Process for producing HFO-1252ZC from the thermal decomposition of chlorodifluoromethane

Abstract

The process for producing difluoroolefins, particularly 1,1-difluoropropene (HFO-1252zc), involves the thermal decomposition of chlorodifluoromethane (HCFC-22) with either ethylene or ethanol. Compositions containing HFO-1252zc and their uses are also provided herein.

Description

Technical Field

[0001] (Cross-Reference to Related Application) This application claims priority to U.S. Provisional Patent Application No. 63 / 527,100 filed on July 17, 2023, the entire disclosure of which is incorporated herein by reference.

[0002] (Field of the Invention) The present invention relates to processes, compositions, and uses for producing difluoroolefins. Background Art

[0003] Over the past several decades, the fluorocarbon industry has been working to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which are being phased out as a result of the Montreal Protocol. The response for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents, and propellants. These new compounds, such as the most widely used HFC refrigerants at present, HFC-134a and HFC-125, have a zero ozone depletion potential (ODP), and thus are not affected by current regulations mandating phase-out as a result of the Montreal Protocol. In addition to the problem of ozone depletion, another environmental concern in many of these applications is global warming. HFC refrigerants such as HFC-134a and HFC-125 have a global warming potential (GWP) of 1,300 and 3,170, respectively, according to the United Nations IPCC Fifth Assessment Report (AR5).

[0004] This regulatory environment is constantly evolving, and properties other than ODP and GWP are now being considered. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have a low global warming potential, but also exhibit low flammability or no flammability at all, provide excellent performance in a variety of applications, and meet evolving regulatory standards. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] U.S. Patent Provisional Application No. 63 / 527,100 [Overview of the project] [Problems that the invention aims to solve]

[0006] In this technological field, there is a need for new refrigerants that meet evolving regulations and provide heat transfer and cooling properties that meet or exceed the effectiveness of conventional refrigerants.

[0007] Some fluoropropenes, such as 1,1-difluoropropene (HFO-1252zc, CH3CH=CF2), are such potential new refrigerants. Therefore, there is a need for efficient and effective methods for preparing difluoropropenes such as HFO-1252zc, as well as their intermediates and compositions. [Means for solving the problem]

[0008] The present invention relates to a process for producing difluoroolefins by thermal decomposition of hydrochlorofluorocarbons and hydrocarbons or hydrocarbon derivatives. In some embodiments, the difluoroolefin is difluoropropene. In some embodiments, the difluoroolefin is HFO-1252zc.

[0009] In one embodiment, the present invention relates to a process for producing HFO-1252zc. This process includes contacting chlorodifluoromethane (HCFC-22) with either a hydrocarbon or a hydrocarbon derivative in a heated reaction zone to form HFO-1252zc.

[0010] In one embodiment, the present invention relates to a composition comprising HFO-1252zc and one or more additional compounds selected from chlorodifluoromethane (HCFC-22), ethylene (HC-1150), 2-fluoropropene (HFO-1261yf), 1,1-difluorocyclopropane (HFC-C252), 1,1,1-trifluoropropane (HFC-263fb), 3,3,3-trifluoropropene (HFO-1243zf), octafluorocyclobutane (FC-C318), hexafluorocyclobutane (HFC-C336), hexafluorobutane (HFC-374) isomers, and chlorofluoropropene (HCFO-1251).

[0011] In one embodiment, the present invention relates to a composition comprising HFO-1252zc and one or more additional compounds selected from chlorodifluoromethane (HCFC-22), ethane, ethanal, chloroethane, ethanol, and 3,3,4,4-tetrafluoro-1-butene.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in the field to which the present invention pertains. In the event of any conflict, including definitions, this specification shall prevail. Similar or equivalent methods and materials to those described herein may be used in carrying out or testing embodiments of the present invention, but preferred methods and materials are described below. Furthermore, the materials, methods, and examples are illustrative only and not intended to be limiting. [Modes for carrying out the invention]

[0013] The above summary and the following "Modes for Carrying Out the Invention" and drawings are for illustrative and descriptive purposes only and do not limit the present invention as defined in the attached claims. Any one or more other features and advantages of the embodiments will become apparent from the following "Modes for Carrying Out the Invention," drawings, and claims.

[0014] In one embodiment, the present invention relates to a process for producing HFO-1252zc by thermal decomposition of a mixed feed material containing HCFC-22 and hydrocarbons (such as ethylene) or hydrocarbon derivatives (such as ethanol) at a temperature in the range of 450°C to 800°C in the absence of an additive catalyst. The residence time in the reactor may be about 5 to about 180 seconds.

[0015] Before describing the details of the embodiments described herein, certain terms are defined or clarified as follows:

[0016] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variations thereof are intended to encompass non-exclusive inclusion. For example, a process, method, article, or apparatus containing a list of elements is not necessarily limited to those elements alone, and may also include other elements not expressly listed for or specific to such process, method, article, or apparatus. Furthermore, unless expressly stated otherwise, “or” means an inclusive “or” and not an exclusive “or.” For example, condition A or B satisfies one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0017] The transitional phrase "consisting essentially of" is used to define compositions and methods that include materials, steps, features, components, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, components, or elements do not substantially affect the fundamental and novel characteristics of the claimed invention, in particular the mechanism of operation for achieving any of the desired results of the processes of the invention. The term "consisting essentially of" has an intermediate meaning between "including" and "consisting of".

