as HFC refrigerants, HFC-134a, and HFC-125, have zero ozone depletion potential (ODP) and are therefore unaffected by the current Montreal Protocol phase-out provisions. In addition to ozone depletion, global warming is another environmental concern for many of these applications. According to the UN IPCC Fifth Assessment Report (AR5), HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWPs) of 1,300 and 3,170, respectively.

[0004] This regulatory environment is constantly evolving, and the characteristics taken into consideration 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 variety of applications, and meet the standards of evolving regulations.

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

[0006] Some fluoroolefins, such as 1,1-difluoropropylene (HFO-1252zc) (CF2═CHCH3) and E / Z-1,2-difluoroethylene (E / Z-HFO-1132) (CFH=CFH), are potential new refrigerants of this class. There remains a need for efficient and effective methods for preparing low-GWP and low- or zero-ODP fluoroolefin compounds, as well as methods for preparing these low-GWP and low- or zero-ODP fluoroolefin compounds, and their compositions. Summary of the Invention

[0007] In one embodiment, the present invention relates to a method for producing a fluoroolefin compound of formula (I):

[0008] R 1 CX 1 =CY 1 Z 1 (I)

[0009] In the compound of formula (I), R 1 X represents H, Cl, F, or C1-C4 alkyl groups. 1 Is it H, F, or Cl, Y 1 It is H, F, or Cl, and Z 1 It is H, Cl, or F.

[0010] In one embodiment, a method for producing a fluoroolefin of formula (I) includes contacting a compound of formula (II) with hydrogen gas:

[0011] R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 (II)

[0012] In the compound of formula (II), R 2 X represents H, Cl, F, or C1-C4 alkyl groups. 2 Is it H, F, Cl or Br, Y 3 It is H, Cl, Br or F, X 3 and Y 2 They are the same or different and are independently Cl or Br, and Z 2 It is H, Cl, or F.

[0013] 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. Detailed Implementation

[0014] The foregoing overview, along with the following detailed description and accompanying drawings, are exemplary and illustrative only and do not constitute a limitation on the invention as defined in the appended claims. Further features and benefits of any one or more embodiments will become apparent from the following detailed description, drawings, and claims.

[0015] 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).

[0016] 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...".

[0017] 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.

[0018] 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”.

[0019] 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. This 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.

[0020] 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.

[0021] As used in this article, 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 mol% using a calculated or measured response factor. See https: / / www.chromatographytoday.com / news / gc-mdgc / 32 / breaking-news / what-is-a-response-factor / 31169.

[0022] As used herein, the term “about” is intended to account for variations due to experimental error (e.g., adding or subtracting approximately 10%, ±1%, ±2%, ±3, … ±10% of the indicated value). Unless otherwise expressly stated, all measurements reported herein should be understood to be modified by the term “about”, whether or not the term is explicitly used.

[0023] The compounds mentioned in this disclosure may be represented by codes, chemical structures, and / or chemical names based on the naming conventions for fluorine-containing compounds. For convenience and reference, selected compounds with codes, structures, and chemical names are provided in Table 1.

[0024]

[0025] Some compounds present in the compositions of this invention may exist as different configurational isomers or stereoisomers. Examples of such compounds include, but are not limited to, HCFO-1241xb and HCFO-1251zb. This invention is intended to include all single configurational isomers, single stereoisomers, or any combination or mixture thereof. Single or multiple isomers of the same compound may be used in any proportion.

[0026] In some embodiments, the present invention relates to a method for producing fluoroolefins of formula (I):

[0027] R 1 CX 1 =CY 1 Z 1 (I)

[0028] In the compound of formula (I), R 1X represents H, Cl, F, or C1-C4 alkyl groups. 1 Is it H, F, or Cl, Y 1 It is H, F, or Cl, and Z 1 It is H, Cl, or F.

[0029] In some embodiments, a method for producing a fluoroolefin of formula (I) includes contacting a compound of formula (II) with hydrogen gas:

[0030] R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 (II)

[0031] In the compound of formula (II), R 2 X represents H, Cl, F, or C1-C4 alkyl groups. 2 Is it H, F, Cl or Br, Y 3 It is H, Cl, Br or F, X 3 and Y 2 They are the same or different and are independently Cl or Br, and Z 2 It is H, Cl, or F.

[0032] Preferably, the contact between the compound of formula (II) and H2 is carried out in the gas phase. More preferably, the contact is carried out in the presence of a catalyst, the amount of which is sufficient to form a composition comprising the compound of formula (I).

[0033] In some embodiments, the compounds of formula (I) include 1,1-difluoropropylene (HFO-1252zc) (CF2=CHCH3) or E / Z-1,2-difluoroethylene (E / Z-HFO-1132) (CHF=CHF) or E / Z-1-chloro-1,2-difluoroethylene (E / Z-HCFO-1122a) (CClF=CHF) or E / Z-1,2-dichloro-1,2-difluoroethylene (E / Z-CFO-1112) (CClF=CClF).

[0034] In some embodiments, the compounds of formula (II) include 1,2-dichloro-1,1-difluoropropane (HCFC-252dc) or 1,2-dichloro-1,2-difluoroethane (HCFC-132).

[0035] In some embodiments, the present invention relates to a method for producing (preparing) HFO-1252zc and compositions thereof. In some embodiments, the present invention relates to a method for producing (preparing) HFO-1252zc and compositions thereof from HCFC-252dc.

