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WO2025072102A1 - Compositions stabilisées contenant du fluoroéthylène, procédé de stockage et/ou de transport de celles-ci - Google Patents

Compositions stabilisées contenant du fluoroéthylène, procédé de stockage et/ou de transport de celles-ci Download PDF

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Publication number
WO2025072102A1
WO2025072102A1 PCT/US2024/048054 US2024048054W WO2025072102A1 WO 2025072102 A1 WO2025072102 A1 WO 2025072102A1 US 2024048054 W US2024048054 W US 2024048054W WO 2025072102 A1 WO2025072102 A1 WO 2025072102A1
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Prior art keywords
hfo
hfc
refrigerant
hcfo
fluoroethylene
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PCT/US2024/048054
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Inventor
Sheng Peng
Xuehui Sun
Karl Robert KRAUSE
Konstantinos Kontomaris
Mary E. Koban
Anthony F. STASIO
Robert Daniel LOUSENBERG
Luke David SIMONI
Joshua Hughes
Jason R. Juhasz
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Chemours Co FC LLC
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Chemours Co FC LLC
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Publication of WO2025072102A1 publication Critical patent/WO2025072102A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons

Definitions

  • the present invention relates broadly to stabilized compositions comprising at least one fluoroethyelene and at least one stabilizer which inhibits or prevents the fluoroethyelene from undergoing decomposition and other undesired reactions.
  • 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
  • Embodiment 4 The stabilized composition of any of Embodiments 1-3, wherein the stabilizer comprises a compound which is chemically inert with respect to the at least one fluoroethylene.
  • Embodiment 5 The stabilized composition of any of Embodiments 1-4, wherein the stabilizer comprises at least one compound, preferably at least one refrigerant, which has a boiling point that differs from a boiling point of the fluoroethylene by at least 5°C, preferably by at least 10°C, more preferably by at least 20°C.
  • the stabilizer comprises at least one compound, preferably at least one refrigerant, which has a boiling point that differs from a boiling point of the fluoroethylene by at least 5°C, preferably by at least 10°C, more preferably by at least 20°C.
  • Embodiment 6 The stabilized composition of any of Embodiments 1-5, wherein the stabilizer comprises at least one compound, preferably at least one refrigerant, which has a boiling point that differs from a boiling point of the fluoroethylene by at least 30°C, preferably by at least 40°C, more preferably by at least 50°C.
  • the stabilizer comprises at least one compound, preferably at least one refrigerant, which has a boiling point that differs from a boiling point of the fluoroethylene by at least 30°C, preferably by at least 40°C, more preferably by at least 50°C.
  • Embodiment 11 The stabilized composition of any of Embodiments 1-5, wherein the at least one stabilizer is selected from the group consisting of hydrocarbons comprising at least one of cyclic monoterpene; lipophilic organic compounds including tocopherols such as a-tocopherol; and phenols, aromatic organic compounds having at least one chemical moiety -CeH ⁇ OH), including benzene-1,4-diol.
  • the at least one stabilizer is selected from the group consisting of hydrocarbons comprising at least one of cyclic monoterpene; lipophilic organic compounds including tocopherols such as a-tocopherol; and phenols, aromatic organic compounds having at least one chemical moiety -CeH ⁇ OH), including benzene-1,4-diol.
  • Embodiment 14 The stabilized composition of any of Embodiments 1-12, wherein the fluoroethylene comprises HFO-Z-1132, and the stabilized composition further comprises at least one additional compound selected from the group consisting of HFO-1132a, HFO-1141, HFC-143, HCFO-1131a, HCFO-1122, HCFO- 1131(E), HCFO-1122a, HCFO-1131(Z), ethane, HFC-161 , CFO-1112(E), CFO- 1112(Z), HFC-152a and combinations thereof.
  • Embodiment 15 The stabilized composition of any of Embodiments 1-12, wherein the fluoroethylene comprises HFO-1132a, and the stabilized composition further comprises at least one additional compound selected from the group consisting of dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1 ,1-difluoroethane (HFC-142b), 1,1,1 -trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1- chloro-2,2-difluoroethylene (HCFO-1122), fluoroethylene (HFO-1141) and combinations thereof.
  • CFC-12 dichlorodifluoromethane
  • CFC-13 chlorotrifluoromethane
  • CFC-23 trifluoromethane
  • difluoromethane CFC-32
  • Embodiment 16 The stabilized composition of any of Embodiments 1- 5, wherein the stabilized composition comprises a refrigerant blend comprising the at least one fluoroethylene and at least one other refrigerant compound selected from CO 2 , HFO-1234ze(E), HFO-1234ze(Z), HFO-1336mzz(E), HFO-1336mzz(Z), H FC- 32, HFC-152a, HFC-125, HFC-134a, HCFO-1233zd(E), HCFO-1233zd(Z), HFC-143, HFC-143a, HFC-134, HFC-227ea, CFC-12, HFO-1243zf, HFO-1224yd(Z), HFO- 1233xf, HCFO-1131a, HCFO-1122a(Z), HFO-1234yc, HFO-1234ye(E), HFO- 1234ye(Z), HFO-1234zc, HFO-1243yc, HFO-1243zc, HFO-1243zc
  • Embodiment 17 The stabilized composition of any of Embodiments 1-16, wherein the at least one stabilizer is selected from the group consisting of HCI, HF, HFC-142b, HFC-32, HCFO-1122, HCFO-1122a, HCFO-1131 , HFC-152a, ethane and combinations thereof.
  • Embodiment 18 The stabilized composition of any of Embodiments 1-17, wherein the conditions of storage and transport comprise a temperature of up to 54.5°C.
  • Embodiment 19 The stabilized composition of any of Embodiments 1-18, wherein the stabilized composition is free of or substantially free of Group A Fluorinated Substances.
  • Embodiment 20 The stabilized composition of any of Embodiments 1-18, wherein degradation products of the stabilized composition are free of or substantially free of Group A Fluorinated Substances.
  • Embodiment 21 A container comprising the stabilized composition of any of Embodiments 1-20.
  • Embodiment 22 The container of Embodiment 21 , wherein the stabilized composition is miscible at temperatures up to 54.5°C and a pressure rating of about 145 psig or greater.
  • Embodiment 23 The container of any of Embodiments 21-22, wherein the container comprising the stabilized composition is transported from a first location (e.g., a manufacturing facility) to a second location remote from the first location (e.g., a use facility).
  • a first location e.g., a manufacturing facility
  • a second location remote from the first location e.g., a use facility
  • Embodiment 24 The container of any of Embodiments 21-23, wherein the fluoroethylene comprises a liquid at a temperature from about -60°C to about 54.5°C.
  • Embodiment 25 The container of any of Embodiments 21-24, wherein the oxygen and/or water concentration in the gas and/or liquid phases in the container ranges from about 3 vol ppm up to less than about 3,000 vol ppm at a temperature of about 25°C.
  • Embodiment 26 The container of any of Embodiments 21-25, wherein the container has a pressure rating at about 145 psig or greater.
  • Embodiment 27 A method for stabilizing a fluoroethylene for storage and transport, the method comprising mixing the fluoroethylene with at least one stabilizer in a suitable container to form a stabilized mixture in a liquid state, wherein the at least one stabilizer inhibits the fluoroethylene from undergoing at least one of decomposition, disproportionation, or polymerization under conditions of storage and transport.
