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WO2025193251A1 - Procédé de production de compositions fluorooléfiniques par hydrodéchloration catalytique d'hydrochlorofluorocarbures et compositions associées - Google Patents

Procédé de production de compositions fluorooléfiniques par hydrodéchloration catalytique d'hydrochlorofluorocarbures et compositions associées

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Publication number
WO2025193251A1
WO2025193251A1 PCT/US2024/037163 US2024037163W WO2025193251A1 WO 2025193251 A1 WO2025193251 A1 WO 2025193251A1 US 2024037163 W US2024037163 W US 2024037163W WO 2025193251 A1 WO2025193251 A1 WO 2025193251A1
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WO
WIPO (PCT)
Prior art keywords
hcfc
hfo
hcfo
group
percent
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PCT/US2024/037163
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English (en)
Inventor
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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Filing date
Publication date
Application filed by Chemours Co FC LLC filed Critical Chemours Co FC LLC
Publication of WO2025193251A1 publication Critical patent/WO2025193251A1/fr
Pending legal-status Critical Current
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

Definitions

  • the present invention is directed to processes for producing fluoroolefins, more particularly difluoroolefins, by catalytic hydrodechlorination of hydrochlorofluorocarbons (HCFCs), and compositions thereof.
  • HCFCs hydrochlorofluorocarbons
  • 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
  • HFO-1252zc 1 ,1 -difluoropropene
  • E/Z-HFO-1132 E/Z-HFO-1132
  • the present invention is directed to a method of producing a fluoroolefin compound of formula (I):
  • R 1 represents a H, Cl, F or a C1-C4 alkyl group
  • X 1 is H, F or Cl
  • Y 1 is H, F or Cl
  • Z 1 is H, Cl or F.
  • a method of producing a fluoroolefin of formula (I) comprises contacting a compound of formula (II) with hydrogen:
  • R 2 represents a H, Cl, F or a C1-C4 alkyl group
  • X 2 is H, F, Cl or Br
  • Y 3 is H, Cl, Br, or F
  • X 3 and Y 2 are the same or different and are each independently Cl or Br
  • Z 2 is H, Cl or F.
  • 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.
  • the term ‘consisting essentially of’ occupies a middle ground between “comprising” and “consisting of.”
  • GC/FID peak area correlates to the amount of a compound present as a proportion of the total area of all detected peaks. FID area% can be converted to mol% using response factors either calculated or measured. See https://www.chromatographytoday.com/news/gc-mdgc/32/breaking-news/what-is-a- response-factor/31169.
  • 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.
  • the present invention is directed to a method of producing a fluoroolefin of formula (I):
  • R 1 represents a H, Cl, F or a C1-C4 alkyl group
  • X 1 is H, F or Cl
  • Y 1 is H, F or Cl
  • Z 1 is H, Cl or F.
  • a method of producing a fluoroolefin of formula (I) comprises contacting a compound of formula (II) with hydrogen:
  • R 2 represents a H, Cl, F or a C1-C4 alkyl group
  • X 2 is H, F, Cl or Br
  • Y 3 is H, Cl, Br, or F
  • X 3 and Y 2 are the same or different and are each independently Cl or Br
  • Z 2 is H, Cl or F.
  • the contacting of the compound of formula (II) with H2 is performed in the vapor phase. Also preferably, the contacting is performed in the presence of a catalyst in an amount sufficient to form a composition comprising a compound of formula (I).
  • the compound of formula (II) includes 1 ,2-dichloro-1 ,1- difluoropropane (HCFC-252dc) or 1 ,2-dichloro-1 ,2-difluoroethane (HCFC-132).
  • the present invention relates to processes for producing (making) HFO-1252zc and compositions thereof. In some embodiments, the present invention relates to processes for producing (making) HFO-1252zc and compositions thereof from HCFC-252dc.
  • the present invention relates to making HFO-1252zc and involves the following reaction:
  • the feed composition which is contacted with H2 to form HFO-1252zc comprises, consists essentially of, or consists of HCFC-252dc and one or more additional compounds selected from HCFC-262fc, HCFO-1233xf, HCFO- 1242zf, acetone, HCFC-262db, HCFC-253db, HCFO-1223xd, C 4 H 6 CIF, HCFO-1232xf, E-HCFO-1241xb, Z-HCFO-1241xb and HCFO-1335.