[0018] The transitional phrase "consisting of" excludes any unspecified elements, steps, or components. In the context of claims, such a phrase would close off the claim to materials other than those listed, excluding impurities normally associated with the materials. If the phrase "consists of" appears within a clause in the body of the claim rather than immediately following the preamble, it is limited to the elements described within that clause only, and other elements are not excluded from the claim as a whole.

[0019] If applicants define an invention or part thereof using non-limiting terms such as "includes," it should be readily understood that (unless otherwise specified) such descriptions should be interpreted to include inventions that essentially consist of or comprise the same term.

[0020] Furthermore, the use of "a" or "an" is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that it has a different meaning.

[0021] When an amount, concentration, or other value or parameter is given as any of a range, a preferred range, or a list of preferred upper values and / or preferred lower values, these shall be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred upper value and any lower range limit or preferred lower value, regardless of whether the ranges are separately disclosed. Where a numerical range is recited herein, unless otherwise indicated, this range is intended to include its endpoints and all integers and fractions within the range.

[0022] As used herein, GC / FID peak area correlates with the amount of a compound present as a percentage of the total area of all detected peaks. FID area percent can be converted to mole percent using calculated or measured response factors.

[0023] As used herein, the term "about" is meant to account for variations due to experimental error (for example, approximately plus or minus 10%, ±1%, ±2%, ±3, ... ±10% of the indicated value). It is to be understood that all measurements reported herein, unless otherwise stated, are modified by the term "about", whether or not the term "about" is explicitly used.

[0024] Particular embodiments disclosed herein relate to processes for producing HFO-1252zc by contacting a hydrochlorofluorocarbon, such as chlorodifluoromethane, with a halogen-free compound including, but not limited to, ethanol or ethylene, at elevated temperature.

[0025] One embodiment disclosed herein relates to pyrolyzing a mixed feed containing hydrochlorofluorocarbon and a hydrocarbon or hydrocarbon derivative in the absence of an added catalyst to produce difluoropropene, more preferably HFO-1252zc.

[0026] In one embodiment, the pyrolysis that achieves the production of HFO-1252zc from hydrochlorofluorocarbons and hydrocarbons or hydrocarbon derivatives is appropriately carried out at a temperature of about 470°C to about 750°C. In another embodiment, the pyrolysis is carried out at a temperature of about 500°C to about 700°C. In yet another embodiment, the pyrolysis is carried out at a temperature of about 550°C to about 650°C. The pyrolysis temperature is the temperature of the gas at approximately the midpoint within the reaction zone.

[0027] In another embodiment, the residence time of the gas in the reaction zone is approximately 5 seconds to approximately 180 seconds. In yet another embodiment, the residence time is one of approximately 5 seconds, approximately 10 seconds, approximately 15 seconds, approximately 20 seconds, approximately 25 seconds, approximately 30 seconds, approximately 35 seconds, approximately 40 seconds, approximately 45 seconds, approximately 50 seconds, approximately 55 seconds, approximately 60 seconds, approximately 65 seconds, approximately 70 seconds, approximately 75 seconds, approximately 80 seconds, approximately 85 seconds, approximately 90 seconds, approximately 95 seconds, or approximately 100 seconds, up to one of approximately 150 seconds, approximately 155 seconds, approximately 160 seconds, approximately 165 seconds, approximately 170 seconds, approximately 175 seconds, or approximately 180 seconds or less.

[0028] In some embodiments, the hydrofluorocarbon is chlorodifluoromethane (HCFC-22, CHF2Cl). In some embodiments, the hydrocarbon is ethylene. In some embodiments, the hydrocarbon derivative is an alcohol hydrocarbon derivative, more preferably ethanol. In some embodiments, the hydrofluorocarbon is HCFC-22 and the hydrocarbon is ethylene. In some embodiments, the hydrofluorocarbon is HCFC-22 and the hydrocarbon derivative is ethanol.

[0029] Specific embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc by thermal decomposition of HCFC-22 at a temperature of about 470°C to about 750°C, preferably at least about 500°C, in the presence of either ethanol or ethylene.

[0030] Pyrolysis can be carried out in the presence of one or more unreactive diluent gases that do not react under pyrolysis conditions. Such unreactive diluent gases include inert gases such as nitrogen, argon, and / or helium. It is noteworthy that the amount of inert gas, such as nitrogen, constitutes approximately 20–80% (by volume or moles) of the material flow supplied to the pyrolysis reactor. Nitrogen is a preferred inert gas because it is relatively inexpensive.

[0031] Specific embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc by exposing a mixture of HCFC-22, ethanol or ethylene, and optionally nitrogen, to a thermal decomposition temperature.

[0032] Embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc by contacting HCFC-22 with either ethanol or ethylene in the presence of heat at temperatures of about 470°C to about 750°C, preferably about 500°C to about 700°C, preferably about 500°C, about 550°C, about 600°C, about 650°C, or about 700°C, and all values ​​and ranges in between.

[0033] Embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc by contacting HCFC-22 with either ethanol or ethylene in the presence of heat at a temperature of about 470°C to about 750°C and a gas residence time in the reaction zone of about 5 to about 180 seconds.