  • Embodiment 28 The method of Embodiment 27, wherein the at least one stabilizer is selected from the group consisting of CO2, HFO-1234ze(E), HFO- 1234ze(Z), HFO-1336mzz(E), HFO-1336mzz(Z), HFC-32, HFC-152a, HFC-125, HFC-134a, HCFO-1233zd(E), HCFO-1233zd(Z), HFC-143, HFC-143a, HFC-134, HFC-227ea, CFC-12, HFO-1243zf, HFO-1224yd(Z), HFO-1233xf, HCFO-1131a, HCFO-1122a(Z), HFO-1234yc, HFO-1234ye(E), HFO-1234ye(Z), HFO-1234zc, HFO-1243yc, HFO-1243zc, HFO-1243ye(E), HFO-1243ye(Z), HFO-1243ze(E), HFO-1243ze(E),
  • Embodiment 29 The method of Embodiment 28, wherein the weight percent ratio of the stabilizer to the fluoroethylene is from 5:95 to 95:5, or 20:80 to 95:5, or 40:60 to 95:5, or 20:80 to 90: 10, or 30:70 to 80:20, or 40:60 to 70:30, or 50:50 to 60:40.
  • Embodiment 30 The method of Embodiment 27, wherein the at least one stabilizer is selected from the group consisting of polyol esters, polyalkylene glycols, and polyvinyl ethers.
  • Embodiment 31 The method of Embodiment 30, wherein an amount of the stabilizer is about 1 wt.% to about 30 wt.% based on the total weight of the stabilized composition.
  • Embodiment 32 The method of Embodiment 27, wherein the at least one stabilizer is selected from the group consisting of hydrocarbons comprising at least one of cyclic monoterpene; lipophilic organic compounds including tocopherols such as a-tocopherol; and phenols, aromatic organic compounds having at least one chemical moiety -CeH ⁇ OH), including benzene-1,4-diol.
  • the at least one stabilizer is selected from the group consisting of hydrocarbons comprising at least one of cyclic monoterpene; lipophilic organic compounds including tocopherols such as a-tocopherol; and phenols, aromatic organic compounds having at least one chemical moiety -CeH ⁇ OH), including benzene-1,4-diol.
  • Embodiment 33 The method of Embodiment 32, wherein an amount of the stabilizer is 0.001 wt.% to about 1 wt.% based on the total weight of the stabilized composition.
  • Embodiment 34 The method of any of Embodiments 27-32, wherein the fluoroethylene comprises HFO-E-1132, and the stabilized composition further comprises at least one additional compound selected from the group consisting of acetylene, ethane, propane, ethylene, 1,2-dichloro-1 ,2-difluoroethane (HFC-132), 1 ,1 ,2-trifluoroethane (HFC-143), 1 ,1,1 -trifluoroethane (HFC-143a), 1-chloro-1,2- difluoroethylene (HCFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2- fluoroethylene (HCFO-1131), 1 ,2-difluoroethylene (HFO-Z-1132), HFC-32, HFC-125, HFO-1141, HFC-161, CFO-1112(E), CFO-1112(Z), HFC-152a and combinations thereof.
  • HFC-132 1,2-dichloro-1 ,
  • Embodiment 35 The method of any of Embodiments 27-32, wherein the fluoroethylene comprises HFO-Z-1132, and the stabilized composition further comprises at least one additional compound selected from the group consisting of HFO-1132a, HFO-1141 , HFC-143, HCFO-1131a, HCFO-1122, HCFO-1131(E), HCFO-1122a, HCFO-1131(Z), ethane, HFC-161 , CFO-1112(E), CFO-1112(Z), HFC- 152a and combinations thereof.
  • Embodiment 36 The method of any of Embodiments 27-32, wherein the fluoroethylene comprises HFO-1132a, and the stabilized composition further comprises at least one additional compound selected from the group consisting of dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1 ,1-difluoroethane (HFC-142b), 1,1,1 -trifluoroethane (HFC-143a), tetrafluoroethylene (FO-1114), 1- chloro-2,2-difluoroethylene (HCFO-1122), fluoroethylene (HFO-1141) and combinations thereof.
  • CFC-12 dichlorodifluoromethane
  • CFC-13 chlorotrifluoromethane
  • CFC-23 trifluoromethane
  • difluoromethane CFC-32
  • Embodiment 37 The method of any of Embodiments 27-36, wherein the stabilized composition comprises a refrigerant blend comprising the at least one fluoroethylene and at least one other refrigerant compound selected from CO2, HFO- 1234ze(E), HFO-1234ze(Z), HFO-1336mzz(E), HFO-1336mzz(Z), HFC-32, HFC- 152a, HFC-125, HFC-134a, HCFO-1233zd(E), HCFO-1233zd(Z), HFC-143, HFC- 143a, HFC-134, HFC-227ea, CFC-12, HFO-1243zf, H FO-1224yd (Z), HFO-1233xf, HCFO-1131a, HCFO-1122a(Z), HFO-1234yc, HFO-1234ye(E), HFO-1234ye(Z), HFO-1234zc, HFO-1243yc, HFO-1243zc, HFO-1243zc,
  • Embodiment 38 The method of Embodiment 27, wherein the at least one stabilizer is selected from the group consisting of HCI, HF, HFC-142, HFC-32, HCFO-1122, HCFO-1122a, HCFO-1131 , HFC-152a, ethane and combinations thereof.
  • Embodiment 39 The method of any of Embodiments 27-38, wherein the stabilized composition is free of or substantially free of Group A Fluorinated Substances.
  • Embodiment 40 The method of any of Embodiments 27-38, wherein degradation products of the stabilized composition are free of or substantially free of Group A Fluorinated Substances.
  • Embodiment 41 A method for stably storing and/or transporting a composition comprising a fluoroethylene, the method comprising carrying out the method of any of Embodiments 27 to 40 to form a stabilized mixture stored in the container in a liquid state; and storing and/or transporting the container comprising the stabilized mixture in the liquid state.
  • FIG. 1 is a perspective view of a refrigerant distribution system according to an embodiment of the present disclosure.
  • FIG. 2 is a front view of a vertical ton tank, according to an embodiment.
  • FIG. 3 is a side view of a vertical ton tank, according to an embodiment.
  • FIG. 4A is an expanded front view of the internal piping of the vertical ton tank, according to an embodiment.
  • FIG. 4B is an expanded side view of the internal piping of the vertical ton tank, according to an embodiment.
  • FIG. 5 shows the piping couplers of the vertical ton tank, according to an embodiment.
  • FIG. 6 is a view of the bottom portion of a vertical ton tank, according to an embodiment.
  • FIG. 7 is an expanded top view of the valve configuration of a vertical ton tank, according to an embodiment.
  • FIG. 8 is an expanded side view of the valve configuration of a vertical ton tank, according to an embodiment.
  • FIG. 9 is a view of a vertical ton tank having a bottom protective collar, according to an embodiment.
  • FIG. 10 shows a door as part of bottom protective collar of a vertical ton tank, according to an embodiment.
  • the present invention provides a stabilized composition comprising at least one fluoroethylene and an effective amount of at least one stabilizer.
  • a stabilized composition comprising at least one fluoroethylene and an effective amount of at least one stabilizer.
  • stabilized it is meant to refer to a composition in which the propensity of the fluoroethylene compound(s) to undergo reactions such as decomposition, polymerization, disproportionation and the like, particularly under certain conditions associated with packaging, storage, handling and transport, is inhibited or suppressed.