[0036] In some embodiments, the present invention relates to the preparation of HFO-1252zc and to the following reaction:

[0037] CClF2CHClCH3 (HCFC-252dc) + H2→CF2=CHCH3 (HFO-1252zc) + 2HCl

[0038] In some embodiments, the feed composition contacting H2 to form HFO-1252zc comprises HCFC-252dc and one or more additional compounds, substantially composed of or consisting of therefrom, the additional compounds being selected from HCFC-262fc, HCFO-1233xf, HCFO-1242zf, acetone, HCFC-262db, HCFC-253db, HCFO-1223xd, C4H6ClF, HCFO-1232xf, E-HCFO-1241xb, Z-HCFO-1241xb, and HCFO-1335. In some embodiments, based on the total weight of the composition, HCFC-252dc comprises about 0.1% by weight to about 99.9% by weight, or about 40% by weight to about 99.9% by weight, or about 90% by weight to about 99.9% by weight, including all integers and ranges therein.

[0039] In some embodiments, the total amount of additional compounds in the HCFC-252dc feed composition can be between greater than 0% by weight and about 15% by weight, expressed as a percentage of GC-FID peak area (e.g., the total amount of the composition), and all values ​​and ranges therebetween. In some embodiments, the total amount of additional compounds in the HCFC-252dc feed composition can be greater than 0% and less than one of 15%, 14%, 13%, 12%, 11%, 10%, 9%, 9%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%, and all values ​​and ranges therebetween.

[0040] In some embodiments, based on the total amount of the composition, the total amount of additional compounds in the HCFC-252dc feed composition can be between greater than 0% and less than 0.1%, greater than 0% and less than 0.01%, between greater than 0.0001% and less than 0.3%, greater than 0.0001% and less than 0.2%, greater than 0.0001% and less than 0.1%, greater than 0.0001% and less than 0.01%, or greater than 0.0001% and less than 0.001%, and all values ​​and ranges therein.

[0041] In some embodiments, based on the total amount of the feed composition, each additional compound in the HCFC-252dc feed composition may be present in an amount between greater than 0% and less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5%, or less than 0.1%, or less than 0.01%, or less than 0.005%, or greater than 0.001% and less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5%, or less than 0.1%, or less than 0.01%, or less than 0.005%, provided that the additional compound... The total amount of the compound is greater than 0.0001% and less than 15%, greater than 0.0001% and less than 10%, greater than 0.0001% and less than 8%, greater than 0.0001% and less than 7%, greater than 0.0001% and less than 6%, greater than 0.0001% and less than 5%, greater than 0.0001% and less than 4%, greater than 0.0001% and less than 3%, greater than 0.0001% and less than 2%, greater than 0.0001% and less than 1%, greater than 0.0001% and less than 0.5%, or greater than 0.0001% and less than 0.1%.

[0042] One embodiment of the invention disclosed herein relates to a method of contacting HCFC-252dc with hydrogen in the gas phase in the presence of a catalyst to form a product mixture or composition comprising HFO-1252zc. More specifically, in certain embodiments disclosed herein, HCFC-252dc is converted to HFO-1252zc via a hydrodechlorination reaction in the gas phase in the presence of a catalyst.

[0043] In some embodiments, the present invention relates to methods for producing (preparing) E-HFO-1132 and Z-HFO-1132 and compositions thereof. In some embodiments, the present invention relates to methods for producing (preparing) E-HFO-1132 and Z-HFO-1132 and compositions thereof from HCFC-132.

[0044] In some embodiments, the present invention relates to the preparation of E / Z-HFO-1132 and to the following reaction:

[0045] CHClFCCHClF (HCFC-132) + H2→CFH=CFH (E / Z-HFO-1132) + 2HCl

[0046] In some embodiments, the feed composition that contacts H2 to form E / Z-HFO-1132 comprises HCFC-132 and one or more additional compounds, substantially composed of or consisting of therefrom, the additional compounds being selected from HCFC-132C (1,1-dichloro-1,2-difluoroethane), HCFC-132a (1,1-dichloro-2,2-difluoroethane), CFO-1112 (1,2-dichloro-1,2-difluoroethylene), CFO-1112a (1,1-dichloro-2,2-difluoroethylene), HCFC-142 (1-chloro-2,2-difluoroethane), HCFC-142a (1-chloro-1,2-difluoroethane), and HFC-152 (1,2-difluoroethane). In some embodiments, based on the total weight of the composition, HCFC-132 accounts for about 0.1% to about 99.9% by weight, or about 40% to about 99.9% by weight, or about 90% to about 99.9% by weight, including all integers and ranges therein.

[0047] In some embodiments, the total amount of additional compounds in the HCFC-132 feed composition can be between greater than 0% by weight and about 15% by weight, expressed as a percentage of GC-FID peak area (e.g., the total amount of the composition), and all values ​​and ranges therebetween. In some embodiments, the total amount of additional compounds in the HCFC-132 feed composition can be greater than 0% and less than one of 15%, 14%, 13%, 12%, 11%, 10%, 9%, 9%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%, and all values ​​and ranges therebetween.

[0048] In some embodiments, based on the total amount of the composition, the total amount of additional compounds in the HCFC-132 feed composition can be between greater than 0% and less than 0.1%, greater than 0% and less than 0.01%, between greater than 0.0001% and less than 0.3%, greater than 0.0001% and less than 0.2%, greater than 0.0001% and less than 0.1%, greater than 0.0001% and less than 0.01%, or greater than 0.0001% and less than 0.001%, and all values ​​and ranges therein.