[0034] Specific embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc by heating a mixture of HCFC-22 and either ethanol or ethylene to a temperature of about 470°C to about 750°C, preferably about 500°C to about 700°C, preferably about 500°C, about 550°C, about 600°C, about 650°C, or about 700°C, and all values ​​and ranges in between.

[0035] Specific embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc by heating a mixture of HCFC-22 and either ethanol or ethylene to a temperature of about 470°C to about 750°C with a gas residence time in the reaction zone of about 5 to about 180 seconds.

[0036] Embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc using HCFC-22 in the presence of nitrogen, optionally in the presence of nitrogen, in a molar ratio of about 0.3:1 to about 2:1 for HCFC-22 to ethylene or HCFC-22 to ethanol, in the presence of either ethanol or ethylene. Nitrogen may be present in an amount of 20 to 80% based on the total amount of reactant flow. The reaction is preferably carried out in the absence of a catalyst.

[0037] Embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc by contacting HCFC-22 with HCFC-22 at a temperature of about 500°C to about 750°C in the presence of either ethanol or ethylene, and optionally in the presence of nitrogen, at a molar ratio of about 0.3:1 to about 2:1 for HCFC-22 to ethylene or HCFC-22 to ethanol. Nitrogen may be present in an amount of 20 to 80% based on the total amount of the reactant stream. The reaction is preferably carried out in the absence of a catalyst.

[0038] Embodiments of the present invention disclosed herein relate to a process for producing HFO-1252zc by contacting HCFC-22 with either ethanol or ethylene, and optionally with nitrogen, in a molar ratio of about 0.3:1 to about 2:1 for HCFC-22 to ethylene or HCFC-22 to ethanol, at a temperature of about 500°C to about 750°C for a residence time of about 5 seconds to about 180 seconds. Nitrogen may be present in an amount of 20 to 80% based on the total amount of the reactant stream. The reaction is preferably carried out in the absence of a catalyst.

[0039] One embodiment disclosed herein relates to a process for producing HFO-1252zc by subjecting HCFC-22 and ethanol to thermal decomposition.

[0040] One embodiment disclosed herein relates to a process for producing HFO-1252zc by subjecting HCFC-22 and ethanol to thermal decomposition in the presence of a nitrogen diluent, wherein the amount of nitrogen is preferably 20-80% of the feed material stream containing HCFC-22, ethanol, and N2.

[0041] One embodiment disclosed herein relates to a process for producing HFO-1252zc by thermally decomposing HCFC-22 and ethanol in the presence of a diluent such as nitrogen, wherein the molar ratio of HCFC-22 to ethanol is about 0.3:1 to about 2:1.

[0042] In some embodiments, the thermal decomposition reaction of HCFC-22 and ethanol to form HFO-1252zc is carried out at a pressure of about 0 psig to about 300 psig, and the pressure is not limited to 1 psig, 2 psig, 3 psig, 4 psig, 5 psig, 10 psig, 15 psig, 20 psig, 25 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, 100 psig, 125 psig, 150 psig, 175 psig, 200 psig, 250 psig, or 300 psig, and those This includes all values ​​and ranges between 0, 1 psig, 2 psig, 3 psig, 4 psig, 5 psig, 10 psig, 15 psig, 20 psig, 25 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, 100 psig, 125 psig, or 150 psig and between 175 psig, 200 psig, 250 psig, or 300 psig, or between approximately 0.5 psig and approximately 5 psig, or between approximately 0.5 psig and approximately 2.5 psig, or between approximately 0.5 and approximately 1.5 psig, including all values ​​and ranges in between.

[0043] One embodiment disclosed herein is a process for producing HFO-1252zc by thermally decomposing HCFC-22 and ethanol in a molar ratio of about 0.3:1 to about 2:1 in the presence of a diluent such as nitrogen, wherein the amount of nitrogen is 20 to 80% of the feed material stream containing HCFC-22, ethanol, and N2, and the reaction pressure is about 0 psig to about 300 psig, but is not limited to 1 psig, 2 psig, 3 psig, 4 psig, 5 psig, 10 psig, 15 psig, 20 psig, 25 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, 100 psig, 125 psig, 150 psig This includes all values ​​and ranges between sig, 175psig, 200psig, 250psig, or 300psig, and 0, 1psig, 2psig, 3psig, 4psig, 5psig, 10psig, 15psig, 20psig, 25psig, 30psig, 40psig, 50psig, 60psig, 70psig, 80psig, 90psig, 100psig, 125psig, or 150psig and between 175psig, 200psig, 250psig, or 300psig, or between approximately 0.5psig and approximately 5psig, or between approximately 0.5psig and approximately 2.5psig, or between approximately 0.5 and approximately 1.5psig.

[0044] One embodiment disclosed herein relates to a process for producing HFO-1252zc by subjecting HCFC-22 and ethylene to thermal decomposition.

[0045] One embodiment disclosed herein relates to a process for producing HFO-1252zc by subjecting HCFC-22 and ethylene to thermal decomposition in the presence of a nitrogen diluent, wherein the amount of nitrogen is preferably 20-80% of the feed material stream containing HCFC-22, ethylene, and N2.