  • inhibitor By “inhibit”, “inhibited”, “suppress” or “suppressed” it is meant that the propensity of the fluoroethylene compound(s) to undergo reactions such as decomposition including, but not limited to, polymerization, disproportionation and the like, has been eliminated or at least reduced relative to the propensity of the composition without the stabilizer to an extent that the composition is safe for storage and transport.
  • an effective amount it is meant to refer to a sufficient amount of the at least one stabilizer compound to achieve the desired result of inhibiting the fluoroethylene compound(s) from undergoing reactions, such as decomposition including, but not limited to, polymerization, disproportionation and the like, particularly under certain conditions associated with storage, handling and transport.
  • the present invention enables safe storage, transportation and handling of a fluoroethylene-containing composition, particularly a difluoroethylene-containing composition, and more particularly a composition comprising HFO-1132a, HFO-E- 1132 or HFO-Z-1132, in the form of a liquid mixture including a stabilizer.
  • the present invention is directed to a container for longterm containment of a fluoroethylene composition, particularly a composition comprising a difluoroethylene, such as HFO-1132, HFO-E-1132 or HFO-Z-1132, preferably in the form of the liquid mixture just described.
  • a fluoroethylene composition particularly a composition comprising a difluoroethylene, such as HFO-1132, HFO-E-1132 or HFO-Z-1132, preferably in the form of the liquid mixture just described.
  • the long-term containment will occur under conditions of varying temperature, but the liquid mixture is preferably stably stored at temperatures up to about 54.5°C (130°F). The liquid mixture remains stable at temperatures up to about 54.5°C during storage and shipping. Further, at the temperatures encountered during shipping or storage, no chemical interaction occurs between the fluoroethylene and stabilizer components of the mixture (liquid or vapor).
  • long-term containment is meant storage or transportation of the liquid mixture for at least 6 hours.
  • the present invention is directed to a container which stably stores a composition comprising HFO-E-1132, preferably neat HFO-E-1132, the container being maintained at a temperature up to about 54.5°C and having a pressure rating at about 1000 psig or greater, preferably about 1500 psig or greater, more preferably about 2000 psig or greater, the container being configured to be stored and/or shipped via conventional routes, such as by rail, road, water, etc.
  • the present invention is directed to a container which stably stores a composition comprising HFO-E-1132, preferably blends comprising HFO-E-1132, the container being maintained at a temperature up to about 54.5°C and having a pressure rating at about 145 psig or greater, or about 240 psig or greater, or 500 psig or greater, preferably about 1000 psig or greater, the container being configured to be stored and/or shipped via conventional routes, such as by rail, road, water, etc.
  • the present invention is directed to a container which stably stores a composition comprising HFO-Z-1132, either neat or blends, the container being maintained at a temperature up to about 54.5°C and having a pressure rating at about 145 psig or greater, preferably about 240 psig or greater, or more preferably about 500 psig or greater, the container being configured to be stored and/or shipped via conventional routes, such as by rail, road, water, etc.
  • compositions comprising, “comprising”, “includes”, “including”, “has”, “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, 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 composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, 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 are true (or present).
  • 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’.
  • fluoroethylene describes compounds which include two carbon atoms connected by a double bond and further include at least one fluorine atoms, optionally at least one hydrogen atom, and optionally at least one chlorine atom.
  • the fluoroethylene is a hydrofluoroethylene.
  • the fluoroethylene is a difluoroethylene.
  • the difluoroethylene comprises (Z)-1,2-difluoroethylene (HFO-Z- 1132).
  • the difluoroethylene comprises (E)-1,2-difluoroethylene (HFO-E-1132). In one embodiment, the difluoroethylene is HFO-Z-1132 and HFO-E- 1132. In one embodiment, the difluoroethylene comprises 1 ,1 -difluoroethylene (HFO-1132a).
  • the fluoroethylene component of the stabilized composition comprises HFO-1132(E), HFO-1132(Z) and/or HFO-1132a.
  • the fluoroethylene comprises HFO-1132(E), HFO- 1132(Z) and/or HFO-1132a having a purity of greater than 99 wt%, greater than 99.5 wt% pure, and in some cases greater than 99.5 to 99.98 wt% pure.
  • the fluoroethylene component of the stabilized composition or process is formed, purified, and/or obtained by a process known in the art.
  • the fluoroethylene component is (E)- 1 ,2-difluoroethylene or Z-1 ,2-difluoroethylene formed and/or purified by a process described in U.S. Pat. App. Pub. No. 2021/0107850, the entire disclosure of which is hereby incorporated by reference.
  • the fluoroethylene component is (E)-1 ,2-difluoroethylene or Z-1,2-difluoroethylene formed and/or purified by a process described in U.S.
  • the fluoroethylene component is 1,1-difluoroethylene formed and/or purified by a process described in U.S. Pat. No. 7,294,747, the entire disclosure of which is hereby incorporated by reference. It will be understood by those skilled in the art that the present invention is not limited to a fluoroethylene component being produced by one of the aforementioned processes, and encompasses such a component being produced by any process known in the art.
  • a stabilized composition comprises at least one fluoroethylene component, a stabilizer, and at least one additional compound.
  • the at least one additional compound includes at least one fluoroolefin.
  • the at least one additional compound includes at least two additional compounds.
  • the at least one additional compound includes a hydrocarbon such as propane and butane.
  • fluoroolefin describes compounds which comprise carbon atoms, fluorine atoms, and optionally hydrogen atoms.
  • the fluoroolefins used in the compositions of the present invention comprise compounds with 2 to 12 carbon atoms.
  • the fluoroolefins comprise compounds with 3 to 10 carbon atoms, and in yet another embodiment the fluoroolefins comprise compounds with 3 to 7 carbon atoms.
  • the present invention is intended to include all single configurational isomers, single stereoisomers, or any combination thereof.
  • F11E is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers of 1,1,1 ,4,4,4-hexafluorobut-2-ene in any ratio.
  • HFO- 1132a is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers of 1 ,2-difluoroethylene in any ratio.
  • the at least one additional compound is selected from dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1 ,1-difluoroethane (HFC-142b), 1,1,1 -trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1- chloro-2,2-difluoroethylene (HCFO-1122), acetylene, ethylene, propane, 1,2- dichloro-1 ,2-difluoroethane (HFC-132), 1,1,2-trifluoroethane (HFC-143), 1-chloro- 1 ,2-difluoroethylene (HCFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2- fluoroethylene (HCFO-1131), (E)-1 ,2-difluoro
  • the amount of the at least one additional compound can range, by weight, from about 1 to about 2000 ppm, about 10 to about 1000 ppm, about 100 to about 500 ppm, about 50 to about 200 ppm, about 10 to about 100 ppm, greater than about 0.1%, or any value, range, or any value or sub-range therebetween, based on the total weight of the refrigerant portion of the stabilized composition.
  • the fluoroethylene component is 1,1- difluoroethylene (HFO-1132a) and the at least one additional compound is selected from dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trifluoromethane (CFC-23), difluoromethane (CFC-32), 1-chloro-1 ,1-difluoroethane (HFC-142b), 1,1,1 -trifluoroethane (HFC-143a), tetrafluoroethylene (HFO-1114), 1- chloro-2,2-difluoroethylene (HCFO-1122), fluoroethylene (HFO-1141), HFO-1234yf and combinations thereof, in an amount of greater than 0 and, in some cases, about 0.01% by weight based on the total weight of the refrigerant portion.