[0049] In some embodiments, based on the total amount of the feed composition, each additional compound in the HCFC-132 feed composition may be present in an amount between greater than 0% and less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5%, or less than 0.1%, or less than 0.01%, or less than 0.005%, or greater than 0.001% and less than 4%, or less than 3%, or less than 2%, or less than 1%, or less than 0.5%, or less than 0.1%, or less than 0.01%, or less than 0.005%, provided that the additional compound... The total amount of the substance is greater than 0.0001% and less than 15%, greater than 0.0001% and less than 10%, greater than 0.0001% and less than 8%, greater than 0.0001% and less than 7%, greater than 0.0001% and less than 6%, greater than 0.0001% and less than 5%, greater than 0.0001% and less than 4%, greater than 0.0001% and less than 3%, greater than 0.0001% and less than 2%, greater than 0.0001% and less than 1%, greater than 0.0001% and less than 0.5%, or greater than 0.0001% and less than 0.1%.

[0050] One embodiment of the invention disclosed herein relates to a method of contacting HCFC-132 with hydrogen in the gas phase in the presence of a catalyst to form a product mixture or composition comprising HFO-1132(E) and HFO-1132(Z). More specifically, in certain embodiments disclosed herein, HCFC-132 is converted to HFO-1132(E) and HFO-1132(Z) by a hydrodechlorination reaction in the gas phase in the presence of a catalyst.

[0051] Reactors suitable for gas-phase reactions can be used. In some embodiments, heated reactors are used, and the reactors are provided with suitable thermal control. Many reactor configurations are possible, including packed bed tube or tower reactors operating in batch, semi-batch, or continuous modes. In addition to the reactors disclosed herein, preheaters and gasifiers, heat exchangers, feed and effluent lines, units associated with mass transfer, contact vessels (premixers), distillation columns, and valves associated with reactors, heat exchangers, vessels, towers, and units used in the methods of the various embodiments disclosed herein should be constructed of corrosion-resistant materials. For example, gas-phase reactors and other components may be made of or filled with materials such as, but not limited to, Hastelloy. ® It can be registered under the trademark Inconel ® Inconel (nickel-chromium alloy) purchased commercially from Special Metals Corp. ® (or can be trademarked Monel) ®Nickel-copper alloy or other nickel alloy chips or nickel alloy filaments, or other materials inert to the reactants, are commercially available from Specialty Metals Company (New Hartford, NY).

[0052] In some embodiments, the hydrodechlorination reaction of the feed compound (i.e., a compound of formula (II), such as HCFC-252dc or HCFC-132) with H2 is carried out in the presence of a catalyst. In some embodiments, the hydrogenation catalyst that can be used comprises Group IB and / or Group IIB metals, and more specifically Group IB and Group IIB metals. In a preferred embodiment, the hydrogenation catalyst that can be used comprises copper (Cu) and zinc (Zn). The catalyst can be unsupported or supported. In one embodiment, the Cu-Zn metal is supported on a support such as alumina, SiC, or carbon, preferably carbon. In some embodiments, the metal catalyst is supported on carbon, and the carbon support / carrier includes carbon, acid-washed carbon, activated carbon, and / or a three-dimensional matrix carbon-containing material. In one embodiment, the catalyst is Zn-Cu / C. In one embodiment, the catalyst comprises about 2 wt% to about 20 wt% copper and about 0.5 wt% to about 10 wt% zinc. In one embodiment, the catalyst is 3% Zn-8% Cu / C. If the catalyst becomes deactivated, it can be easily regenerated by any means known in the art.

[0053] It has been found that using Zn-Cu catalysts for the catalytic hydrodechlorination of compounds of formula (II) (e.g., HCFC-252dc and / or HCFC-132) is effective for the highly selective production of compounds of formula (I) (e.g., HFO-1252zc and / or E / Z-HFO-1132).

[0054] In some implementations, for example where R 1 It is a C1-C4 alkyl group, such as HFO-1252zc formed by the hydrogenation and dechlorination reaction of HCFC-252dc, which is related to R 1 CX 1 =CY 1 Z 1 The product selectivity is at least about 70 mol%, or at least about 80 mol%, or at least about 90 mol%, or at least about 95 mol%, or at least about 96 mol%, or at least about 97 mol%.

[0055] In some implementations, for example where R 1 It is H, F, or Cl, such as E / Z-HCFO-1132 formed by the hydrodechlorination reaction of HCFC-132, for R 1 CX1 =CY 1 Z 1 The product selectivity is at least about 30 mol%, or at least about 32 mol%, or at least about 34 mol%, or at least about 36 mol%, or at least about 38 mol%, or at least about 40 mol%.

[0056] As used in this article, the term "for R" 1 CX 1 =CY 1 Z 1 "Product selectivity" refers to the percentage of Ro obtained by the method compared to the total molar amount of all products obtained. 1 CX 1 =CY 1 Z 1 The mole percentage.

[0057] Optionally, the catalyst can be pretreated (pre-activated) with H2. This pretreatment can be accomplished, for example, by placing the catalyst in a suitable vessel and then passing H2 through the catalyst at an elevated temperature. In one embodiment, such a vessel can be a reactor for performing a hydrodechlorination reaction. If the metal packing material of the reactor is catalytically active, H2 can pass through the surface of the metal packing material for its activation. In one embodiment, the pretreatment time is from about 15 minutes to about 300 minutes, preferably about 120 minutes, and the pretreatment temperature is from about 100°C to about 500°C, or from about 200°C to about 450°C, preferably about 450°C.

