WO2025019202A2 - Procédé de fabrication de hfo-1252zc par pyrolyse de chlorodifluorométhane - Google Patents

Procédé de fabrication de hfo-1252zc par pyrolyse de chlorodifluorométhane Download PDF

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WO2025019202A2
WO2025019202A2 PCT/US2024/037158 US2024037158W WO2025019202A2 WO 2025019202 A2 WO2025019202 A2 WO 2025019202A2 US 2024037158 W US2024037158 W US 2024037158W WO 2025019202 A2 WO2025019202 A2 WO 2025019202A2
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psig
hfc
hcfc
hfo
reaction zone
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WO2025019202A3 (fr
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Xuehui Sun
Robert D. Lousenberg
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Chemours Co FC LLC
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Chemours Co FC LLC
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Priority to AU2024295977A priority Critical patent/AU2024295977A1/en
Priority to CN202480045987.0A priority patent/CN121487911A/zh
Publication of WO2025019202A2 publication Critical patent/WO2025019202A2/fr
Publication of WO2025019202A3 publication Critical patent/WO2025019202A3/fr
Priority to MX2026000335A priority patent/MX2026000335A/es
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons

Definitions

  • HFC refrigerants such as HFC-134a and HFC-125 respectively have global warming potentials (GWP) of 1,300 and 3,170 according to the UN's IPCC Fifth Assessment Report (AR5).
  • GWP global warming potentials
  • AR5 UN's IPCC Fifth Assessment Report
  • the present invention relates to processes of making a difluoroolefin by pyrolysis of a hydrochlorofluorocarbon and hydrocarbon or hydrocarbon derivative.
  • the difluoroolefin is a difluoropropene.
  • the difluoroolefin is HFO-1252zc.
  • the invention relates to a process for producing HFO- 1252zc. The process comprises contacting chlorodifluoromethane (HCFC-22) and one of a hydrocarbon and a hydrocarbon derivative in a heated reaction zone to form HFO-1252zc.
  • the invention relates to a composition
  • 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).
  • chlorodifluoromethane HCFC-22
  • ethylene HC-1150
  • 2-fluoropropene HFO-1261yf
  • 1,1- difluorocyclopropane HFC-
  • the invention relates to a composition
  • 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.
  • the present invention relates to processes of making HFO- 1252zc by pyrolysis of a mixed feed containing HCFC-22 and a hydrocarbon (such as ethylene) or a hydrocarbon derivative (such as ethanol), in the absence of added catalyst, by pyrolysis at temperatures ranging from 450°C to 800°C.
  • a hydrocarbon such as ethylene
  • a hydrocarbon derivative such as ethanol
  • Residence time in the reactor may span from about 5 seconds to about 180 seconds.
  • certain terms are defined or clarified as follows.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or.
  • a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B is true (or present).
  • the transitional phrase “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention.
  • HFO- 1252zc As used herein, the term “about” is meant to account for variations due to experimental error (e.g., plus or minus approximately 10% of the indicated value. ⁇ 1%, ⁇ 2%, ⁇ 3, ... ⁇ 10%). All measurements reported herein are understood to be modified by the term “about,” whether or not the term is explicitly used, unless explicitly stated otherwise.
  • Certain embodiments disclosed herein relate to a process of making HFO- 1252zc by contacting a hydrochlorofluorocarbon, such as chlorodifluoromethane, with a halogen-free compound, including but not limited to ethanol or ethylene, at an elevated temperature.
  • One embodiment disclosed herein relates to the pyrolysis of a mixed feed containing a hydrochlorofluorocarbon and a hydrocarbon or hydrocarbon derivative, in the absence of added catalyst, to produce a difluoropropene, and more preferably HFO-1252zc.
  • the pyrolysis which accomplishes the production of HFO-1252zc from the hydrochlorofluorocarbon and hydrocarbon or hydrocarbon derivative is suitably conducted at a temperature between about 470°C to about 750°C. In another embodiment, the pyrolysis is conducted at a temperature of from about 500°C to about 700°C.
  • the pyrolysis is conducted at a temperature of from about 550°C to about 650°C.
  • the pyrolysis temperature is the temperature of the gases inside the reaction zone at about the mid-point.
  • the residence time of gases in the reaction zone is from about 5 second to about 180 seconds.
  • the residence time is one of about 5 seconds, about 10 seconds, about 15 seconds, about 20 seconds, about 25 seconds, about 30 seconds, about 35 seconds, about 40 seconds, about 45 seconds, about 50 seconds, about 55 seconds, about 60 seconds, about 65 seconds, about 70 seconds, about 75 seconds, about 80 seconds, about 85 seconds, about 90 seconds, about 95 seconds, or about 100 seconds to one of less than about 150 seconds, less than about 155 seconds, less than about 160 seconds, less than about 165 seconds, less than about 170 seconds, less than about 175 seconds or less than or equal to about 180 seconds.