  • CFC-12 dichlorodifluoromethane
  • CFC-13 chlorotrifluoromethane
  • CFC-23 trifluoromethane
  • the total amount of the additional compounds is between greater than 0 and 0.3 wt.%, between greater than 0 and 0.1 wt. %, between greater than 0 and 0.02 wt.% or between greater than 0 and about 0.01 wt. %, based on the total weight of the refrigerant portion of the composition.
  • the fluoroethylene component is (E)-1 ,2- difluoroethylene ((E)-HFO-1132) and the at least one additional compound is selected from acetylene, ethane, ethylene, propane, 1,2-dichloro-1 ,2-difluoroethane (HFC-132), 1 ,1 ,2-trifluoroethane (HFC-143), 1,1 ,1 -trifluoroethane (HFC-143a), 1- chloro-1,2-difluoroethylene (HCFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2- fluoroethylene (HCFO-1131), 1 ,2-difluoroethylene (HFO-Z-1132), HFC-32, HFC-125, HFO-1141, HFC-161, CFO-1112(E), CFO-1112(Z), HFC-152a, HFO-1234yf and combinations thereof, in an amount of greater than 0 and, in some additional compound is selected from acety
  • the total amount of the additional compounds is between greater than 0 and 0.3 wt.%, between greater than 0 and 0.1 wt. %, between greater than 0 and 0.02 wt.% or between greater than 0 and about 0.01 wt. %, based on the total weight of the refrigerant portion of the composition, inclusive of all intervening values and ranges.
  • the fluoroethylene component is (Z)-1 ,2- difluoroethylene ((Z)-HFO-1132) and the at least one additional compound is selected from HFO-1132a, HFO-1141 , HFC-143, HCFO-1131a, HCFO-1122, HCFO- 1131 (E), HCFO-1122a, HCFO-1131 (Z), ethane, HFC-161 , CFO-1112(E), CFO- 1112(Z), HFC-152a, CO 2 , HFO-1234ze(E), HFO-1234ze(Z), HFO-1336mzz(E), HFO-1336mzz(Z), HCFO-1233zd(E), HCFO-1122a(Z), HFO-1234yc, HFO- 1234ye(E), HFO-1234ye(Z), HFO-1234zc, HFO-1243yc, HFO-1243zc, HFO- 1243ye(E), HFO-1243ye
  • the total amount of the additional compounds is between greater than 0 and 0.3 wt.%, between greater than 0 and 0.1 wt. %, between greater than 0 and 0.02 wt.% or between greater than 0 and about 0.01 wt. %, based on the total weight of the refrigerant portion of the composition, inclusive of all intervening values and ranges.
  • the stabilized composition comprises a stabilizer and a refrigerant blend including at least one fluoroethylene and at least one other compound.
  • a composition may further comprise any of the additional compounds listed above.
  • the at least one fluoroethylene is preferably a difluoroethylene selected from HFO-Z-1132, HFO-E-1132, and HFO-1132a.
  • the at least one other compound of the refrigerant blends may be selected from fluoroolefins, hydrofluorocarbons, hydrocarbons, dimethyl ether, CF3I, ammonia, carbon dioxide (CO2), and mixtures thereof, meaning mixtures of any of the additional compounds listed in this paragraph.
  • the amount of the other refrigerant compound can range from about 1 to about 90 wt%, about 5 to about 75 wt%, and in some cases about 10 to about 50 wt%, inclusive of all intervening values and ranges.
  • the at least one other compound of the refrigerant blends may be selected from, CO 2 , HFO-1234ze(E), HFO-1234ze(Z), HFO- 1336mzz(E), HFO-1336mzz(Z), HFC-32, HFC-152a, HFC-125, HFC-134a, HCFO- 1233zd(E), HCFO-1233zd(Z), HFO-1234yf, HFC-143, HFC-143a, HFC-134, CFC- 12, HFO-1243zf, HFO-1224yd(Z), HFO-1233xf, HCFO-1131a, HCFO-1122a(Z), HFO-1234yc, HFO-1234ye(E), HFO-1234ye(Z), HFO-1234zc, HFO-1243yc, HFO- 1243zc, HFO-1243ye(E), HFO-1243ye(Z), HFO-1243ze(E), HFO-1243ze(Z), HFO-1243ze(
  • the at least one other compound of the refrigerant blends may be selected from CO 2 , HFO-1234ze(E), HFO-1234ze(Z), HFO- 1336mzz(E), HFO-1336mzz(Z), HFC-32, HFC-152a, HFC-125, HCFO-1233zd(E), HCFO-1233zd(Z), HFC-143a, HFC-134, CFC-12, HFO-1243zf, HCFO-1131a, HCFO-1122a(Z), HFO-1234yc, HFO-1234ye(E), HFO-1234ye(Z), HFO-1234zc, HFO-1234yf, HFO-1243yc, HFO-1243zc, HFO-1243ye(E), HFO-1243ye(Z), HFO- 1243ze(E), HFO-1243ze(Z), HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO- 1243ze(Z), HFO-12
  • the at least one other compound includes a fluoroolefin, such as any of the fluoroolefins listed above.
  • the amount of the other fluoroolefins can range from about 1 to about 90 wt%, about 5 to about 75 wt%, and in some cases about 10 to about 50 wt%, inclusive of all intervening values and ranges.
  • the at least one other compound comprises one or more hydrofluorocarbons.
  • the hydrofluorocarbon (HFC) compounds of the present invention comprise saturated compounds containing carbon, hydrogen, and fluorine. Of particular utility are hydrofluorocarbons having 1-7 carbon atoms and having a normal boiling point of from about -90°C to about 80°C. Hydrofluorocarbons are commercial products available from a number of sources, or may be prepared by methods known in the art.
  • hydrofluorocarbon compounds include but are not limited to fluoromethane (CH3F, HFC-41), difluoromethane (CH2F2, HFC- 32), trifluoromethane (CHF3, HFC-23), pentafluoroethane (CF3CHF2, HFC-125), 1,1,2,2-tetrafluoroethane (CHF2CHF2, HFC-134), 1,1,1,2-tetrafluoroethane (CF3CH2F, HFC-134a), 1,1,1 -trifluoroethane (CF3CH3, HFC-143a), 1,1- difluoroethane (CHF2CH3, HFC-152a), fluoroethane (CH3CH2F, HFC-161),
  • examples of suitable hydrofluorocarbons comprise at least one member selected from HFC-32, HFC-125, HFC-134a, HFC-152a, HFC- 236fa, and HFC-227ea.
  • the amount of hydrofluorocarbon can range from about 1 to about 90 wt%, about 5 to about 75 wt%, and in some cases about 10 to about 50 wt%, inclusive of all intervening values and ranges.
  • the at least one other compound comprises one or more hydrocarbons.
  • the hydrocarbons of the present invention comprise compounds having only carbon and hydrogen. Of particular utility are compounds having 3-7 carbon atoms. Hydrocarbons are commercially available through numerous chemical suppliers.
  • hydrocarbons include but are not limited to propane, n-butane, isobutane, cyclobutane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, 2-methylpentane, 2,2- dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, cyclohexane, n-heptane, and cycloheptane.
  • the at least one other compound comprises carbon dioxide (CO2), which is commercially available from various sources or may be prepared by methods known in the art.