  • the HCFC-252dc constitutes about 0.1 wt% to about 99.9 wt.%, or about 40 wt.% to about 99.9 wt.%, or about 90 wt.% to about 99.9 wt.%, based on the total weight of the composition, inclusive of all integers and ranges therebetween.
  • the total amount of additional compounds of the HCFC-252dc feed composition may be between greater than 0 and about 15 wt.% expressed by GC-FID peak area percent, e.g., the total amount of the composition, and all values and ranges therebetween. In some embodiments, the total amount of additional compounds of the HCFC-252dc feed composition may be between greater than 0 and less than one of 15 percent, 14 percent, 13 percent, 12 percent, 11 percent, 10 percent, 9 percent, 9 percent, 7 percent, 6 percent, 5 percent, 4 percent, 3 percent, 2 percent, or 1 percent and all values and ranges therebetween.
  • the total amount of additional compounds of the HCFC-252dc feed composition may be between greater than 0 and less than 0.1 percent, greater than 0 and less than 0.01 percent, between greater than 0.0001 and less than 0.3 percent, greater than 0.0001 and less than 0.2 percent, greater than 0.0001 and less than 0.1 percent, greater than 0.0001 and less than 0.01 percent, or greater than 0.0001 and less than 0.001 percent based on the total amount of the composition and all values and ranges therebetween.
  • each additional compound of the HCFC-252dc feed composition may be present in an amount of between greater than 0 and less than 4 percent, or less than 3 percent, or less than 2 percent, or less than 1 percent, or less than 0.5 percent, or less than 0.1 percent, or less than 0.01 percent, or less than 0.005 percent, or greater than 0.001 and less than 4 percent, or less than 3 percent, or less than 2 percent, or less than 1 percent, or less than 0.5 percent, or less than 0.1 percent, or less than 0.01 percent, or less than 0.005 percent, based on the total amount of the feed composition with the proviso that the total amount of the additional compounds 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 0.0001 and less than
  • One embodiment of the invention disclosed herein relates to processes of contacting HCFC-252dc with hydrogen in the vapor phase, in the presence of a catalyst, to form a product mixture or composition comprising HFO-1252zc. More particularly, in certain embodiments disclosed herein, HCFC-252dc is converted to HFO-1252zc by hydrodechlorination in the vapor phase in the presence of a catalyst.
  • the present invention relates to processes for producing (making) E-HFO-1132 and Z-HFO-1132 and compositions thereof. In some embodiments, the present invention relates to processes for producing (making) E- HFO-1132 and Z-HFO-1132 and compositions thereof from HCFC-132.
  • the present invention relates to making E/Z-HFO-1132 and involves the following reaction:
  • the feed composition which is contacted with H 2 to form E/Z-HFO-1132 comprises, consists essentially of, or consists of HCFC-132 and one or more additional compounds 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).
  • the HCFC-132 constitutes about 0.1 wt% to about 99.9 wt.%, or about 40 wt.% to about 99.9 wt.%, or about 90 wt.% to about 99.9 wt.%, based on the total weight of the composition, inclusive of all integers and ranges therebetween.
  • the total amount of additional compounds of the HCFC-132 feed composition may be between greater than 0 and about 15 wt.% expressed by GC-FID peak area percent, e.g., the total amount of the composition, and all values and ranges therebetween. In some embodiments, the total amount of additional compounds of the HCFC-132 feed composition may be between greater than 0 and less than one of 15 percent, 14 percent, 13 percent, 12 percent, 11 percent, 10 percent, 9 percent, 9 percent, 7 percent, 6 percent, 5 percent, 4 percent, 3 percent, 2 percent, or 1 percent and all values and ranges therebetween.
  • the total amount of additional compounds of the HCFC-132 feed composition may be between greater than 0 and less than 0.1 percent, greater than 0 and less than 0.01 percent, between greater than 0.0001 and less than 0.3 percent, greater than 0.0001 and less than 0.2 percent, greater than 0.0001 and less than 0.1 percent, greater than 0.0001 and less than 0.01 percent, or greater than 0.0001 and less than 0.001 percent based on the total amount of the composition and all values and ranges therebetween.