[0046] One embodiment disclosed herein relates to a process for producing HFO-1252zc by thermally decomposing HCFC-22 and ethylene in the presence of a diluent such as nitrogen, wherein the ratio of HCFC-22 to ethylene is about 0.3:1 to about 2:1.

[0047] In some embodiments, the thermal decomposition reaction of HCFC-22 and ethylene to form HFO-1252zc is carried out at a pressure of about 0 psig to about 300 psig, and the pressure is not limited to 1 psig, 2 psig, 3 psig, 4 psig, 5 psig, 10 psig, 15 psig, 20 psig, 25 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, 100 psig, 125 psig, 150 psig, 175 psig, 200 psig, 250 psig, or 300 psig, and in between. This includes all values ​​and ranges, including 0, 1 psig, 2 psig, 3 psig, 4 psig, 5 psig, 10 psig, 15 psig, 20 psig, 25 psig, 30 psig, 40 psig, 50 psig, 60 psig, 70 psig, 80 psig, 90 psig, 100 psig, 125 psig, or 150 psig, and between 175 psig, 200 psig, 250 psig, or 300 psig, or between approximately 0.5 psig and approximately 5 psig, or between approximately 0.5 psig and approximately 2.5 psig, or between approximately 0.5 and approximately 1.5 psig, and all values ​​and ranges in between.

[0048] One embodiment disclosed herein relates to a process for producing HFO-1252zc by thermally decomposing HCFC-22 and ethylene in a molar ratio of about 0.3:1 to about 2:1 in the presence of a diluent such as nitrogen, wherein the amount of nitrogen is 20 to 80% of the feed material stream containing HCFC-22, ethylene, and N2, and the reaction pressure is about 0 psig to about 300 psig.

[0049] Any of the processes described herein further include a step of recovering HFO-1252zc. In some embodiments, any of the processes disclosed herein may further include a step of separating, recovering, and recycling an unconverted feed selected from one of chlorodifluoromethane, ethanol, and ethene (e.g., into a heated reaction zone).

[0050] Specific embodiments of the present invention disclosed herein are compositions comprising, essentially consisting of, or comprising HFO-1252zc and one or more additional compounds specified in Table 1 other than HFO-1252zc.

[0051] [Table 1]

[0052] Embodiments disclosed herein include HFO-1252zc and HCFC-22, ethylene (HC-1150, CH2=CH2), 2-fluoropropene (HFO-1261yf, CH2=CF-CH3), 1,1-difluorocyclopropane (HFC-C252, cyclic CF2-CH2CH2), 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3), 3,3,3-trifluoropropene (HF The present invention relates to compositions comprising, or essentially composed of, one or more additional compounds selected from O-1243zf (CF3CH=CH2), octafluorocyclobutane (FC-C318, cyclic CF2CF2CF2CF2), hexafluorocyclobutane (HFC-C336, cyclic CF2CF2CF2CH2), C4H6F4 (HFC-374) isomers, and C3H4ClF (HCFO-1251).

[0053] Embodiments disclosed herein relate to compositions comprising, consisting of, or essentially consisting of HFO-1252zc and one or more additional compounds selected from HCFC-22, HC-1150, HFO-1261yf, HFC-C252, HFC-263fb, FC-C318, HFC-C336, HFC-374 isomers, and HCFO-1251.

[0054] Embodiments disclosed herein relate to compositions comprising, consisting of, or essentially consisting of HFO-1252zc and one or more additional compounds selected from the isomers of HC-22, HC-1150, HFC-263fb, HFC-C252, FC-C318, HFC-C336, and HFC-374.

[0055] Embodiments disclosed herein relate to compositions comprising, consisting of, or essentially consisting of HFO-1252zc and one or more additional compounds selected from the isomers of HC-1150, HCFC-22, HFO-1243zf, HFC-263fb, FC-C318, HFC-C336, and HFC-374.

[0056] Embodiments disclosed herein relate to compositions comprising, consisting of, or essentially consisting of HFO-1252zc and one or more additional compounds selected from HCFC-22, ethane, ethanal, chloroethane, ethanol, and 3,3,4,4-tetrafluoro-1-butene.

[0057] Embodiments disclosed herein relate to compositions comprising, consisting of, or essentially consisting of HFO-1252zc and one or more additional compounds selected from chloroethane, ethanol, and 3,3,4,4-tetrafluoro-1-butene.

[0058] In preferred embodiments, compositions according to the present invention are free from or substantially free from Group A fluorinated substances. In one embodiment, as used herein, “Group A fluorinated substance” includes a substance that (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon atom is not bonded to H / Cl / Br / I) and (ii) meets the criteria for persistence in soil / sediments and water. The criteria are set forth in Annex XIII (Section 1.1.1) of the European Union's REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, accessed May 2, 2023), which is referenced in the Regulatory Report Annex XV dated March 22, 2023, and whose disclosures are incorporated into this document by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed May 2, 2023).

[0059] In another embodiment, as used herein, “Group A fluorinated substance” has a Henry’s Law constant of 250 Pa * m 3 The amount is less than or equal to / mol and contains any substance that includes at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (the carbon is not bonded to H / Cl / Br / I).

[0060] In the embodiments, TFA is an example of a Group A fluorinated substance, but is not limited to it.