  • CO2 carbon dioxide
  • the amount of CO2 can range from about 1 to about 90 wt%, about 5 to about 75 wt%, and in some cases about 10 to about 50 wt%, inclusive of all intervening values and ranges.
  • ionic liquid stabilizers are selected from the group consisting of emim BF4 (1-ethyl-3-methylimidazolium tetrafluoroborate); bmim BF4 (1-butyl-3- methylimidazolium tetraborate); emim PF6 (1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF6 (1-butyl-3-methylimidazolium hexafluorophosphate), all of which are available from Fluka (Sigma-Aldrich).
  • the preferred extreme pressure additives include mixtures of (A) tolyltriazole or substituted derivatives thereof, (B) an amine (e.g. Jeffamine M-600) and (C) a third component which is (i) an ethoxylated phosphate ester (e.g. Antara LP-700 type), or (ii) a phosphate alcohol (e.g. ZELEC 3337 type), or (iii) a Zinc dialkyldithiophosphate (e.g.
  • Lubrizol 5139, 5604, 5178, or 5186 type or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1 ,3,4-triadiaZole derivative (e. g. Curvan 826) or a mixture thereof.
  • Additional examples of additives which may be used are given in US. Pat. No. 5,976,399 (Schnur, 5:12-6:51 , hereby incorporated by reference).
  • Acid number is measured according to ASTM D664-01 in units of mg KOH/ g.
  • the total halides concentration, the fluorine ion concentration, and the total organic acid concentration is measured by ion chromatography.
  • Chemical stability of the refrigerant system is measured according to ASHRAE 97: 2007 (RA 2017) “Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems”. The viscosity of the lubricant is tested at 40°C according to ASTM D-7042.
  • Mouli et al. (WO 2008/027595 and WO 2009/042847) teach the use of alkyl silanes as a stabilizer in compositions containing fluoroethylenes. Phosphates, phosphites, epoxides, and phenolic additives also have been employed in certain compositions. These are described for example by Kaneko (U.S. Pat. App. Pub. No. 2007/0290164) and Singh et al. (U.S. Pat. App. Pub. No. 2006/0116310). All of these aforementioned applications are expressly incorporated herein by reference.
  • one or more of these optional components need not be blended with the stabilizer and fluoroethylene component for storage and transport. Instead, the optional component(s) may be added to the composition after storage or transport is complete and use of the composition is desired, for example as a working fluid or a component of a refrigerant blend.
  • the stabilizer is desired to be separated from the fluoroethylene or fluoroethylene blend before use of the fluoroethylene or fluoroethylene blend (i.e., after storage or transport), in order to utilize the fluoroethylene or fluoroethylene blend, for example as a working fluid or as a component of a refrigerant blend.
  • the formulation of the stabilized composition is altered by removal of the stabilizer (e.g., by distillation) to obtain a blend comprising HFO-1132a, HFO-1132(E) or HFO-1132(Z) and one or more other refrigerants, or to obtain neat HFO-1132a, HFO-1132(E) or HFO-1132(Z) which can then be utilized to make new blends.
  • the stabilizer e.g., by distillation
  • one or more of the above-discussed optional components or one or more blend components such as those discussed above may be added to the composition after storage or transport is complete, the stabilizer(s) has/have been removed, and utilization of the composition is desired.
  • a refrige rant is a compound or mixture of compounds that function as a heat transfer fluid in a cycle, where the fluid undergoes a phase change from a liquid to a gas (or vapor) and back.
  • the stabilizer preferably comprises a liquid at a temperature from about -80°C to about 40°C.
  • the stabilizer is preferably a liquid at temperatures typically encountered during storage, transport and handling of the stabilized composition, namely at temperatures up to 54.5°C.
  • the fluoroethylene preferably comprises a liquid at a temperature from about -60°C to about 54.5°C.
  • the fluoroethylene is preferably a liquid at temperatures typically encountered during storage, transport and handling of the stabilized composition, namely at temperatures up to 54.5°C.
  • the stabilizer remains blended with the fluoroethylene in the liquid phase during packaging, storage, transport and handling.
  • One embodiment of the invention relates to storing any of the foregoing compositions, preferably in the liquid phase, within a sealed container where the oxygen and/or water concentration in the gas and/or liquid phases ranges from about 3 vol ppm up to less than about 3,000 vol ppm at a temperature of about 25°C, about 5 vol ppm up to less than about 1 ,000 vol ppm, and in some cases about 5 vol ppm up to less than about 500 vol ppm.
  • the present invention relates to a distribution system 100, as shown in FIG. 1, for any of the foregoing fluoroethylene compositions.
  • a delivery vessel 110 containing any of the foregoing fluoroethylene compositions 115 may be transported from a first location to a second location.
  • the delivery vessel 110 may be transported by any suitable mode of transportation.
  • a polymer inhibitor material can be introduced into distribution system 100.
  • the polymer inhibitor material can reduce (or eliminate formation of) unwanted polymeric materials.
  • the polymer inhibitor material can be introduced in response to detection of an oxidant concentration exceeds a threshold. While any suitable polymer inhibitor can be employed, examples of suitable inhibitors are disclosed in International Application Publication No. WO 2019/213004A1; the disclosure of which is hereby incorporated by reference.
  • the distribution system 100 includes means to separate the stabilizer from the refrigerant portion of the fluoroethylene composition.
  • the stabilizer may be removed from the stabilized composition by any method known in the art, before reaching the distribution vessel 130, in the distribution vessel 130 or after leaving the distribution vessel 130.
  • a compressor may be used to preferentially separate the stabilizer from the refrigerant portion of the composition.
  • Other methods to separate the stabilizer from the stabilized composition include, but are not limited to scrubbing, distillation, fractionation, adsorption, and combinations thereof.
  • the fluoroethylene composition 115 may be sampled during and/or after transfer to the distribution vessel 130, by a monitoring system 120. More particularly, the composition 115 may be sampled by the monitoring system 120 either before or after the stabilizer has been separated therefrom.
  • the monitoring system 120 may include a distribution sensor 125 configured to sample the fluoroethylene composition 115, for example within the distribution vessel 130.
  • the monitoring system 120 receives at least one distribution parameter of the fluoroethylene composition 115 from the distribution sensor 125.
  • the monitoring system 120 employs an in-line apparatus for detecting the presence of a distribution parameter.
  • the in-line apparatus can be located at any suitable location or locations within the distribution system. For example, an in-line GC/MS apparatus for detecting the presence of oxidants.
  • the at least one distribution parameter may include temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, and combinations thereof.
  • NAGs include atmospheric gases (which is typically comprised of 78% nitrogen, 21% oxygen, and about 1% argon), accumulated in the vapor phase of refrigerants where the solubility of air in the refrigerant liquid phase is relatively low. While reducing the total amount of NAG contained within said refrigerant (dissolved within the liquid refrigerant) may be desirable, it is typically more desirable to reduce the oxygen containing portion of the NAG preferentially over the nitrogen portion.
  • the oxygen containing portion may increase the propensity of the refrigerant to decompose or form unwanted polymeric materials.
  • the monitoring system 120 determines whether the at least one distribution parameter is below at least one distribution predetermined threshold. If the at least one distribution parameter is below the at least one distribution predetermined threshold, the fluoroethylene composition 115 is suitable for further distribution.
  • At least one distribution predetermined threshold includes a temperature of no more than 100°C, moisture level of 10 ppm by weight, per AHRI 700 (2016), a NAG concentration of less than 1.5 volume percent at 25°C, per AHRI 700 (2016), and combinations thereof.