[0058] In one embodiment, the heated reactor is used for the reaction of H2 with a compound of formula (II) (e.g., HCFC-252dc or HCFC-132). Many reactor configurations are possible, including horizontal or vertical orientation of the reactor and the reaction sequence of the compound of formula (II) with H2. In one embodiment of the invention, the compound of formula (II) may initially be vaporized and fed as a gas into the reactor. In one embodiment, the reactor may be empty. In another embodiment, the reactor is filled with suitable packing material, such as a nickel-based alloy, such as Hastelloy. ® It can be registered under the trademark Inconel ® Nickel-chromium alloy (hereinafter referred to as Inconel) purchased from a specialty metals company ® (or can be trademarked Monel) ® Nickel-copper alloy or other nickel alloy chips or nickel alloy filaments, commercially available from Specialty Metals Company (New Hartford, NY), or other materials that are inert to the reactants and products and allow for efficient mixing of the compound of formula (II) and H2 vapor. Those skilled in the art will understand that a pre-reactor can be utilized.

[0059] In some implementations, an inert dilution gas is used as R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 A carrier gas for the compound (e.g., HCFC-252dc or HCFC-132). In one embodiment, the carrier gas is selected from HCl, nitrogen, argon, helium, carbon dioxide, or fluorinated carbon. In some embodiments, the carrier gas is mixed with the compound of formula (II) and H2 and vaporized in a reactor.

[0060] In some implementations, H2 used for the gas-phase reaction reacts with R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 The molar ratio is from about 1:1 to about 50:1. In one embodiment, R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 The H2 content is HCFC-252dc, and the molar ratio of the total amount of H2 to HCFC-252dc in the gas phase reactor is approximately 1:1 to approximately 50:1. In another embodiment, R... 2 CX 2 Y 2 -CX 3 Y 3 Z 2 The substance is HCFC-132, and the molar ratio of the total amount of H2 to HCFC-132 in the gas phase reactor is about 5:1 to about 40:1.

[0061] In the presence of a catalyst, R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 The suitable temperature for the gas-phase hydrodechlorination reaction of (e.g., HCFC-252dc or HCFC-132) with H2 is about 60°C to about 300°C, or about 180°C to about 280°C.

[0062] In the presence of a catalyst, R 2 CX 2 Y 2 -CX 3 Y 3 Z 2Suitable reactor pressures for the gas-phase hydrodechlorination reaction of compounds (e.g., HCFC-252dc or HCFC-132) with H2 are about 0 psig to about 200 psig, or about 10 psig to about 150 psig.

[0063] In the presence of a catalyst, R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 The appropriate reaction time for the gas-phase hydrodechlorination reaction of (e.g., HCFC-252dc or HCFC-132) with H2 can vary from about 5 seconds to about 300 seconds, or from about 10 seconds to about 120 seconds.

[0064] In all the embodiments disclosed herein, R is included. 2 CX 2 Y 2 -CX 3 Y 3 Z 2 The product stream of a compound (e.g., HFO-1252zc, E-HFO-1132 and / or Z-HFO-1132) may contain additional members, including unreacted precursor materials such as HCFC-252dc for HFO-1252dc and HCFC-132 for E / Z-HFO-1132.

[0065] In some embodiments, based on the total amount of the product mixture, the amount of HFO-1252zc produced is greater than about 10%, preferably greater than about 20%, more preferably greater than about 30%, and most preferably greater than about 35%. In some embodiments, based on the total amount of the product mixture, the amounts of E-HFO-1132 and Z-HFO-1132 produced are greater than about 1%, or greater than about 2%, preferably greater than about 3%, more preferably greater than about 4%, and most preferably greater than about 5%.

[0066] In some embodiments, the method of the present invention further includes separation and / or purification (e.g., distillation, fractionation, adsorption, absorption, etc., or any combination of such methods) to recover the desired product (R) from the mixture produced by the hydrodechlorination reaction. 1 CX 1 =CY 1 Z 1 For example, HFO-1252zc, E-HFO-1132 and / or Z-HFO-1132) or to enhance the desired product (R 1 CX 1 =CY 1 Z 1For example, the content of HFO-1252zc, E-HFO-1132 and / or Z-HFO-1132.

[0067] Some embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or consisting of R-1252zc, and further comprising one or more additional members, including hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrochlorofluorocarbons (HCFCs), hydrofluoroolefins (HFOs), and hydrochlorofluoroolefins (HFCOs).

[0068] Certain embodiments of the invention disclosed herein relate to compositions comprising, or consisting substantially of, HFO-1252zc and one or more additional compounds selected from propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db.

[0069] Some embodiments of the invention disclosed herein relate to compositions comprising, based on the total amount of the composition, more than about 10%, preferably more than about 20%, more preferably more than about 30%, and most preferably more than about 35% of HFO-1252zc, substantially consisting of or consisting of; and further comprising one or more additional compounds selected from propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db.

[0070] In some embodiments, under the reaction conditions disclosed herein, for example, a mixture of H2 and HCFC-252dc is converted into a reaction mixture comprising HCl and a composition comprising HFO-1252zc and one or more additional compounds selected from propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db, based on the total weight of the composition. In some embodiments, HFO-1252zc comprises from about 0.1% by weight to about 99.9% by weight, or from about 20% by weight to about 40% by weight, including all integers and ranges therein.

[0071] One embodiment of the invention disclosed herein is a composition comprising, substantially comprising, or comprising HFO-1252zc, wherein HFO-1252zc is present in an amount greater than or greater than about 20%, or greater than or greater than about 30%, or greater than about 35% and less than about 100%, or less than about 50%, or less than about 40%, and in all values ​​and ranges therebetween.

[0072] Some embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or consisting of E-HFO-1132 and Z-HFO-1132, and the compositions further comprising one or more additional members, including HFC, HCC, HCFC, HFO, and HFCO.