[0061] With regard to the presence of Group A fluorinated substances in this composition, the term "not present" as used herein means that the amount of such substances in the composition is so low that it is undetectable, but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of gas or liquid samples, and / or ion chromatography by analysis of water samples after bubbling a thermal fluid through water. Such methodologies are well known to those skilled in the art. With regard to the presence of Group A fluorinated substances in this composition, the phrase "substantially absent" as used herein means that the amount of such substances in the composition can be determined by gas chromatography (GC) techniques, such as gas chromatography with a flame ionization detector or electron capture detector, or GC coupled with a mass detector (gas chromatography / mass spectral (GC / MS) method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS) techniques, or by high-performance liquid chromatography (HPLC) or high-performance liquid chromatography-mass spectrometry (high-performance liquid chromatography-mass spectrometry). This means that, when measured by spectrometry (HPLC-MS) techniques, the TFA standard is greater than 0% by weight and less than or equal to 5% by weight, greater than 0% by weight and less than or equal to 4% by weight, greater than 0% by weight and less than or equal to 3% by weight, greater than 0% by weight and less than or equal to 2% by weight, greater than 0% by weight and less than or equal to 1% by weight, and all values ​​and ranges in between. The TFA analytical standard can be used with either gas chromatography or ion chromatography and is available, for example, from Sigma Aldrich.

[0062] In preferred embodiments, the decomposition products of the composition according to the present invention are free from or substantially free from Group A fluorinated substances. With respect to the formation of Group A fluorinated substances as decomposition products of the composition, the term “free from” as used herein means that the theoretical molar yield of such substances in the air, soil / sediment and water environmental compartments generated during the tropospheric decomposition of the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by GC techniques, e.g., GC or GC / MS methods using flame ionization detectors or electron capture detectors, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. With respect to the formation of Group A fluorinated substances by this composition, the phrase "substantially free" as used herein means that the theoretical molar yield of such substances in the air, soil / sediment, and water environmental compartments generated during the tropospheric decomposition of the composition is greater than 0% and 5% or less, greater than 0% and 4% or less, greater than 0% and 3% or less, greater than 0% and 2% or less, greater than 0% and 1% or less, and all values ​​and ranges in between, when measured by GC techniques, e.g., GC or GC / MS using a flame ionization detector or electron capture detector, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.

[0063] Specific embodiments of the present invention disclosed herein relate to compositions containing, essentially derived from, or comprising HFO-1252zc, and not containing or substantially containing Group A fluorinated substances. In some embodiments, the compositions of the present invention contain, essentially derived from, or comprising HFO-1252zc, and the decomposition products of such compositions are not containing or substantially containing Group A fluorinated substances as defined herein.

[0064] Certain embodiments of the present invention disclosed herein relate to compositions comprising, essentially comprising, or comprising HFO-1252zc and one or more additional compounds, which are free from or substantially free from Group A fluorinated substances. In some embodiments, the compositions of the present invention comprise, essentially comprising, or comprising HFO-1252zc and one or more additional compounds, and the decomposition products of such compositions are free from or substantially free from Group A fluorinated substances as defined herein.

[0065] As disclosed herein, the conversion of HCFC-22 is carried out at temperatures above approximately 500°C, i.e., under thermal decomposition conditions. Thermal decomposition, as used herein, means a chemical change that occurs by heating in the absence of a catalyst. A thermal decomposition reactor generally includes three zones: a) a preheating zone in which the reactants are brought close to the reaction temperature; b) a reaction zone in which the reactants reach the reaction temperature and are at least partially thermally decomposed to form the product and any by-products; and c) a quenching zone in which the flow leaving the reaction zone is cooled to stop the thermal decomposition reaction. Laboratory-scale reactors have a reaction zone, but the preheating and quenching zones may be omitted.

[0066] The reactor for pyrolysis may be of any shape suitable for the process, but is preferably a cylindrical tube, either straight or coiled. Although not critical, such reactors typically have an inner diameter of about 1.3 to about 5.1 cm (about 0.5 to about 2 inches). Heat is applied to the outside of the tube, and the chemical reaction takes place inside the tube. The reactor and its associated feed lines, outflow lines and associated units should be constructed of materials resistant to hydrogen fluoride, at least with respect to the surfaces exposed to the reactants and products. Typical constituent materials include stainless steel, particularly austenitic stainless steel; well-known high-nickel alloys such as nickel-copper alloys marketed under the trademark Monel® by Special Metals Corp. (New Hartford, New York); nickel-based alloys marketed under the trademark Hastelloy® by Haynes International (Kokomo, Indiana) (hereinafter referred to as "Hastelloy®"); nickel-chromium alloys marketed under the trademark Inconel® by Special Metals Corp.; and copper-clad steel.

[0067] If the reactor is exposed to high temperatures, the reactor may be constructed of two or more materials. For example, the outer surface layer of the reactor should be selected for its ability to maintain structural integrity and withstand corrosion at the thermal decomposition temperature, while the inner surface layer of the reactor should be selected from a material that is resistant to attack by reactants and products, i.e., inert to reactants and products. In the process of the present invention, the product hydrogen fluoride is corrosive to certain materials. Therefore, the reactor may be constructed from an outer material selected for its physical strength at high temperatures, and an inner material selected for its resistance to corrosion by reactants and products at the thermal decomposition temperature.