  • at least one distribution predetermined threshold includes a temperature of no more than 120°C, moisture level of 10 ppm by weight, per AHRI 700 (2016), a NAG concentration of less than 0.9 volume percent at 25°C, per AHRI 700 (2016), and combinations thereof.
  • the one distribution predetermined threshold includes a temperature of no more than 100°C, moisture level of 10 ppm by weight, per AHRI 700 (2016), a NAG concentration of less than 0.9 volume percent at 25°C, per AHRI 700 (2016).
  • the distribution system 100 may transfer at least a portion of the fluoroethylene refrigerant composition 115 to an end user.
  • a distribution line 111 is connected to the distribution vessel 130 via a distribution valve 151.
  • the operation of the distribution valve 151 may be regulated by the monitoring system 120, based on user inputs, data from one or more sensors, other data, and combinations thereof.
  • the distribution valve 151 may be used to regulate the flow of the fluoroethylene refrigerant composition 115.
  • the pressure within the distribution line may be regulated by one or more distribution pumps 152.
  • one or more distribution sensors 125 are configured to sample the fluoroethylene refrigerant composition 115 within the distribution line 111.
  • the monitoring system 120 receives at least one distribution parameter (e.g., temperature, moisture concentration, NAG concentration, acidity, and combinations thereof) of the fluoroethylene refrigerant composition 115 from the one or more distribution sensors 125.
  • the monitoring system 120 determines whether the at least one distribution parameter is below at least one predetermined threshold. If the at least one distribution parameter is below the at least one predetermined threshold, the refrigerant composition 115 is suitable for transmission to the end user.
  • FIG. 1 shows a sensor 125 on the distribution line 111, in other embodiments, sensor 125 on the distribution line 111 may be omitted.
  • a rack system 160 may be used to deliver the refrigerant composition 115 to one or more end user refrigerant systems 175.
  • the rack system 160 allows the refrigerant composition 115 to be simultaneously delivered to a plurality of end user refrigerant systems 175.
  • One or more distribution sensors 125 are configured to sample the refrigerant composition 115 within the distribution line 111.
  • the monitoring system 120 receives at least one distribution parameter (e.g., temperature, moisture concentration, NAG concentration, acidity, and combinations thereof) of the refrigerant composition 115 from the one or more distribution sensors 125, and determines whether the at least one distribution parameter is below at least one distribution predetermined threshold. If the at least one distribution parameter is below the at least one rack line predetermined threshold, the refrigerant composition 115 is provided to the end user.
  • at least one distribution parameter e.g., temperature, moisture concentration, NAG concentration, acidity, and combinations thereof
  • the distribution line 111 may include a plurality of distribution line branches 170. Each distribution line branch 170 may be configured to independently deliver the refrigerant composition 115 to the end user.
  • the distribution line branches 170 may further include a distribution line branch valve 171, which is able to regulate the flow of the refrigerant composition 115 in the distribution line branch 170.
  • the distribution line branches may also include one or more distribution line sensors 125 configured to sample the refrigerant composition 115 within the distribution line branch 170.
  • the monitoring system 120 receives at least one distribution line parameter (e.g., temperature, moisture concentration, NAG concentration, acidity, and combinations thereof) of the refrigerant composition 115 from the one or more distribution line sensors 125, and determines whether the at least one distribution line parameter is below at least one distribution line predetermined threshold. If the at least one distribution line parameter is below the at least one distribution line predetermined threshold, the refrigerant composition 115 is provided to the end user via a rack transfer valve 173.
  • the distribution line branches 170 may additionally include a backflow prevention device 174, to prevent the backflow of the refrigerant composition 115 and possible introduction of external materials.
  • the rack transfer valve 173 may include a nozzle portion configured to be detachably in fluid communication with an end user system refrigerant system 175.
  • the monitoring system 120 determines the at least one distribution line parameter is above the at least one distribution line predetermined threshold, one or more properties of the refrigerant composition 115 may need to be adjusted to form an acceptable refrigerant composition which meets the desired specifications.
  • the monitoring system 120 may close one or more valves 151, 171, 173, to discontinue the dispensing of the refrigerant composition 115.
  • the distribution line branch 170 may be detached from the end user system refrigerant system 175, to prevent the unacceptable refrigerant composition from being transferred to the end user system refrigerant systems 175.
  • the distribution line branch 170 may then be detachably connected to a recovery system 180.
  • the distribution line branch 170 may then be purged of the unacceptable refrigerant composition.
  • the recovery system 180 includes a recovery line 181, configured to selectively or detachably connect to the distribution line branch 170, allowing the unacceptable refrigerant composition to be transferred to one or more recovery vessels 182.
  • the one or more recovery vessels 182 may store the unacceptable refrigerant composition until it is treated by a treatment unit 190, having one or more treatment modules.
  • the treatment modules may alter the composition of the unacceptable refrigerant composition to return the properties of the unacceptable refrigerant composition to within the desired specifications.
  • the recovery system 180 may additionally include one or more recovery system sensors 183, which may sample the properties of the unacceptable refrigerant composition in the one or more recovery vessels 182 and/or after treatment by the one or more treatment modules.
  • the monitoring system 120 may receive one or more recovery parameters from the one or more recovery sensors 183.
  • the recovery parameters may include temperature, moisture concentration, non-condensable material concentration (e.g., oxygen concentration), insoluble particulate concentration, color, and/or acidity (e.g., total acid number).
  • the monitoring system 120 may then direct the unacceptable refrigerant composition to the one or more treatment modules of the treatment unit
  • the treatment unit 190 includes a dehydration module
  • the dehydration module 191 may be used to remove water from the unacceptable refrigerant composition.
  • the dehydration module 191 may contact the unacceptable refrigerant composition with a desiccant, such as molecular sieves.
  • the dehydration may result in the concentration of the one or more impurities being reduced to less than one or more predetermined thresholds in the unacceptable refrigerant composition.
  • the moisture concentration may be altered, resulting in a moisture level of less than 20 ppm by weight, per AHRI 700 (2016).
  • the moisture concentration may be altered, resulting in a moisture level of less than 10 ppm by weight, per AHRI 700 (2016).
  • the treatment unit 190 includes an inert gas purge module 192.
  • the inert gas purge module 192 may contact the unacceptable refrigerant composition with an inert gas, such as nitrogen, argon, or xenon, to displace dissolved reactive gases in the unacceptable refrigerant composition.
  • the inert gas may include dry nitrogen.
  • the inert gas purge may result in the concentration of the one or more components being altered to less than one or more predetermined thresholds in the unacceptable refrigerant composition.
  • the concentration of non-condensable materials may be altered, resulting in a concentration of less than 1.5 volume percent at 25°C, per AHRI 700 (2016).
  • the treatment unit 190 includes a NAG reduction unit 193.
  • the NAG reduction unit 133 may contact the unacceptable refrigerant composition with a reducing agent, such as a metal powder, which may react with oxygen or other oxidizable components of the unacceptable refrigerant composition.
  • the reducing agent may include iron powder.
  • Treatment by the NAG reduction unit 193 may result in the concentration of one or components of the unacceptable refrigerant composition being reduced to less than one or more predetermined thresholds in the unacceptable refrigerant composition.
  • the concentration of non-condensable materials may be altered, resulting in a concentration of NAG (and other oxidants) being less than 1.5 volume percent at 25°C, per AHRI 700 (2016).