  • the hydrofluorocarbon is chlorodifluoromethane (HCFC-22, CHF2Cl). In some embodiments, the hydrocarbon is ethylene.
  • the hydrocarbon derivative is an alcohol hydrocarbon derivative, and more preferably ethanol.
  • the hydrofluorocarbon is HCFC-22 and the hydrocarbon is ethylene.
  • the hydrofluorocarbon is HCFC-22 and the hydrocarbon derivative is ethanol.
  • the pyrolysis can be conducted in the presence of one or more unreactive diluent gases, which diluent gases do not react under the pyrolysis conditions.
  • unreactive diluent gases include the inert gases nitrogen, argon, and/or helium.
  • the amount of inert gas, such as nitrogen makes up about 20-80% (by volume or mol) of the feed stream to the pyrolysis reactor.
  • Nitrogen is a preferred inert gas because of its comparatively low cost.
  • Embodiments of the invention disclosed herein relate to processes of making HFO-1252zc by contacting HCFC-22 and one of ethanol or ethylene in the presence of heat at a temperature between about 470°C to about 750°C, preferably at a temperature between about 500°C and about 700°C, preferably at a temperature of about 500°C, about 550°C, about 600°C, about 650°C or about 700°C, and all values and ranges therebetween.
  • Embodiments of the invention disclosed herein relate to processes of making HFO-1252zc by contacting HCFC-22 and one of ethanol or ethylene in the presence of heat at a temperature between about 470°C to about 750°C and with a residence time of gases in the reaction zone of from about 5 to about 180 seconds.
  • Certain embodiments of the invention disclosed herein relate to processes of making HFO-1252zc by heating a mixture of HCFC-22 and one of ethanol or ethylene to a temperature between about 470°C to about 750°C, preferably at a temperature between about 500°C and about 700°C, preferably at a temperature of about 500°C, about 550°C, about 600°C, about 650°C or about 700°C, and all values and ranges therebetween.
  • Certain embodiments of the invention disclosed herein relate to processes of making HFO-1252zc by heating a mixture of HCFC-22 and one of ethanol or ethylene to a temperature between about 470°C to about 750°C in a reaction zone with a residence time of gases in the reaction zone of from about 5 to about 180 seconds.
  • Embodiments of the invention disclosed herein relate to processes of making HFO-1252zc with HCFC-22 in the presence of one of ethanol or ethylene, at a mole ratio of HCFC-22:ethylene or HCFC-22:ethanol of about 0.3:1 to about 2:1, optionally in the presence of nitrogen.
  • Nitrogen can be present in an amount of 20- 80% based on the total amount of the reactant stream.
  • Embodiments of the invention disclosed herein relate to processes of making HFO-1252zc by contacting HCFC-22 in the presence of one of ethanol or ethylene, optionally in the presence of nitrogen, at mole ratio of HCFC-22:ethylene or HCFC-22:ethanol of about 0.3:1 to about 2:1 at a temperature between about 500°C and about 750°C. Nitrogen can be present in an amount of 20-80% based on the total amount of the reactant stream.
  • the reaction is preferably carried out in the absence of a catalyst.
  • Embodiments of the invention disclosed herein relate to processes of making HFO-1252zc by contacting HCFC-22 in the presence of one of ethanol or ethylene, optionally in the presence of nitrogen, at mole ratio of HCFC-22:ethylene or HCFC-22:ethanol of about 0.3:1 to about 2:1 at temperature between about 500°C and about 750°C with a residence time of about 5 seconds to about 180 seconds.
  • Nitrogen can be present in an amount of 20-80% based on the total amount of the reactant stream.
  • the reaction is preferably carried out in the absence of a catalyst.
  • One embodiment disclosed herein relate to a process of making HFO- 1252zc by subjecting HCFC-22 and ethanol to pyrolysis.
  • One embodiment disclosed herein relate to a process of making HFO- 1252zc by subjecting HCFC-22 and ethanol in the presence of a nitrogen diluent to pyrolysis, preferably wherein the amount of nitrogen is between 20 and 80% of the feed stream comprising HCFC-22, ethanol, and N2.
  • One embodiment disclosed herein relate to a process of making HFO- 1252zc by subjecting HCFC-22 and ethanol, in the presence of a diluent such as nitrogen, to pyrolysis, wherein the ratio of HCFC-22:ethanol is between about 0.3:1 to about 2:1.
  • the pyrolysis reaction of HCFC-22 and ethanol to form HFO-1252zc is carried out at a pressure of between about 0 psig and about 300 psig, including but 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 all values and ranges therebetween, including 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