[0073] Certain embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or consisting of, E-HFO-1132, Z-HFO-1132 and one or more additional compounds selected from F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HCFC-142b, HFO-1132a, HFO-1141, E-HCFO-1122a, and Z-HCFO-1122a.

[0074] Some embodiments of the invention disclosed herein relate to compositions comprising, based on the total amount of the composition, more than about 3%, preferably more than about 4%, more preferably more than about 5% of E-HFO-1132 and Z-HFO-1132, substantially consisting of or consisting of therein, and further comprising one or more additional compounds selected from F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HCFC-142b, HFO-1132a, HFO-1141, E-HCFO-1122a, and Z-HCFO-1122a.

[0075] In some embodiments, under the reaction conditions disclosed herein, for example, a mixture of H2 and HCFC-132 is converted into a reaction mixture comprising HCl and a composition comprising E-HFO-1132 and Z-HFO-1132 and one or more additional compounds selected from F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HCFC-142b, HFO-1132a, HFO-1141, E-HCFO-1122a, and Z-HCFO-1122a. In some embodiments, based on the total weight of the composition, E-HFO-1132 and Z-HFO-1132 account for about 0.1% to about 10% by weight, or about 1% to about 5% by weight, or about 3% to about 5% by weight, including all integers and ranges therein.

[0076] One embodiment of the invention disclosed herein is a composition comprising, substantially comprising, or comprising of E-HFO-1132 and Z-HFO-1132, wherein E-HFO-1132 and Z-HFO-1132 are present in amounts greater than or greater than about 1%, or greater than about 2%, or greater than about 3%, or greater than about 4%, or greater than about 5% and less than about 100%, or less than about 20%, or less than about 10%, and all values ​​and ranges therebetween.

[0077] In a preferred embodiment, the composition according to the invention is free of or substantially free of Group A fluorinated substances. In one embodiment, as used herein, “Group A fluorinated substances” includes any substance that satisfies the following criteria: (i) contains at least one fully fluorinated methyl (–CF3) or methylene (–CF2–) carbon atom (without any H / Cl / Br / I attached thereto); as well as(ii) It complies with the persistence criteria in soil / sediments and water as set out in Annex XIII (Section 1.1.1) of the EU REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, accessed 2 May 2023), and the publication of that criterion is cited in Annex XV Restriction Report of 22 March 2023, the publication of which is incorporated herein by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed 2 May 2023).

[0078] In another implementation, as used herein, “Group A fluorides” includes the Henry's Law constant. < 250Pa*m 3 / mol and Any substance containing at least one fully fluorinated methyl (–CF3) or methylene (–CF2–) carbon atom (without any H / Cl / Br / I attached to it).

[0079] In the implementation plan, Group A fluorinated substances include, but are not limited to, TFA.

[0080] As used herein, the phrase "free of" relating to the presence of Group A fluorinated substances in the compositions of the present invention means that, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector (by analyzing gas or liquid samples), and / or ion chromatography (by analyzing water samples after bubbling a hot fluid through water), the amount of such substances in the composition is sufficiently low to be undetectable, including but not limited to 0%. Such methods are well known to those skilled in the art. As used herein, the phrase "substantially free of" relating to the presence of Group A fluorinated substances in the compositions of the present invention means that, when measured by gas chromatography (GC) techniques, such as gas chromatography (GC) with a flame ionization or electron capture detector, or GC coupled with a mass detector (GC / MS method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS), or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography-mass spectrometry (HPLC-MS), the amount of such substances in the composition is >0% by weight and < 5% by weight, or >0% by weight and < 4% by weight, or >0% by weight and < 3% by weight, or >0% by weight and < 2% by weight, or >0% by weight and <1% by weight, and all values ​​and ranges therebetween. TFA analytical standards can be used for gas chromatography or ion chromatography and are available from sources such as Sigma Aldrich.

[0081] In a preferred embodiment, the degradation products of the compositions according to the invention are free from or substantially free from Group A fluorides. As used herein, the phrase “free from” regarding the formation of Group A fluorides from the degradation products of the compositions of the invention means that, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is sufficiently low to be undetectable, including but not limited to 0%. As used herein, the phrase “substantially free from” regarding the formation of Group A fluorides from the compositions of the invention means that, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is >0% and ≤ 5%, or >0% and ≤ 4%, or >0% and ≤ 3%, or >0% and ≤ 2%, or >0% and ≤ 1%, and all values ​​and ranges in between.

[0082] Certain embodiments of the invention disclosed herein relate to compositions comprising, substantially consisting of, or consisting of HFO-1252zc or E / Z-HFO-1132, and containing little or no Group A fluorinated substances. In some embodiments, the compositions of the invention comprise, substantially consisting of, or consisting of HFO-1252zc or E / Z-HFO-1132, and the degradation products of such compositions contain little or no Group A fluorinated substances as defined herein.

[0083] Certain embodiments of the invention disclosed herein relate to compositions comprising HFO-1252zc or E / Z-HFO-1132 and one or more additional members, substantially composed of or consisting of thereof, selected from HFCs, HCCs, HCFCs, HFOs, HFCOs, C2-C4 alkanes, and C2-C4 alkenes. In some embodiments, such compositions are free of or substantially free of Group A fluorinated substances and / or the degradation products of such compositions are free of or substantially free of Group A fluorinated substances as defined herein.