  • a condenser is used in conjunction with a cooling medium that is sufficiently cold enough to condense the refrigerant and allow the NAGs pass through with minimal loss of refrigerant.
  • a compressor can be used in conjunction with the condenser to increase the pressure and enhance condensation of the refrigerant at a higher temperature.
  • a membrane that is selective for NAGs in employed.
  • a membrane is positioned in a manner sufficient for the NAGs to pass through the membrane and in turn are removed while the refrigerant does not permeate thereby separating the NAGs from the refrigerant.
  • the treatment unit 190 includes a filtration module 194.
  • the filtration module 194 may separate one or more insoluble particulates from the unacceptable refrigerant composition 115.
  • the filtration module 194 may separate a plurality of insoluble particles from the unacceptable refrigerant composition by filtration.
  • the unacceptable refrigerant composition 115 is filtered through an at least 0.01 micrometer screen, an at least 0.03 micrometer screen, an at least 0.05 micrometer screen, an at least 0.08 micrometer screen, an at least 0.1 micrometer screen, or an at least 0.15 micrometer screen.
  • the unacceptable refrigerant composition is filtered through a 0.1 micrometer screen.
  • the filtration may result in the concentration of the one or more components being altered to less than the one or more predetermined thresholds in the unacceptable refrigerant composition.
  • Another method of removing relatively large unwanted materials comprises using physical sieves. Larger mesh sieves on the order of 50 microns down to 10 microns can be used to remove metals, particulate materials and residue (e.g., fluoropolymer particles).
  • the concentration of the one or more components may be altered resulting in an oil concentration of below 0.5 weight percent.
  • the concentration of the one or more components may be altered resulting in a reduction in the concentration of dyes.
  • the color of the unacceptable refrigerant composition is altered to a Byk-Gardner color value of less than 3, preferably less than 2 and most preferably equal to 1.
  • Another embodiment of this invention is employing several sieves within a series configuration such that refrigerant flows through all of the sieves removing different particulates and contaminants at each sieve or filter.
  • Another method for removing unwanted contaminant type materials comprises using vapor transfer and refrigerant recovery where the unwanted polymeric type material remains in a liquid heel.
  • the polymer or other higher molecular weight material is at a concentration that is still soluble in the refrigerant (or refrigerant blend) and therefore physical screening is not effective.
  • Vapor transfer conveys the refrigerant in vapor form, from one cylinder to a different cylinder, leaving the unwanted heavier, polymeric material in the original cylinder.
  • Vapor transfer and refrigerant recovery can be used in combination with the VTT (described below). Heat blanket or external cylinder heating can also be applied to the cylinders to aid in vapor transfer.
  • Driers can also be used to lower moisture levels and in combination with any of the above-mentioned methods.
  • the stabilized compositions described herein may be stored, transported, or handled in a variety of containers, including drums, cylinders, tanks, or other suitable storage vessels.
  • the containers may be made of any suitable material, including, but not limited to, stainless steel, aluminum, or composite materials.
  • the container for storing the foregoing compositions can be constructed of any suitable material and design that is capable of sealing the compositions therein while maintaining liquid phase. Examples of suitable containers comprise pressureresistant containers such as a tank, a filling cylinder, and a secondary filing cylinder.
  • the container can be constructed from any suitable material which do not react with the stabilized composition, such as carbon steel, manganese steel, or chromiummolybdenum steel, among other low-alloy steels, stainless steels, and in some cases aluminum alloys.
  • the container can include a pierce top or valves suitable for dispensing flammable substances.
  • the container storing any of the foregoing compositions may be transported from a first location to a second location remote from the first location.
  • the first location may be the manufacturing facility where the stabilized composition is formed
  • the second location may be a use facility - either an intermediate use facility such as a facility for separation of the stabilizer or for blending of the stabilized composition with one or more other refrigerants to make new blends, or an end use facility.
  • the container may be transported by any suitable mode of transportation, such as transport via ocean, road and/or rail.
  • the present invention involves a container which enables distribution, blending, transport, transfer, storage, recovery and usage of refrigerant.
  • the container is a 500 L to 1000 L, or more specifically, 750 L to 950 L or more specifically 850 L to 950 L vertical cylinder designed for holding, transferring or conveying flammable compositions. Due to the vertical orientation, it lends itself to ease of processing of said refrigerant. It should be noted that any vertical cylinder designed for flammable refrigerants, can also be conveniently used for non-flammable refrigerants.
  • the vertical ton tank has specific design parameters, which in the combinations noted below, make it uniquely useful in conjunction with other processes mention above.
  • the container is a vertical ton tank (VTT) cylinder.
  • VTT vertical ton tank
  • the VTT cylinder is designed such that pressure vessel is vertically oriented which implies that the cylinder is upright (vertical) during use, transport and storage.
  • the specific orientation lends towards smaller physical footprint at a potential distribution location as footprint (m2) may be limited.
  • the vertical orientation design lends itself favorably towards the actual conveyance of the VTT cylinder.
  • the VTT cylinder can be conveniently loaded onto a forklift without any loss of gravity or unusual positioning as is the case with the horizontal ton tank.
  • the design of the base of the VTT cylinder is also designed to improve product conveyance.
  • the bottom of the VTT cylinder has an integrated pallet with openings for the forklift tines. Therefore, the described VTT cylinder can safely and conveniently be used to physically move flammable refrigerants from one location to another location.
  • the pressure, flammability and volume will follow the appropriate design codes.
  • the VTT cylinder will follow the ASME design construction and pressure rating, while in the EU the VTT cylinder will follow ADR, and in Japan the VTT cylinder will follow HPGL.
  • FIGS. 2 and 3 show a front and side view of an embodiment of the vertical ton tank (VTT) with dip tubes.
  • Dip tubes 62 and 65 are shown with 1/2-inch and 1- inch connections at the top and bottom of the tank. The attachments of dip tubes 62 and 65 to the top flange 60 and bottom flange 61 are also pictured.
  • the VTT has been designed to include two flanges marked as (top flange 60) and (bottom flange 61).
  • the bottom and top flanges aid in opening the VTT tanks and taking visual inspection or easy inspection with a scoping process, such as a boroscope.
  • the flanges also aid in easy removal of any debris that could collect from impurities.
  • the flanges are shown in FIGS. 2 and 3.
  • FIG. 5 illustrates the location and orientation of the drain pipes.
  • the smaller piping details are given in elements 83, 84, 85 (smaller flange) which connects to %-inch pipe 64 which then leads out to a connector.
  • the larger piping details are given in elements 87, 88, and 89 which connects to a 1-inch pipe 63.
  • FIGS. 5 and 6 are expanded top and side views of the bottom portion of the (VTT). These diagrams show elements in more detail and how they configure into the main bottom flange.
  • PTFE gaskets As shown which ensure that no additional contamination comes from gaskets. PTFE gaskets have been found to innocuous with HFO type products and therefore need to be used in combination with this design.
  • the tank further includes dry bulk couplers (DBC) which limit the amount of refrigerant that can be released during refrigerant transfer.
  • Dry bulk couplers have a specific locking mechanism which stops product transfer until the unlocking mechanism is engaged. After the unlocking mechanism is engaged, product is transferred. This mechanism reduces release of flammable products down to less than 1 gram and is very desirable in this VTT design.