  • One embodiment disclosed herein relates to a process of making HFO- 1252zc by subjecting HCFC-22 and ethanol, at a mole ratio of about 0.3:1 to about 2:1, in the presence of a diluent such as nitrogen, to pyrolysis, wherein the amount of nitrogen is between 20 and 80% of the feed stream comprising HCFC-22, ethanol, and N 2 , and wherein the pressure of the reaction is between about 0 psig and about 300 psig, including but 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 all values and ranges
  • One embodiment disclosed herein relate to a process of making HFO- 1252zc by subjecting HCFC-22 and ethylene to pyrolysis.
  • One embodiment disclosed herein relate to a process of making HFO- 1252zc by subjecting HCFC-22 and ethylene in the presence of a nitrogen diluent to pyrolysis, preferably wherein the amount of nitrogen is between 20 and 80% of the feed stream comprising HCFC-22, ethylene, and N2.
  • One embodiment disclosed herein relate to a process of making HFO- 1252zc by subjecting HCFC-22 and ethylene, in the presence of a diluent such as nitrogen, to pyrolysis, wherein the ratio of HCFC-22:ethylene is between about 0.3:1 to about 2:1.
  • the pyrolysis reaction of HCFC-22 and ethylene to form HFO-1252zc is carried out at a pressure of between about 0 psig and about 300 psig, including but 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 all values and ranges therebetween, including 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
  • One embodiment disclosed herein relates to a process of making HFO- 1252zc by subjecting HCFC-22 and ethylene at a mole ratio of about 0.3:1 to about 2:1, in the presence of a diluent such as nitrogen, to pyrolysis, wherein the amount of nitrogen is between 20 and 80% of the feed stream comprising HCFC-22, ethylene, and N 2 , and wherein the pressure of the reaction is between about 0 psig and about 300 psig.
  • Any of the processes described herein further comprise recovering HFO- 1252zc.
  • any of the processes disclosed herein may further comprise separating, recovering and recycling unconverted feeds selected from one of chlorodifluoromethane, ethanol, and ethene (e.g., to the heated reaction zone).
  • Certain embodiments of the invention disclosed herein are compositions comprising, consisting essentially of, or consisting of HFO-1252zc and one or more additional compounds identified in Table 1 other than HFO-1252zc. Table 1 Ashrae Ref.
  • Embodiments disclosed herein relate to compositions comprising, consisting of or consisting essentially 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.
  • Embodiments disclosed herein relate to compositions comprising, consisting of or consisting essentially of HFO-1252zc and one or more additional compounds selected from HC-22, HC-1150, HFC-263fb, HFC-C252, FC-C318, HFC- C336, and HFC-374 isomers.
  • Embodiments disclosed herein relate to compositions comprising, consisting of or consisting essentially of HFO-1252zc and one or more additional compounds selected from HC-1150, HCFC-22, HFO-1243zf, HFC-263fb, FC-C318, HFC-C336, and HFC-374 isomers. [0054] Embodiments disclosed herein relate to compositions comprising, consisting of or consisting essentially 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.
  • compositions comprising, consisting of or consisting essentially of HFO-1252zc and one or more additional compounds selected from chloroethane, ethanol and 3,3,4,4-tetrafluoro-1-butene.
  • compositions according to the present invention are free of or substantially free of Group A Fluorinated Substances.
  • Group A Fluorinated Substances includes any substance that (i) contains at least one fully fluorinated methyl (–CF3) or methylene (–CF2–) carbon atom (without any H/Cl/Br/I attached to it); and (ii) meets the criterion for persistence in soil/sediment and water established 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 as accessed on May 2, 2023) and referenced in the Annex XV Restriction Report dated March 22, 2023, the disclosure of which is hereby incorporated by reference (https://echa.europa.eu/documents/10162/f605d4b5-7c17- 7414-8823-b49b9fd43aea as accessed on May 2, 2023).
  • Group A Fluorinated Substances includes any substance that has a Henry’s Law constant ⁇ 250 Pa*m 3 /mol and contains at least one fully fluorinated methyl (–CF3) or methylene (– CF2–) carbon atom (without any H/Cl/Br/I attached to it).
  • Group A Fluorinated Substances include, but are not limited to, TFA.
  • the phrase "free of" as used herein with respect to the presence of Group A Fluorinated Substances in the present compositions means that the amount of such substances in the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas sample or liquid sample, and/or ion chromatography by analysis of a water sample after bubbling the thermal fluid through water.
  • Such methodologies are well known to those skilled in the art.
  • compositions according to the present invention are free of or substantially free of Group A Fluorinated Substances.