[0084] Certain embodiments of the invention disclosed herein relate to blend compositions comprising, or substantially comprising, HFO-1252zc or E / Z-HFO-1132 and one or more refrigerant compounds selected from HFCs, HCCs, HCFCs, HFOs, HFCOs, C2-C4 alkanes, and C2-C4 olefins. In some embodiments, such blend compositions are free of or substantially free of Group A fluorinated substances, and / or the degradation products of such blend compositions are free of or substantially free of Group A fluorinated substances as defined herein.

[0085] Certain embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or consisting of, one or more additional members selected from propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db, and the compositions are free from or substantially free from Group A fluorinated substances, and / or the degradation products of such compositions are free from or substantially free from Group A fluorinated substances as defined herein.

[0086] Certain embodiments of the invention disclosed herein relate to blend compositions comprising HFO-1252zc, one or more other refrigerant compounds, and one or more additional members selected from propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db. In some embodiments, such blend compositions are free of or substantially free of Group A fluorinated substances, and / or the degradation products of such blend compositions are free of or substantially free of Group A fluorinated substances as defined herein.

[0087] Certain embodiments of the invention disclosed herein relate to compositions comprising, substantially comprising, or consisting of, E-HFO-1132, Z-HFO-1132 and one or more additional members selected from F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HFO-1132a, HCFC-142b, HFO-1141, E-HCFO-1122a, and Z-HCFO-1122a, and the compositions are free from or substantially free from Group A fluorinated substances, and / or the degradation products of such compositions are free from or substantially free from Group A fluorinated substances as defined herein.

[0088] Certain embodiments of the invention disclosed herein relate to blend compositions comprising HFO-1132, Z-HFO-1132, one or more other refrigerant compounds, and one or more additional members selected from F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HFO-1132a, HCFC-142b, HFO-1141, E-HCFO-1122a, and Z-HCFO-1122a. In some embodiments, such blend compositions are free of or substantially free of Group A fluorinated substances, and / or the degradation products of such blend compositions are free of or substantially free of Group A fluorinated substances as defined herein.

[0089] In some embodiments, at least a portion of any composition disclosed herein comprises recycled material.

[0090] The invention will now be described with reference to the following embodiments. Example 1: Hydrodechlorination of HCFC-252dc to HFO-1252zc using a 12% Cu / C catalyst.

[0091] Six ml of 12% Cu / C catalyst was loaded into a 12-inch Inconel (0.5-inch OD) reactor tube. The 12% Cu / C catalyst was activated with H2 at 450 °C for 2 hours. Then, HCFC-252dc and H2 were fed into the reactor, and tests were performed under the reaction conditions listed in Table 2 below. The reactor effluent was analyzed by GC-MS-FID.

[0092]

[0093] Example 2: Hydrodechlorination of HCFC-252dc to HFO-1252zc using a 3%Zn-8%Cu / C catalyst.

[0094] Six ml of 1 / 8" pellets of 3% Zn-8% Cu / C catalyst were loaded into a 12-inch long Inconel (0.5-inch OD) reactor tube. The catalyst was activated with H2 at 450°C for 2 hours. Then, HCFC-252dc and H2 were fed into the reactor, and tests were performed under the reaction conditions listed in Table 3 below. The reactor effluent was analyzed by GC-MS-FID, and detailed GC analysis of the products at 8 hours is provided in Table 4.

[0095]

[0096]

[0097]

[0098]

[0099] The results showed that using the Zn-Cu / C catalyst instead of the Cu / C catalyst resulted in higher selectivity for the production of HFO-1252zc. Furthermore, the Zn-Cu / C catalyst exhibited significantly better stability than the Cu / C catalyst. The product selectivity for HFO-1252zc using the Zn-Cu / C catalyst was approximately 90 mol% or higher, approximately 93 mol% or higher, approximately 94 mol% or higher, approximately 95 mol% or higher, approximately 96 mol% or higher, or approximately 97 mol% or higher. Example 3: Hydrodechlorination of HCFC-132 to HFO-1132 using a 3%Zn-8%Cu / C catalyst.

[0100] Six ml of 1 / 8" pellets of 3% Zn-8% Cu / C catalyst were loaded into a 12-inch long Inconel (0.5-inch OD) reactor tube. The catalyst was activated with H2 at 450°C for 2 hours. Then, HCFC-132 and H2 were fed into the reactor, and tests were conducted under the reaction conditions provided in Table 5 below. The reactor effluent was analyzed by GC-MS-FID, and detailed GC analysis results at the 9th hour of reaction time are provided in Table 6.

[0101]

[0102]

[0103] Therefore, the method of the present invention provides a way to produce (prepare) fluoroolefin compound R using a low-cost catalyst. 1 CX 1 =CY 1 Z 1 Methods such as HFO-1252zc or E / Z-HFO-1132, low-cost catalysts are effective for the production of fluoroolefin compounds with high selectivity. Additional implementation plan

[0104] Implementation Scheme 1. A method for preparing a fluoroolefin of formula (I), the method comprising contacting a compound of formula (II) with hydrogen in the gas phase in the presence of a catalyst comprising Group IB and Group IIB metals:

[0105] R 1 CX 1 =CY 1 Z 1 (I)

[0106] R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 (II)

[0107] In equation (I), R 1 X represents H, Cl, F, or C1-C4 alkyl groups. 1 Is it H, F, or Cl, Y 1 It is H, F, or Cl, and Z 1 It is H, Cl, or F, and in formula (II), R 2 X represents H, Cl, F, or C1-C4 alkyl groups. 2 Is it H, F, Cl or Br, Y 3 It is H, Cl, Br or F, X 3 and Y 2 They are the same or different and are independently Cl or Br, and Z 2 It is H, Cl, or F.