  • the combination of the DBC to this process aids in ease of product transfer, increases safety and limits and any unintentional exposure of refrigerant and/or contaminant.
  • These are elements 122, 124 and 125 in the drawing.
  • Adaptors from the metal piping to the DBC are element 123.
  • DBC brands are commonly known as Denver Gardner TODO, Econosto valves, and Dixon valves.
  • the VTT has a bottom collar that latches in place to protect the bottom valves associated with VTT.
  • the collar keeps the forklift tines from potentially hitting the lower valves and/or flanges and therefore protects product.
  • the bottom collar can be zip tied to aid in anti-counterfeit detection. Any braking of a certified zip lock can indicate that the product has been potentially tampered with.
  • FIG. 5 depicts how the collar fits over the valves.
  • FIG. 6 shows protective door which may further protect the valves when the tank is not connected externally.
  • the container for storage, transport and handling of any of the foregoing compositions may be as described in U.S. Patent Application Publication No. 2022/0136748, the entire disclosure of which is incorporated herein by reference.
  • the container for storage, transport and handling of any of the foregoing compositions may be selected from DGT4B240ET12-20M1031 , DOT-3A2200, DOT-3AA2200, DOT-3AX2200, DOT-3AAX2200, DOT-3T2200 and DOT-39 cylinders.
  • the container for storage, transport and handling of any of the foregoing compositions comprising HFO-Z-1132 is a DOT4B240ET12-20M1031 cylinder.
  • the container for storage, transport and handling of any of the foregoing compositions comprising HFO-E-1132 or HFO-1132a is one of a DOT-3A2200, DOT-3AA2200, DOT-3AX2200, DOT- 3AAX2200, DOT-3T2200 or DOT-39 cylinder.
  • the present invention utilizes systems and methods for controlling and monitoring parameters, such as pressure, temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, and combinations thereof, of any of the foregoing stabilized compositions, particularly during storage, transport and handling, as described in U.S. Patent Application Publication No. 2022/0136748, the entire disclosure of which is incorporated herein by reference.
  • the storage container for any of the foregoing compositions is a high- pressure vessel.
  • the container for storage, transport and handling of any of the foregoing compositions is a sealed container where the NAG concentration in the gas and/or liquid phases is less than 1.5 vol.% at a temperature of about 21 °C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions stabilisées contenant au moins un fluoroéthyelène et au moins un stabilisant qui stabilise le fluoroéthyelène, en particulier dans des contextes d'expédition et de stockage.
PCT/US2024/048054 2023-09-29 2024-09-24 Compositions stabilisées contenant du fluoroéthylène, procédé de stockage et/ou de transport de celles-ci Pending WO2025072102A1 (fr)

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US202363541472P 2023-09-29 2023-09-29
US63/541,472 2023-09-29

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US5976399A (en) 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
CA2557873A1 (fr) 2004-04-29 2005-11-10 Honeywell International Inc. Compositions contenant des olefines substituees par du fluor
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WO2008027595A1 (fr) 2006-09-01 2008-03-06 E. I. Du Pont De Nemours And Company Agents stabilisants d'alkylsilane pour fluoroléfines
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EP3153560A1 (fr) * 2014-06-06 2017-04-12 Asahi Glass Company, Limited Milieu actif pour cycle thermique, composition pour système à cycle thermique et système à cycle thermique
WO2019213004A1 (fr) 2018-04-30 2019-11-07 The Chemours Company Fc, Llc Compositions de fluorooléfines stabilisées et leurs procédés de production, de stockage et d'utilisation
WO2020035690A1 (fr) 2018-08-14 2020-02-20 Mexichem Fluor S.A. De C.V. Composition de fluide frigorigène et utilisation associée
WO2020135569A1 (fr) 2018-12-26 2020-07-02 中国人民解放军军事科学院军事医学研究院 Composé d'éthylènediamine et son utilisation
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WO2023287695A1 (fr) 2021-07-12 2023-01-19 The Chemours Company Fc, Llc Compositions de fluoroéthylène stabilisées et leurs procédés de stockage et d'utilisation
EP4227390A1 (fr) * 2020-10-09 2023-08-16 Daikin Industries, Ltd. Composition contenant un fluide frigorigène

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4755316A (en) 1987-10-23 1988-07-05 Allied-Signal Inc. Refrigeration lubricants
US5152926A (en) 1989-06-02 1992-10-06 Union Carbide Chemicals & Plastics Technology Corporation Refrigerant lubricant compositions
US5976399A (en) 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
US7294747B2 (en) 2003-10-17 2007-11-13 Arkema France Method of producing 1,1-difluoroethane and application thereof for the production of 1,1-difluoroethylene
US20060116310A1 (en) 2004-04-16 2006-06-01 Honeywell International Inc. Compositions of HFC-152a and CF3I
CA2557873A1 (fr) 2004-04-29 2005-11-10 Honeywell International Inc. Compositions contenant des olefines substituees par du fluor
US20070290164A1 (en) 2004-09-14 2007-12-20 Idemitsu Kosan Co., Ltd. Refrigerator Oil Composition
WO2008027595A1 (fr) 2006-09-01 2008-03-06 E. I. Du Pont De Nemours And Company Agents stabilisants d'alkylsilane pour fluoroléfines
WO2009018117A1 (fr) 2007-07-27 2009-02-05 E. I. Du Pont De Nemours And Company Compositions contenant des fluoro-oléfines, et leurs utilisations
WO2009042847A1 (fr) 2007-09-28 2009-04-02 E. I. Du Pont De Nemours And Company Compositions stabilisatrices à base d'un liquide ionique
US20110272624A1 (en) 2008-04-04 2011-11-10 Dow Global Technologies Llc Refrigerant composition
US8961812B2 (en) 2010-04-15 2015-02-24 E I Du Pont De Nemours And Company Compositions comprising Z-1,2-difluoroethylene and uses thereof
EP3153559A1 (fr) * 2014-06-06 2017-04-12 Asahi Glass Company, Limited Fluide de travail pour cycle thermique, composition pour système à cycle thermique et système à cycle thermique
EP3153560A1 (fr) * 2014-06-06 2017-04-12 Asahi Glass Company, Limited Milieu actif pour cycle thermique, composition pour système à cycle thermique et système à cycle thermique
WO2019213004A1 (fr) 2018-04-30 2019-11-07 The Chemours Company Fc, Llc Compositions de fluorooléfines stabilisées et leurs procédés de production, de stockage et d'utilisation
WO2020035690A1 (fr) 2018-08-14 2020-02-20 Mexichem Fluor S.A. De C.V. Composition de fluide frigorigène et utilisation associée
WO2020135569A1 (fr) 2018-12-26 2020-07-02 中国人民解放军军事科学院军事医学研究院 Composé d'éthylènediamine et son utilisation
US20220136748A1 (en) 2019-03-08 2022-05-05 The Chemours Company Fc, Llc. Methods and containers for transporting, transferring, storing and using refrigerants
US20210107850A1 (en) 2019-06-07 2021-04-15 Daikin Industries, Ltd. Method for producing reaction gas containing (e)-1,2-difluoroethylene
EP4227390A1 (fr) * 2020-10-09 2023-08-16 Daikin Industries, Ltd. Composition contenant un fluide frigorigène
WO2023287695A1 (fr) 2021-07-12 2023-01-19 The Chemours Company Fc, Llc Compositions de fluoroéthylène stabilisées et leurs procédés de stockage et d'utilisation

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