  • the phrase "free of" as used herein with respect to the formation of Group A Fluorinated Substances as degradation products of the present compositions means that the theoretical molar yield of such substances in environmental compartments of air, soil/sediment and water produced during tropospheric degradation of the compositions is sufficiently low so as to not be detectable, including but not limited to 0%, when measured by GC techniques, for example GC with a flame ionization or electron-capture detector or GC/MS method, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques.
  • compositions comprising, consisting essentially of, or consisting of HFO-1252zc, and are free of or substantially free of Group A Fluorinated Substances.
  • compositions of the present invention comprise, consist essentially of, or consist of HFO-1252zc, and degradation products of such compositions are free of or substantially free of Group A Fluorinated Substances, as defined herein.
  • Certain embodiments of the invention disclosed herein relate to compositions comprising, consisting essentially of, or consisting of HFO-1252zc and one or more of the additional compounds, and are free of or substantially free of Group A Fluorinated Substances.
  • compositions of the present invention comprise, consist essentially of, or consist of HFO-1252zc and one or more of the additional compounds, and degradation products of such compositions are free of or substantially free of Group A Fluorinated Substances, as defined herein.
  • conversion of HCFC-22 is conducted at temperatures above about 500°C, i.e., under pyrolytic conditions. Pyrolysis, as the term is used herein, means a chemical change produced by heating in the absence of catalyst.
  • Pyrolysis reactors generally comprise three zones: a) a preheat zone, in which reactants are brought close to the reaction temperature; b) a reaction zone, in which reactants reach reaction temperature and are at least partially pyrolyzed, and products and any byproducts form; and c) a quench zone, in which the stream exiting the reaction zone is cooled to stop the pyrolysis reaction.
  • Laboratory-scale reactors have a reaction zone, but the preheating and quenching zones may be omitted.
  • the reactor for carrying out the pyrolysis may be of any shape consistent with the process, but is preferably a cylindrical tube, either straight or coiled.
  • reactors typically have an inner diameter of from about 1.3 to about 5.1 cm (about 0.5 to about 2 inches). Heat is applied to the outside of the tube, with the chemical reaction taking place on the inside of the tube.
  • the reactor and its associated feed lines, effluent lines and associated units should be constructed, at least as regards the surfaces exposed to the reactants and products, of materials resistant to hydrogen fluoride.
  • Typical materials of construction include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as nickel-copper alloys commercially available from Special Metals Corp.
  • the reactor may be constructed of more than one material.
  • the outer surface layer of the reactor should be chosen for the ability to maintain structural integrity and resist corrosion at the pyrolysis temperature, while the inner surface layer of the reactor should be chosen of materials resistant to attack by, that is, inert to, the reactant and products.
  • the reactor may be constructed of an outer material chosen for physical strength at high temperatures and an inner material chosen for resistance to corrosion by the reactants and products under the temperature of the pyrolysis.
  • 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 that makes up the reactor packing.
  • a number of reactor configurations are possible, including but not limited to, packed bed tube or column reactors, operated in batch, semi-batch or continuous modes.
  • HCFC-22, ethylene and N 2 were fed through mass flow controllers into the reactor.
  • the reaction test conditions are listed on Table 2 below.
  • the reactor effluent was analyzed by online GC-MS-FID. The results of the analysis are listed in Tables 3-5 below.
  • HFO-1252zc 1,1-difluoropropene (HFO-1252zc) comprising contacting chlorodifluoromethane (HCFC-22) and one of a hydrocarbon and a hydrocarbon derivative in a heated reaction zone to form HFO-1252zc.
  • Embodiment 2 The process of Embodiment 1, wherein the contacting of HCFC-22 and the hydrocarbon or hydrocarbon derivative occurs in the absence of an added catalyst.
  • Embodiment 3 The process of any of Embodiments 1 to 2, wherein the reaction zone is heated to a temperature of between 500°C and 750°C, preferably a temperature selected from one of 550°C, 575°C, 600°C, 625°C and 650°C.
  • Embodiment 4 The process of any of Embodiments 1 to 3, wherein HCFC- 22 and the hydrocarbon or hydrocarbon derivative are vaporized prior to contact in the reaction zone.
  • Embodiment 5. The process of any of Embodiments 1 to 4, wherein HCFC- 22 is fed to the heated reaction zone at a molar excess.