[0068] In some embodiments, the free volume of the reaction zone is at least about 80%, preferably at least about 90%, and more preferably about 95%. The free volume is the volume of the reaction zone minus the volume of the material constituting the reactor packing.

[0069] Several reactor configurations are possible, including, but not limited to, packed-bed tube or column reactors operated in batch, semi-batch, or continuous mode. In addition to the reactors disclosed herein, preheaters and vaporizers, heat exchangers, feed lines and discharge lines, units related to mass transfer, contact vessels (premixers), distillation columns, and valves related to the reactors, heat exchangers, vessels, columns, and units used in the processes of the various embodiments disclosed herein, must be constructed of corrosion-resistant materials.

[0070] Next, embodiments of the present invention will be described with reference to the following examples. [Examples]

[0071] Example 1: Pyrolysis of HCFC-22 by ethylene to produce HFO-1252zc In a 12-inch long, 1 / 2-inch outer diameter Inconel 600 reactor, the reactor was heated to 550°C, 600°C, and 650°C under N2 purging. HCFC-22, ethylene, and N2 were supplied to the reactor through a mass flow control device. The reaction test conditions are listed in Table 2 below. The reactor effluent was analyzed by online GC-MS-FID. The analysis results are listed in Tables 3-5 below.

[0072] [Table 2]

[0073] [Table 3]

[0074] [Table 4]

[0075] [Table 5]

[0076] Example 2: Thermal decomposition of HCFC-22 using ethanol to produce HFO-1252zc The reaction was conducted in a 12-inch long, 1 / 2-inch outer diameter Inconel 600 reactor. Under N2 purging, the reactor was heated to 550°C. HCFC-22 and N2 were supplied to the reactor through a mass flow control device. Ethanol was supplied by pump. The reaction test conditions are listed in Table 6 below. The reactor effluent was analyzed by online GC-MS-FID. The analysis results are listed in Table 6 below.

[0077] [Table 6]

[0078] [Table 7]

[0079] Other embodiments Embodiment 1. A process for producing 1,1-difluoropropene (HFO-1252zc), comprising the step of contacting chlorodifluoromethane (HCFC-22) with either a hydrocarbon or a hydrocarbon derivative in a heated reaction zone to form HFO-1252zc.

[0080] Embodiment 2. The process according to Embodiment 1, wherein the step of contacting HCFC-22 with a hydrocarbon or hydrocarbon derivative is carried out in the absence of an additive catalyst.

[0081] Embodiment 3. The process according to any one of Embodiments 1 to 2, wherein the reaction zone is heated to a temperature of 500°C to 750°C, preferably selected from one of 550°C, 575°C, 600°C, 625°C, and 650°C.

[0082] Embodiment 4. The process according to any one of Embodiments 1 to 3, wherein HCFC-22 and a hydrocarbon or hydrocarbon derivative are vaporized before contact in the reaction zone.

[0083] Embodiment 5. The process according to any one of Embodiments 1 to 4, wherein HCFC-22 is supplied in a molar excess to a heated reaction zone.

[0084] Embodiment 6. The process according to any one of Embodiments 1 to 5, wherein a diluent is optionally supplied to the reaction zone.

[0085] Embodiment 7. The process according to any one of Embodiments 1 to 6, wherein a heated reaction zone is subjected to thermal decomposition of HCFC-22 and hydrocarbons or hydrocarbon derivatives in the presence of a diluent.

[0086] Embodiment 8. The process according to any one of Embodiments 1 to 7, wherein a heated reaction zone is subjected to thermal decomposition of HCFC-22 and hydrocarbons or hydrocarbon derivatives in the presence of a diluent, and the molar ratio of HCFC-22 to hydrocarbons or HCFC-22 to hydrocarbon derivatives is about 0.3:1 to 2:1.

[0087] Embodiment 9. The process according to any one of Embodiments 1 to 8, wherein the hydrocarbon comprises ethylene, or the hydrocarbon derivative comprises ethanol.

[0088] Embodiment 10. The process according to Embodiment 9, wherein the hydrocarbon is ethylene, the diluent is supplied to a heated reaction zone, and the heated reaction zone is at a temperature sufficient to thermally decompose HFC-22 and ethylene.

[0089] Embodiment 11. The process according to Embodiment 10, wherein the contact step is performed at a pressure in the range of 0 to 300 psig.

[0090] Embodiment 12. The process according to Embodiment 9, wherein the hydrocarbon derivative is ethanol, the diluent is supplied to a heated reaction zone, and the heated reaction zone is at a temperature sufficient to thermally decompose HFC-22 and ethanol.

[0091] Embodiment 13. The process according to Embodiment 12, wherein the contact step occurs at a pressure in the range of 0 to 300 psig.

[0092] Embodiment 14. The process according to Embodiment 10, wherein a heated reaction zone is exposed to HCFC-22 and ethylene at a pressure ranging from 0 to 300 psig in the presence of a diluent.

[0093] Embodiment 15. The process according to Embodiment 12, wherein a heated reaction zone is exposed to HCFC-22 and ethanol at a pressure ranging from 0 to 300 psig in the presence of a diluent.