  • each additional compound of the HCFC-132 feed composition may be present in an amount of between greater than 0 and less than 4 percent, or less than 3 percent, or less than 2 percent, or less than 1 percent, or less than 0.5 percent, or less than 0.1 percent, or less than 0.01 percent, or less than 0.005 percent, or greater than 0.001 and less than 4 percent, or less than 3 percent, or less than 2 percent, or less than 1 percent, or less than 0.5 percent, or less than 0.1 percent, or less than 0.01 percent, or less than 0.005 percent, based on the total amount of the feed composition with the proviso that the total amount of the additional compounds 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%,
  • One embodiment of the invention disclosed herein relates to processes of contacting HCFC-132 with hydrogen in the vapor phase, in the presence of a catalyst, to form a product mixture or composition comprising HFO-1132(E) and HFO-1132(Z). More particularly, in certain embodiments disclosed herein, HCFC-132 is converted to HFO-1132(E) and HFO-1132(Z) by hydrodechlorination in the vapor phase in the presence of a catalyst.
  • Reactors suitable for vapor phase reactions can be used.
  • a heated reactor is used and the reactor is provided with suitable heat control.
  • a number of reactor configurations are possible including packed bed tube or column reactors, operated in batch, semi-batch or continuous modes.
  • preheaters and vaporizers, heat exchangers, feed and effluent lines, units associated with mass transfer, contacting vessels (pre-mixers), distillation columns, and valving associated with reactors, heat exchangers, vessels, columns, and units that are used in the processes of various embodiments disclosed herein should be constructed of materials resistant to corrosion.
  • the vapor phase reactor and other components may be made of or packed with materials such as, but not limited to, Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel® (hereinafter Inconel®) or nickelcopper alloys commercially available from Special Metals Corp. (New Hartford, N.Y.) under the trademark Monel® or other nickel alloy turnings or wool, or other material inert to the reactants.
  • Hastelloy® nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel® (hereinafter Inconel®) or nickelcopper alloys commercially available from Special Metals Corp. (New Hartford, N.Y.) under the trademark Monel® or other nickel alloy turnings or wool, or other material inert to the reactants.
  • the reaction to effect hydrodechlorination of the feed compound (i.e., the compound of formula (II), such as HCFC-252dc or HCFC-132) with H2 is carried out in the presence of a catalyst.
  • hydrogenation catalysts which may be used comprise Group IB and/or 11 B metals, and more particularly a Group IB metal and a Group 11 B metal.
  • hydrogenation catalysts which may be used comprise copper (Cu) and zinc (Zn).
  • the catalyst may be unsupported or supported.
  • the Cu-Zn metal is carried on a support, such as aluminum oxide, SiC or carbon, preferably carbon.
  • the metal catalyst is supported on carbon and the carbon support/carrier comprises carbon, acid-washed carbon, activated carbon, three- dimensional matrix carbonaceous materials.
  • the catalyst is Zn- Cu/C.
  • the catalyst comprises from about 2 to about 20 wt.% copper and about 0.5 to about 10 wt.% zinc.
  • the catalyst is 3%Zn- 8%Cu/C. The catalyst may be readily regenerated by any means known in the art if it becomes deactivated.
  • R 1 is a C1-C4 alkyl group, such as HFO-1252zc formed by the hydrodechlorination of HCFC-252dc
  • R 1 is H, F or Cl, such as E/Z- HCFO-1132 formed by the hydrodechlorination of HCFC-132
  • the catalyst can be pretreated (preactivated) with H2.
  • This pretreatment can be accomplished, for example, by placing the catalyst in a suitable container and thereafter, passing Ho over the catalyst at elevated temperature.
  • a suitable container can be the reactor used to perform the hydrodechlorination reaction.
  • H2 may be passed over the metals packing surface for activation thereof.
  • the pretreatment time is from about 15 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.
  • a heated reactor is used for the reaction of H2 with the formula (II) compound (e.g., HCFC-252dc or HCFC-132).
  • the formula (II) compound may be initially vaporized and fed to the reactor as a gas.
  • the reactor may be empty.
  • the reactor is filled with a suitable packing such as nickel-based alloys such as Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel® (hereinafter Inconel®) or nickel-copper alloys commercially available from Special Metals Corp. (New Hartford, N.Y.) under the trademark Monel® or other nickel alloy turnings or wool, or other material which is inert to the reactants and products and which allows efficient mixing of the formula (II) compound and H2 vapor. It will be understood by those skilled in the art that a prereactor could be utilized.