  • Embodiment 6. The process of any of Embodiments 1 to 5, wherein a diluent is optionally fed to the reaction zone.
  • Embodiment 7. The process of any of 1 to Embodiments 6, wherein the heated reaction zone subjects the HCFC-22 and hydrocarbon or hydrocarbon derivative, in the presence of a diluent, to pyrolysis.
  • Embodiment 8 The process of any of Embodiments 1 to 7, wherein the heated reaction zone subjects the HCFC-22 and the hydrocarbon or hydrocarbon derivative, in the presence of a diluent, to pyrolysis, the ratio of HCFC- 22:hydrocarbon or HCFC-22:hydrocarbon derivative is between about 0.3:1 to 2:1.
  • Embodiment 9 The process of any of Embodiments 1-8, wherein the hydrocarbon comprises ethylene, or wherein the hydrocarbon derivative comprises ethanol.
  • Embodiment 9 wherein the hydrocarbon is ethylene and a diluent is fed to the heated reaction zone, and wherein the heated reaction zone is at a temperature sufficient to pyrolysis HFC-22 and ethylene.
  • Embodiment 11 The process of Embodiment 10, where the contacting occurs at a pressure in the range of 0 to 300 psig.
  • Embodiment 12 The process of Embodiment 9, wherein the hydrocarbon derivative is ethanol and a diluent is fed to the heated reaction zone, and and wherein the heated reaction zone is at a temperature sufficient to pyrolysis HFC-22 and ethanol.
  • Embodiment 13 Embodiment 13
  • Embodiment 12 where the contacting occurs at a pressure in the range of 0 to 300 psig.
  • Embodiment 14 The process of Embodiment 10, wherein the heated reaction zone subjects the HCFC-22 and ethylene, in the presence of a diluent, at a pressure in the range of 0 to 300 psig.
  • Embodiment 15 The process of Embodiment 12, wherein the heated reaction zone subjects the HCFC-22 and ethanol, in the presence of a diluent, at a pressure in the range of 0 to 300 psig.
  • Embodiment 16 The process of any of Embodiments 1 to 15, wherein the heated reaction zone is defined by a pyrolysis reactor.
  • Embodiment 17 The process of any of Embodiments 1 to 16, wherein the heated reaction zone is free of added catalyst.
  • Embodiment 18 The process of any of Embodiments 1 to 17, wherein the heated reaction zone is empty and free of added catalyst.
  • Embodiment 19 The process of any of Embodiments 1 to 18 wherein the heated reaction zone contains an inert support and is free of added catalyst.
  • Embodiment 20 The process of any of Embodiments 1 to 19, further comprising recovering HFO-1252zc.
  • Embodiment 21 Embodiment 21.
  • Embodiment 22 A system for carrying out the process of any of Embodiments 1 to 21, the system comprising a defined source of HCFC-22, a defined source of a hydrocarbon such as ethylene or a hydrocarbon derivative such as ethanol, a vaporizer connected to one of said defined sources, a flow through pyrolysis reactor configured for a contact time of HCFC-22 and the hydrocarbon or hydrocarbon derivative, and optionally nitrogen, between 5 to 180 second and at a temperature of between 500°C and 700°C to make HFO-1252zc.
  • a defined source of HCFC-22 a defined source of a hydrocarbon such as ethylene or a hydrocarbon derivative such as ethanol
  • a vaporizer connected to one of said defined sources
  • a flow through pyrolysis reactor configured for a contact time of HCFC-22 and the hydrocarbon or hydrocarbon derivative, and optionally nitrogen, between 5 to 180 second and at a temperature of between 500°C and 700°C to make HFO-1252zc.
  • Embodiment 23 A composition produced by processes of any of Embodiments 1-21 or the system of Embodiment 22.
  • Embodiment 24 A composition comprising 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).
  • HCFC-22 chlorodi
  • Embodiment 25 The composition of Embodiment 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.
  • Embodiment 26 The composition of Embodiment 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.
  • Embodiment 27 Embodiment 27.
  • Embodiment 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.
  • Embodiment 28 The composition of any of Embodiments 24 to 27, wherein at least one of the additional compounds is a fluorocyclopropane or fluorocyclobutane, preferably at least one of hexafluorocyclobutane and octafluorocyclobutane.
  • Embodiment 29 Embodiment 29.
  • a composition comprising 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.
  • HFO- 1252zc 1,1-difluoropropene
  • additional compounds selected from the group consisting of chlorodifluoromethane (HCFC-22), ethane, ethanal, chloroethane, ethanol, and 3,3,4,4-tetrafluoro-1-butene.
  • Embodiment 30 The composition of Embodiment 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.
  • Embodiment 31 The composition of any of Embodiments 23 to 30, wherein the composition is free of or
  • Embodiment 32 The composition of any of Embodiments 23 to 31, wherein degradation products of the composition are free of or substantially free of Group A Fluorinated Substances.