[0094] Embodiment 16. The process according to any one of Embodiments 1 to 15, wherein a heated reaction zone is defined by a pyrolysis reactor.

[0095] Embodiment 17. The process according to any one of Embodiments 1 to 16, wherein the heated reaction zone does not contain an added catalyst.

[0096] Embodiment 18. The process according to any one of Embodiments 1 to 17, wherein the heated reaction zone is empty and does not contain an added catalyst.

[0097] Embodiment 19. The process according to any one of Embodiments 1 to 18, wherein the heated reaction zone contains an inert support and does not include an added catalyst.

[0098] Embodiment 20. The process according to any one of Embodiments 1 to 19, further comprising the step of recovering HFO-1252zc.

[0099] Embodiment 21. The process according to any one of Embodiments 1 to 20, further comprising the step of separating, recovering and recycling an unconverted feed selected from one of chlorodifluoromethane, ethanol, and ethene.

[0100] Embodiment 22. A system for carrying out any one of the processes of Embodiments 1 to 21, comprising: a specified source of HCFC-22; a specified source of hydrocarbons such as ethylene or hydrocarbon derivatives such as ethanol; a vaporizer connected to one of the specified sources; and a flow pyrolysis reactor configured to produce HFO-1252zc by contacting HCFC-22, hydrocarbons or hydrocarbon derivatives, and optionally nitrogen for 5 to 180 seconds at a temperature of 500°C to 700°C.

[0101] Embodiment 23. A composition produced by the process described in any one of Embodiments 1 to 21 or the system described in Embodiment 22.

[0102] Embodiment 24.1,1-Difluoropropene (HFO-1252zc) and, One or more additional compounds selected from the group consisting of chlorodifluoromethane (HCFC-22), ethylene (HC-1150), 2-fluoropropene (HFO-1261yf), 1,1-difluorocyclopropane (HFC-C252), 1,1,1-trifluoropropane (HFC-263fb), 3,3,3-trifluoropropene (HFO-1243zf), octafluorocyclobutane (FC-C318), hexafluorocyclobutane (HFC-C336), hexafluorobutane (HFC-374) isomers, and chlorofluoropropene (HCFO-1251) and A composition containing the following:

[0103] Embodiment 25. The composition according to Embodiment 24, wherein one or more additional compounds are selected from the group consisting of HCFC-22, HC-1150, HFO-1261yf, HFC-C252, HFC-263fb, FC-C318, HFC-C336, HFC-374 isomers, and HCFO-1251.

[0104] Embodiment 26. The composition according to Embodiment 24, wherein one or more additional compounds are selected from the group consisting of HC-22, HC-1150, HFC-263fb, HFC-C252, FC-C318, HFC-C336, and HFC-374 isomers.

[0105] Embodiment 27. The composition according to Embodiment 24, wherein one or more additional compounds are selected from the group consisting of HC-1150, HCFC-22, HFO-1243zf, HFC-263fb, FC-C318, HFC-C336, and HFC-374 isomers.

[0106] Embodiment 28. The composition according to any one of Embodiments 24 to 27, wherein at least one of the additional compounds is fluorocyclopropane or fluorocyclobutane, preferably at least one of hexafluorocyclobutane and octafluorocyclobutane.

[0107] Embodiment 29.1,1-Difluoropropene (HFO-1252zc) and, One or more additional compounds selected from the group consisting of chlorodifluoromethane (HCFC-22), ethane, ethanal, chloroethane, ethanol, and 3,3,4,4-tetrafluoro-1-butene. A composition containing the following:

[0108] Embodiment 30. The composition according to Embodiment 29, wherein one or more additional compounds are selected from the group consisting of chloroethane, ethanol, and 3,3,4,4-tetrafluoro-1-butene.

[0109] Embodiment 31. The composition according to any one of Embodiments 23 to 30, wherein the composition does not contain or substantially contains a fluorinated substance of Group A.

[0110] Embodiment 32. The composition according to any one of Embodiments 23 to 31, wherein the decomposition products of the composition do not contain or substantially contain Group A fluorinated substances.

[0111] While certain aspects, embodiments, and principles have been described above, it should be understood that this specification is for illustrative purposes only and does not limit the scope of the present invention or the appended claims. The various aspects, embodiments, and principles described above may be used individually or in combination with each other.

Claims

1. A process for producing 1,1-difluoropropene (HFO-1252zc), comprising the step of contacting chlorodifluoromethane (HCFC-22) with either a hydrocarbon or a hydrocarbon derivative in a heated reaction zone to form HFO-1252zc.

2. The process according to claim 1, wherein the step of contacting HCFC-22 with the hydrocarbon or hydrocarbon derivative is carried out in the absence of an additive catalyst.

3. The process according to claim 1 or 2, wherein the reaction zone is heated to a temperature of 500°C to 750°C, preferably a temperature selected from one of 550°C, 575°C, 600°C, 625°C, and 650°C.

4. The process according to any one of claims 1 to 3, wherein HCFC-22 and a hydrocarbon or hydrocarbon derivative are vaporized before contact in the reaction zone.

5. The process according to any one of claims 1 to 4, wherein HCFC-22 is supplied to the heated reaction zone in a molar excess.