[0108] Implementation Scheme 2. The method according to Implementation Scheme 1, wherein the catalyst comprises zinc and copper.

[0109] Implementation Scheme 3. The method according to any one of Implementation Schemes 1 to 2, wherein the catalyst is supported on a support material selected from the group consisting of alumina, SiC and carbon.

[0110] Implementation Scheme 4. The method according to Implementation Scheme 3, wherein the carrier material is carbon.

[0111] Implementation Scheme 5. The method according to any one of Implementation Schemes 1 to 4, wherein the catalyst contains zinc in the range of 1% to 10% and copper in the range of 3% to 15%.

[0112] Implementation Scheme 6. The method according to any one of Implementation Schemes 1 to 5, wherein the catalyst is 3%Zn-8%Cu / C.

[0113] Implementation Scheme 7. The method according to any one of Implementation Schemes 1 to 6, wherein the catalyst is pre-activated with H2.

[0114] Implementation Scheme 8. The method according to Implementation Scheme 7, wherein the preactivation with H2 occurs at a temperature of about 100°C to about 500°C.

[0115] Implementation Scheme 9. The method according to any one of Implementation Schemes 1 to 8, wherein the compound of Formula (II) comprises 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

[0116] Implementation Scheme 10. The method according to Implementation Scheme 9, wherein the feed composition comprising the HCFC-252dc further comprises one or more additional compounds selected from the group consisting of HFC-262fc, HCFO-1233xf, HCFO-1242zf, acetone, HCFC-262db, HCFC-253db, HCFO-1223xd, C4H6ClF, HCFO-1232xf, E-HCFO-1241xb, Z-HCFO-1241xb, and HFO-1335.

[0117] Implementation Scheme 11. The method according to any one of Implementation Schemes 1 to 10, wherein the compound of Formula (I) comprises 1,1-difluoropropylene (HFO-1252zc).

[0118] Implementation Scheme 12. The method according to Implementation Scheme 11, wherein the product composition comprising the HFO-1252zc further comprises one or more additional compounds selected from the group consisting of propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db.

[0119] Implementation Scheme 13. The method according to any one of Implementation Schemes 1 to 8, wherein R 1 CX 1 =CY 1 Z 1 The product selectivity is at least about 30 mol%, or at least about 32 mol%, or at least about 34 mol%, or at least about 36 mol%, or at least about 38 mol%, or at least about 40 mol%, and less than 100 mol%.

[0120] Implementation Scheme 14. The method according to any one of Implementation Schemes 1 to 8 and 13, wherein the compound of Formula (II) comprises 1,2-dichloro-1,2-difluoroethane (HCFC-132).

[0121] Implementation Scheme 15. The method according to Implementation Scheme 14, wherein the feed composition of the HCFC-132 further comprises one or more additional compounds selected from the group consisting of HCFC-132C (1,1-dichloro-1,2-difluoroethane), HCFC-132a (1,1-dichloro-2,2-difluoroethane), CFO-1112 (1,2-dichloro-1,2-difluoroethylene), CFO-1112a (1,1-dichloro-2,2-difluoroethylene), HCFC-142 (1-chloro-2,2-difluoroethane), HCFC-142a (1-chloro-1,2-difluoroethane), and HFC-152 (1,2-difluoroethane).

[0122] Implementation Scheme 16. The method according to any one of Implementation Schemes 1 to 8 and 13 to 15, wherein the compound of Formula (I) comprises E / Z-1,2-difluoroethylene (E / Z-HFO-1132).

[0123] Implementation Scheme 17. The method according to Implementation Scheme 16, wherein the product composition comprises E-HFO-1132 and Z-HFO-1132, and further comprises one or more additional compounds selected from the group consisting of F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HCFC-142b, HFO-1132a, HFO-1141, E-HCFO-1122a and Z-HCFO-1122a.

[0124] Implementation Scheme 18. The method according to any one of Implementation Schemes 1 to 17, wherein R 1 CX 1 =CY 1 Z 1 The hydrodechlorination reaction is carried out at a temperature between about 60°C and about 300°C, preferably between about 180°C and about 280°C.

[0125] Implementation Scheme 19. The method according to any one of Implementation Schemes 1 to 18, wherein R 1 CX 1 =CY 1 Z 1 The hydrodechlorination reaction is carried out at a pressure between about 0 psig and about 200 psig, preferably between about 10 psig and about 150 psig.

[0126] Implementation Scheme 20. A composition comprising HCFC-252dc and one or more additional compounds selected from the group consisting of HFC-262fc, HCFO-1233xf, HCFO-1242zf, acetone, HCFC-262db, HCFC-253db, HCFO-1223xd, C4H6ClF, HCFO-1232xf, E-HCFO-1241xb, Z-HCFO-1241xb, and HFO-1335.

[0127] Implementation Scheme 21. A composition comprising HFO-1252zc and one or more additional compounds selected from the group consisting of propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db.

[0128] Implementation Scheme 22. A composition comprising HCFC-132 and one or more additional compounds selected from the group consisting of HCFC-132C (1,1-dichloro-1,2-difluoroethane), HCFC-132a (1,1-dichloro-2,2-difluoroethane), CFO-1112, CFO-1112a, HCFC-142 (1-chloro-2,2-difluoroethane), HCFC-142a (1-chloro-1,2-difluoroethane), and HFC-152.

[0129] Implementation Scheme 23. A composition comprising E-HFO-1132, Z-HFO-1132 and one or more additional compounds, said additional compounds being selected from the group consisting of F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HCFC-142b, HFO-1132a, HFO-1141, E-HCFO-1122a and Z-HCFO-1122a.