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Abstract

Des procédés de production de difluorooléfines, en particulier de 1,1-difluoropropène (HFO -1252zc), comprennent la pyrolyse de chlorodifluorométhane (HCFC-22) et d'un élément parmi l'éthylène ou l'éthanol. L'invention concerne également des compositions comprenant du HFO-1252zc et leurs utilisations.
PCT/US2024/037158 2023-07-17 2024-07-09 Procédé de fabrication de hfo-1252zc par pyrolyse de chlorodifluorométhane Ceased WO2025019202A2 (fr)

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AU2024295977A AU2024295977A1 (en) 2023-07-17 2024-07-09 Process of making hfo-1252zc from pyrolysis of chlorodifluoromethane
CN202480045987.0A CN121487911A (zh) 2023-07-17 2024-07-09 由氯二氟甲烷的热解制造hfo-1252zc的方法
MX2026000335A MX2026000335A (es) 2023-07-17 2026-01-09 Proceso de preparacion de hfo-1252zc a partir de pirolisis de clorodifluorometano

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US202363527100P 2023-07-17 2023-07-17
US63/527,100 2023-07-17

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WO2025019202A3 WO2025019202A3 (fr) 2025-02-27

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WO2009047535A2 (fr) * 2007-10-12 2009-04-16 Ineos Fluor Holdings Limited Compositions de transfert de chaleur
KR20120093857A (ko) * 2009-10-09 2012-08-23 다우 글로벌 테크놀로지스 엘엘씨 염화 및/또는 불화 프로펜의 제조 방법
CN107406354B (zh) * 2015-03-03 2020-08-28 Ａｇｃ株式会社 含氟烯烃化合物的制造方法
CN112760081B (zh) * 2021-02-09 2022-01-14 浙江大学 一种混合工质及其应用
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MX2026000335A (es) 2026-02-03
AU2024295977A1 (en) 2026-01-22
CN121487911A (zh) 2026-02-06
TW202504881A (zh) 2025-02-01

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