6. The process according to any one of claims 1 to 5, wherein a diluent is optionally supplied to the reaction zone.

7. The process according to any one of claims 1 to 6, wherein the heated reaction zone is subjected to thermal decomposition of the HCFC-22 and the hydrocarbon or hydrocarbon derivative in the presence of a diluent.

8. The process according to any one of claims 1 to 7, wherein the heated reaction zone is subjected to thermal decomposition of the HCFC-22 and the hydrocarbon or hydrocarbon derivative in the presence of a diluent, and the molar ratio of HCFC-22 to hydrocarbon or HCFC-22 to hydrocarbon derivative is about 0.3:1 to 2:

1.

9. The process according to any one of claims 1 to 8, wherein the hydrocarbon comprises ethylene, or the hydrocarbon derivative comprises ethanol.

10. The process according to claim 9, wherein the hydrocarbon is ethylene, a diluent is supplied to the heated reaction zone, and the heated reaction zone is at a temperature sufficient to thermally decompose HFC-22 and ethylene.

11. The process according to claim 10, wherein the contact step is performed at a pressure in the range of 0 to 300 psig.

12. The process according to claim 9, wherein the hydrocarbon derivative is ethanol, a diluent is supplied to the heated reaction zone, and the heated reaction zone is at a temperature sufficient to thermally decompose HFC-22 and ethanol.

13. The process according to claim 12, wherein the contact step is performed at a pressure in the range of 0 to 300 psig.

14. The process according to claim 10, wherein the heated reaction zone is exposed to the HCFC-22 and ethylene at a pressure in the range of 0 to 300 psig in the presence of a diluent.

15. The process according to claim 12, wherein the heated reaction zone is exposed to the HCFC-22 and ethanol at a pressure in the range of 0 to 300 psig in the presence of a diluent.

16. The process according to any one of claims 1 to 15, wherein the heated reaction zone is defined by a pyrolysis reactor.

17. The process according to any one of claims 1 to 16, wherein the heated reaction zone does not contain an additive catalyst.

18. The process according to any one of claims 1 to 17, wherein the heated reaction zone is empty and does not contain an additive catalyst.

19. The process according to any one of claims 1 to 18, wherein the heated reaction zone contains an inert support and does not contain an added catalyst.

20. The process according to any one of claims 1 to 19, further comprising the step of recovering HFO-1252zc.

21. The process according to any one of claims 1 to 20, further comprising the steps of separating, recovering and recycling an unconverted feed material selected from chlorodifluoromethane, ethanol, and ethene.

22. A system for carrying out the process of any one of claims 1 to 21, comprising: a specified source of HCFC-22; a specified source of hydrocarbons such as ethylene or hydrocarbon derivatives such as ethanol; a vaporizer connected to one of the specified sources; and a flow-through pyrolysis reactor configured to produce HFO-1252zc by contacting the HCFC-22, the hydrocarbon or hydrocarbon derivative, and optionally nitrogen for 5 to 180 seconds at a temperature of 500°C to 700°C.

23. A composition produced by the process described in any one of claims 1 to 21 or the system described in claim 22.

24. 1,1-difluoropropene (HFO-1252zc) and, One or more additional compounds selected from the group consisting of chlorodifluoromethane (HCFC-22), ethylene (HC-1150), 2-fluoropropene (HFO-1261yf), 1,1-difluorocyclopropane (HFC-C252), 1,1,1-trifluoropropane (HFC-263fb), 3,3,3-trifluoropropene (HFO-1243zf), octafluorocyclobutane (FC-C318), hexafluorocyclobutane (HFC-C336), hexafluorobutane (HFC-374) isomers, and chlorofluoropropene (HCFO-1251) and A composition containing the following:

25. The composition according to claim 24, wherein the one or more additional compounds are selected from the group consisting of HCFC-22, HC-1150, HFO-1261yf, HFC-C252, HFC-263fb, FC-C318, HFC-C336, HFC-374 isomers, and HCFO-1251.

26. The composition according to claim 24, wherein the one or more additional compounds are selected from the group consisting of HC-22, HC-1150, HFC-263fb, HFC-C252, FC-C318, HFC-C336, and HFC-374 isomers.

27. The composition according to claim 24, wherein the one or more additional compounds are selected from the group consisting of HC-1150, HCFC-22, HFO-1243zf, HFC-263fb, FC-C318, HFC-C336, and HFC-374 isomers.

28. The composition according to any one of claims 24 to 27, wherein at least one of the additional compounds is fluorocyclopropane or fluorocyclobutane, preferably at least one of hexafluorocyclobutane and octafluorocyclobutane.

29. 1,1-difluoropropene (HFO-1252zc) and, One or more additional compounds selected from the group consisting of chlorodifluoromethane (HCFC-22), ethane, ethanal, chloroethane, ethanol, and 3,3,4,4-tetrafluoro-1-butene. A composition containing the following:

30. The composition according to claim 29, wherein the one or more additional compounds are selected from the group consisting of chloroethane, ethanol, and 3,3,4,4-tetrafluoro-1-butene.

31. The composition according to any one of claims 23 to 30, wherein the composition does not contain or substantially contains a fluorinated substance of group A.

32. The composition according to any one of claims 23 to 31, wherein the decomposition products of the composition do not contain or substantially contain group A fluorinated substances.

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