[0130] 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 for preparing a fluoroolefin of formula (I), the method comprising contacting a compound of formula (II) with hydrogen in the gas phase in the presence of a catalyst comprising a Group IB metal and a Group IIB metal: R 1 CX 1 =CY 1 Z 1 (I) R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 (II) wherein in formula (I), R 1 represents H, CI, F or a Ci-C4alkyl group, X 1 is H, F or CI, Y 1 is H, F or CI, and Z 1 is H, CI or F, and wherein in formula (II), R 2 represents H, CI, F or a C1-C4 alkyl group, X 2 is H, F, CI or Br, Y 3 is H, CI, Br or F, X 3 and Y 2 are the same or different and each independently CI or Br, and Z 2 is H, CI or F.

2. The method according to claim 1, wherein the catalyst comprises zinc and copper.

3. The method according to any one of claims 1 to 2, wherein the catalyst is supported on a support material selected from the group consisting of alumina, SiC and carbon.

4. The method according to claim 3, wherein the carrier material is carbon.

5. The method according to any one of claims 1 to 4, wherein the catalyst contains zinc in the range of 1% to 10% and copper in the range of 3% to 15%.

6. The method according to any one of claims 1 to 5, wherein the catalyst is 3%Zn-8%Cu / C.

7. The method according to any one of claims 1 to 6, wherein the catalyst is pre-activated with H2.

8. The method according to claim 7, wherein the preactivation with H2 occurs at a temperature of about 100°C to about 500°C.

9. The method according to any one of claims 1 to 8, wherein the compound of formula (II) comprises 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

10. The method of claim 9, wherein the feed composition comprising the HCFC-252dc further comprises one or more additional compounds selected from the group consisting of HFC-262fc, HCFO-1233xf, HCFO-1242zf, acetone, HCFC-262db, HCFC-253db, HCFO-1223xd, C4H6ClF, HCFO-1232xf, E-HCFO-1241xb, Z-HCFO-1241xb, and HFO-1335.

11. The method according to any one of claims 1 to 10, wherein the compound of formula (I) comprises 1,1-difluoropropylene (HFO-1252zc).

12. The method of claim 11, wherein the product composition comprising the HFO-1252zc further comprises one or more additional compounds selected from the group consisting of propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db.

13. The process of any one of claims 1 to 8, wherein the product of R 1 CX 1 =CY 1 Z 1 is selective by at least about 30 mol%, or at least about 32 mol%, or at least about 34 mol%, or at least about 36 mol%, or at least about 38 mol%, or at least about 40 mol%, and less than 100 mol%.

14. The method according to any one of claims 1 to 8 and 13, wherein the compound of formula (II) comprises 1,2-dichloro-1,2-difluoroethane (HCFC-132).

15. The process of claim 14, wherein the feed composition comprising the HCFC- 132 further comprises one or more additional compounds selected from the group consisting of HCFC-132C (1,1-dichloro-1,2-difluoroethane), HCFC-132a (1,1-dichloro-2,2-difluoroethane), CFO-1112 (1,2-dichloro-1,2-difluoroethylene), CFO-1112a (1,1-dichloro-2,2-difluoroethylene), HCFC-142 (1-chloro-2,2-difluoroethane), HCFC-142a (1-chloro-1,2-difluoroethane), and HFC-152 (1,2-difluoroethane).

16. The process of any one of claims 1 to 8 and 13 to 15, wherein the compound of Formula (I) comprises E / Z-1,2-difluoroethylene (E / Z-HFO-1132).

17. The process of claim 16, wherein the product composition comprises E-HFO- 1132 and Z-HFO-1132, and further comprises one or more additional compounds selected from the group consisting of F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HCFC-142b, HFO-1132a, HFO-1141, E-HCFO-1122a, and Z-HCFO-1122a.

18. The method according to any one of claims 1 to 17, wherein the R 1 CX 1 =CY 1 Z 1 The hydrodechlorination reaction is carried out at a temperature between about 60°C and about 300°C, preferably between about 180°C and about 280°C.

19. The process of any one of claims 1 to 18, wherein the R 1 CX 1 =CY 1 Z 1 hydrodechlorination reaction of Z is conducted at a pressure between about 0 psig and about 200 psig, preferably between about 10 psig and about 150 psig.

20. A composition comprising HCFC-252dc and one or more additional compounds selected from the group consisting of HFC-262fc, HCFO-1233xf, HCFO- 1242zf, acetone, HCFC-262db, HCFC-253db, HCFO-1223xd, C4H6ClF, HCFO- 1232xf, E-HCFO-1241xb, Z-HCFO-1241xb, and HFO-1335.

21. A composition comprising HFO-1252zc and one or more additional compounds selected from the group consisting of propylene, HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomers, HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242, and HCFC-262db.

22. A composition comprising HCFC-132 and one or more additional compounds selected from the group consisting of HCFC-132C (1,1-dichloro-1,2-difluoroethane), HCFC-132a (1,1-dichloro-2,2-difluoroethane), CFO-1112, CFO-1112a, HCFC-142 (1-chloro-2,2-difluoroethane), HCFC-142a (1-chloro-1,2-difluoroethane), and HFC-152.

23. A composition comprising E-HFO-1132, Z-HFO-1132, and one or more additional compounds selected from the group consisting of F-12, FC-13, HCFC-21, CFC-113, HCFC-122a, HCFC-132, HCFC-142b, HFO-1132a, HFO-1141, E-HCFO-1122a, and Z-HCFO-1122a.

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