  • nickel-based alloys such as Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel® (hereinafter Inconel®) or nickel-copper alloys commercially available from Special Metals Corp. (New Hartford, N.Y.) under the trademark Monel® or other nickel alloy turnings or wool, or other material which is inert to the reactants and products and which
  • an inert diluent gas is used as a carrier gas for the R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 compound (e.g., HCFC-252dc or HCFC-132).
  • the carrier gas is selected is HCI, nitrogen, argon, helium, carbon dioxide or fluorinated carbons.
  • the carrier gas is mixed and vaporized with the formula (II) compound and H2 in the reactor.
  • the molar ratio of H2 to R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 for the vapor-phase reaction is from about 1 :1 to about 50:1.
  • R 2 CX 2 Y 2 - CX 3 Y 3 Z 2 is HCFC-252dc, and the molar ratio of H2 to the total amount of the HCFC- 252dc in the vapor phase reactor is from about 1 :1 to about 50:1.
  • R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 is HCFC-132, and the molar ratio of H2 to the total amount of the HCFC-132 in the vapor phase reactor is from about 5:1 to about 40:1.
  • Suitable temperatures for the vapor-phase hydrodechlorination of R 2 CX 2 Y 2 - CX 3 Y 3 Z 2 (e.g., HCFC-252dc or HCFC-132) with H2 in the presence of the catalyst are from about 60°C to about 300°C, or from about 180°C to about 280°C.
  • Suitable reactor pressures for the vapor-phase hydrodechlorination of the R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 (e.g., HCFC-252dc or HCFC-132) compound with H2 in the presence of the catalyst are from about 0 to about 200 psig, or from about 10 to about 150 psig.
  • Suitable reaction times for the vapor-phase hydrodechlorination of R 2 CX 2 Y 2 - CX 3 Y 3 Z 2 may vary from about 5 seconds to about 300 seconds, or from about 10 seconds to about 120 seconds.
  • the product stream comprising the R 2 CX 2 Y 2 -CX 3 Y 3 Z 2 compound may include additional members including unreacted precursor materials, e.g., HCFC- 252dc for HFO-1252dc and HCFC-132 for E/Z-HFO-1132.
  • the amount of HFO-1252zc produced is greater than about 10%, preferably greater than about 20%, more preferably greater than about 30%, most preferably greater than about 35%, based on the total amount of the product mixture.
  • the amount of E-HFO-1132 and Z-HFO-1132 produced is greater than about 1%, or greater than about 2%, preferably greater than about 3%, more preferably greater than about 4%, most preferably greater than about 5%, based on the total amount of the product mixture.
  • separation and/or purification e.g., distillation, fractionation, adsorption, absorption, and the like, or a combination of any such methods
  • compositions comprising, consisting essentially of, or consisting of R-1252zc which further include one or more additional members comprising hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs), hydrofluorochlorocarbons (HCFCs), hydrofluoroolefins (HFOs) and hydrofluorochloroolefins (HFCOs).
  • HFCs hydrofluorocarbons
  • HCCs hydrochlorocarbons
  • HCFCs hydrofluorochlorocarbons
  • HFOs hydrofluoroolefins
  • HFCOs hydrofluorochloroolefins
  • compositions comprising, consisting essentially of, or consisting 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(s), HCFC- 252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242 and HCFC-262db.
  • compositions comprising, consisting essentially of, or consisting of greater than about 10%, preferably greater than about 20%, more preferably greater than about 30%, most preferably greater than about 35% of HFO-1252zc, based on the total amount of the composition, and further including 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(s), HCFC-252dc, E-HCFO-1241xb, Z-HCFO- 1241xb, HCFC-242 and HCFC-262db.
  • a mixture of H2 and HCFC-252dc is converted by the catalytic vapor-phase hydrodechlorination process to a reaction mixture comprising HCI 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(s), HCFC-252dc, E-HCFO-1241xb, Z-HCFO- 1241xb, HCFC-242 and HCFC-262db.
  • the HFO-1252zc constitutes about 0.1 wt% to about 99.9 wt.%, or about 20 wt.% to about 40 wt% based on the total weight of the composition, inclusive of all integers and ranges therebetween.
  • One embodiment of the invention disclosed herein is a composition comprising, consisting essentially of, or consisting of HFO-1252zc, wherein the HFO- 1252zc is present in an amount greater than greater than about 20%, 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 all values and ranges therebetween.
  • compositions comprising, consisting essentially of, or consisting of E-HFO-1132 and Z- HFO-1132, which further include one or more additional members comprising HFCs, HCCs, HCFCs, HFOs and HFCOs.
  • compositions comprising, consisting essentially of, 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.
  • compositions comprising, consisting essentially of, or consisting of greater than about 3%, preferably greater than about 4%, more preferably greater than about 5% of E- HFO-1132 and Z-HFO-1132, based on the total amount of the composition, and further including 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.
  • a mixture of H2 and HCFC-132 is converted by the catalytic vapor-phase hydrodechlorination process to a reaction mixture comprising HCI 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.
  • the E-HFO-1132 and Z-HFO-1132 constitute about 0.1 wt% to about 10 wt.%, or about 1 wt.% to about 5 wt.%, or about 3 wt.% to about 5 wt.%, based on the total weight of the composition, inclusive of all integers and ranges therebetween.
  • One embodiment of the invention disclosed herein is a composition comprising, consisting essentially of, or consisting of E-HFO-1132 and Z-HFO-1132, wherein the E-HFO-1132 and Z-HFO-1132 are present in an amount greater than 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.
  • 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/CI/Br/l 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-b49b
  • 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/CI/Br/l 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.
  • degradation products of 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 or E/Z-HFO-1132, 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 or E/Z-HFO-1132, and degradation products of such compositions are free of or substantially free of Group A Fluorinated Substances, as defined herein.
  • compositions comprising, consisting essentially of, or consisting of HFO-1252zc or E/Z-HFO-1132 and one or more additional members selected from HFCs, HCCs, HCFCs, HFOs, HFCOs, C2-C4 alkanes, and C2-C4 alkenes.
  • such compositions are free of or substantially free of Group A Fluorinated Substances and/or degradation products of such compositions are free of or substantially free of Group A Fluorinated Substances, as defined herein.
  • blend compositions comprising, consisting essentially of, or consisting of 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 alkenes.
  • such blend compositions are free of or substantially free of Group A Fluorinated Substances and/or degradation products of such blend compositions are free of or substantially free of Group A Fluorinated Substances, as defined herein.
  • compositions comprising, consisting essentially of, or consisting of HFO-1252zc 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(s), HCFC-252dc, E- HCFO-1241xb, Z-HCFO-1241xb, HCFC-242 and HCFC-262db, and which are free of or substantially free of Group A Fluorinated Substances, and/or 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 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(s), HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242 and HCFC-262db.
  • such blend compositions are free of or substantially free of Group A Fluorinated Substances and/or degradation products of such blend compositions are free of or substantially free of Group A Fluorinated Substances, as defined herein.
  • compositions comprising, consisting essentially of, 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 which are free of or substantially free of Group A Fluorinated Substances, and/or 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 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.
  • such blend compositions are free of or substantially free of Group A Fluorinated Substances and/or degradation products of such blend compositions are free of or substantially free of Group A Fluorinated Substances, as defined herein.
  • compositions disclosed herein comprises reclaimed materials.
  • HFO-1252zc is produced with higher selectivity using a Zn- Cu/C catalyst rather than a Cu/C catalyst. Also, the stability of a Zn-Cu/C catalyst is much better than a Cu/C catalyst. Using a Zn-Cu/C catalyst, the product selectivity to HFO-1252zcis about 90 mol% or greater, about 93 mol% or greater, about 94 mol% or greater, about 95 mol% or greater, about 96 mol% or greater, or about 97 mol% or greater.
  • Example 3 Hydrodechlorination of
  • Embodiment 1 A process of making a fluoroolefin of formula (I), the process comprising contacting a compound of formula (II) with hydrogen in the vapor phase in the presence of a catalyst comprising a Group IB metal and a Group 11 B metal:
  • R 1 represents a H, Cl, F or a C1-C4 alkyl group
  • X 1 is H, F or Cl
  • Y 1 is H, F or Cl
  • Z 1 is H, Cl or F
  • R 2 represents a H, Cl, F or a C1-C4 alkyl group
  • X 2 is H, F, Cl or Br
  • Y 3 is H, Cl, Br, or F
  • X 3 and Y 2 are the same or different and are each independently Cl or Br
  • Z 2 is H, Cl or F.
  • Embodiment 2 The process of Embodiment 1 , wherein the catalyst comprises zinc and copper.
  • Embodiment 3 The process of any of Embodiments 1 to 2, wherein the catalyst is carried on a support material selected from the group consisting of alumina, SiC and carbon.
  • Embodiment 4 The process of Embodiment 3, wherein the support material is carbon.
  • Embodiment 5 The process of any of Embodiments 1 to 4, wherein the catalyst contains zinc in the range of 1 % to 10% and copper in the range of 3% to 15%.
  • Embodiment 6 The process of any of Embodiments 1 to 5, wherein the catalyst is 3%Zn-8%Cu/C.
  • Embodiment 7 The process of any of Embodiments 1 to 6, wherein the catalyst is pre-activated with H2.
  • Embodiment 8 The process of Embodiment 7, wherein the pre-activation with H2 occurs at a temperature of from about 100°C to about 500°C.
  • Embodiment 9. The process of any of Embodiments 1 to 8, wherein the compound of formula (II) comprises 1,2-dichloro-1 ,1 -difluoropropane (HCFC-252dc).
  • Embodiment 10 The process of Embodiment 9, wherein a 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, C 4 H 6 CIF, HCFO-1232xf, E- HCFO-1241xb, Z-HCFO-1241xb and HFO-1335.
  • Embodiment 11 The process of any of Embodiments 1 to 10, wherein the compound of formula (I) comprises 1 ,1 -difluoropropene (HFO-1252zc).
  • Embodiment 12 The process of Embodiment 11, wherein a 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(s), HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242 and HCFC- 262db.
  • propylene HFO-1261ze, HFO- 1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer(s), HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242 and HCFC- 262db.
  • Embodiment 14 The process of any of Embodiments 1 to 8 and 13, wherein the compound of formula (II) comprises 1,2-dichloro-1 ,2-difluoroethane (HCFC-132).
  • Embodiment 15 The process of Embodiment 14, wherein a 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).
  • HCFC-132C 1,1-dichloro-1 ,2-difluoroethane
  • HCFC-132a (1,1-dichloro-2,2-difluoroe
  • Embodiment 16 The process of any of Embodiments 1 to 8 and 13 to 15, wherein the compound of formula (I) comprises E/Z-1,2-difluoroethylene (E/Z-HFO- 1132).
  • Embodiment 17 The process of Embodiment 16, wherein a 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.
  • Embodiment 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, C 4 H 6 CIF, HCFO- 1232xf, E-HCFO-1241xb, Z-HCFO-1241xb and HFO-1335.
  • Embodiment 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(s), HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242 and HCFC- 262db.
  • propylene HFO-1261ze, HFO-1243zf, HCFC-262fc, E-HCFO-1251zb, Z-HCFO-1251zb, HFC-272fb, HCFC-243 isomer(s), HCFC-252dc, E-HCFO-1241xb, Z-HCFO-1241xb, HCFC-242 and HCFC- 262db.
  • Embodiment 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.
  • HCFC-132C 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- difluor
  • Embodiment 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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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne des procédés de production de fluorooléfines, et plus particulièrement de difluorooléfines telles que le 1,1-difluoropropène, en particulier HFO-1252zc, ou l'E/Z-1,2-difluoroéthylène, par hydrodéchloration catalytique d'hydrochlorofluorocarbures. L'invention concerne également des compositions produites selon ces procédés.
PCT/US2024/037163 2024-03-14 2024-07-09 Procédé de production de compositions fluorooléfiniques par hydrodéchloration catalytique d'hydrochlorofluorocarbures et compositions associées Pending WO2025193251A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416615A1 (fr) * 1989-09-06 1991-03-13 Daikin Industries, Limited Procédé pour la préparation de chlorotrifluoroéthylène
CN1876238A (zh) * 2006-07-07 2006-12-13 宁夏大学 一种氯代烷烃脱氯化氢反应生成氯代烯烃的催化剂及其制备方法
WO2016031777A1 (fr) * 2014-08-25 2016-03-03 旭硝子株式会社 Procédé de production d'une hydrofluorooléfine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416615A1 (fr) * 1989-09-06 1991-03-13 Daikin Industries, Limited Procédé pour la préparation de chlorotrifluoroéthylène
CN1876238A (zh) * 2006-07-07 2006-12-13 宁夏大学 一种氯代烷烃脱氯化氢反应生成氯代烯烃的催化剂及其制备方法
WO2016031777A1 (fr) * 2014-08-25 2016-03-03 旭硝子株式会社 Procédé de production d'une hydrofluorooléfine

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