Stable composition comprising vinyl fluoride, method for storage and / or transportation thereof

Abstract

A stable composition is provided comprising at least one vinyl fluoride and at least one stabilizer that stabilizes the vinyl fluoride, particularly under transport and storage conditions.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of priority to U.S. Provisional Application 63 / 541,472, filed September 29, 2023, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention broadly relates to stable compositions comprising at least one vinyl fluoride and at least one stabilizer that inhibits or prevents the decomposition of vinyl fluoride and other undesirable reactions. Background Technology

[0004] For decades, the fluorocarbon industry has been striving to find alternative refrigerants to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that are being phased out under the Montreal Protocol. Solutions for many applications involve the commercialization of HFC compounds used as refrigerants, solvents, fire extinguishing agents, foaming agents, and propellants. These currently most widely used new compounds, such as HFC refrigerants, HFC-134a, and HFC-125, have zero ozone depletion potential (ODP) and are therefore unaffected by the current Montreal Protocol phase-out provisions. In addition to ozone depletion, global warming is another environmental concern for many of these applications. According to the UN IPCC Fifth Assessment Report (AR5), HFC refrigerants such as HFC-134a and HFC-125 have global warming potentials (GWPs) of 1,300 and 3,170, respectively.

[0005] This regulatory environment is constantly evolving, and the characteristics taken into consideration are no longer limited to ODP and GWP. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have low global warming potential, but also exhibit low or no flammability, provide excellent performance in a variety of applications, and meet the standards of evolving regulations.

[0006] There is a need in the art for novel refrigerants that meet evolving regulations and provide heat transfer and refrigerant properties that meet or exceed the efficiency of conventional refrigerants.

[0007] Some fluoroethylenes, particularly difluoroethylenes such as 1,1-difluoroethylene (HFO-1132a) or E / Z-1,2-difluoroethylene (HFO-Z / E-1132), are potential novel refrigerants. However, HFO-Z / E-1132 has been observed to be a reactive compound under certain conditions, such as superheat or excess air. Due to its reactivity, HFO-Z / E-1132 is highly prone to decomposition under superheat or excess air, posing significant challenges in storage, transportation, and handling. The decomposition of HFO-Z / E-1132 can be exothermic and can lead to the formation of toxic and flammable gases, potentially posing serious safety hazards. These compounds have also been observed to be unstable and may undergo disproportionation reactions, for example, at extreme temperatures encountered during storage, handling, and / or transportation, or may produce unwanted byproducts under certain conditions, such as through contact with other compounds in contaminated systems, such as excess air, oxidizing chemicals, or free radical-generating compounds from various contaminants. This undesirable disproportionation and byproduct formation of difluoroethylene can also occur when it is used as a refrigerant or heat transfer fluid.

[0008] The instability and degradation of vinyl fluoride can occur through any number of different mechanisms. For example, under certain conditions and / or in the presence of undesirable contaminants that may act as initiators, difluoroethylene can oligomerize or homopolymerize. International application WO 2023 / 287695, filed on July 11, 2022 (the entire disclosure of which is incorporated herein by reference), provides a solution to this oligomerization / homogenization problem by adding inhibitory compounds.

[0009] Some difluoroethylene compounds, such as HFO-1132a and HFO-Z / E-1132, may also be prone to disproportionation under certain conditions, such as those encountered during packaging, storage, handling, and transportation. Another potential concern associated with fluoroethylene, particularly HFO-Z-1132 and HFO-E-1132, is the reactivity of the compounds, which under certain conditions, especially those related to storage, handling, and transportation, may lead to the generation of toxic and / or flammable gases.

[0010] Therefore, there is a need in the art for stable fluoroethylene compositions that have a reduced (if not eliminated) tendency to undergo decomposition and / or other undesirable reactions (such as polymerization, disproportionation, etc.), especially during the handling, storage and transfer of fluoroethylene refrigerants and refrigerant blends. Summary of the Invention

[0011] The present invention can improve the stability of compositions containing at least one fluoroethylene, and more particularly at least one difluoroethylene, under certain conditions by adding at least one stabilizer to the composition.

[0012] This invention relates to systems and methods for handling, storing, and transporting vinyl fluoride compositions, particularly vinyl fluoride refrigerants and refrigerant blends, that inhibit vinyl fluoride from undergoing undesirable reactions (such as decomposition, polymerization, disproportionation, etc.).

[0013] "Stabilizer" refers to at least one compound according to the invention, which acts to inhibit or suppress the tendency of vinyl fluoride compounds to undergo undesirable reactions, such as decomposition, including disproportionation, polymerization, etc., especially under certain conditions associated with storage, handling and transportation.

[0014] Implementation Scheme 1: A stable composition comprising at least one vinyl fluoride and an effective amount of at least one stabilizer, wherein the at least one stabilizer inhibits at least one of the at least one vinyl fluoride from undergoing decomposition, disproportionation or polymerization under storage and transportation conditions.

[0015] Implementation Scheme 2: The stable composition according to Implementation Scheme 1, wherein the fluoroethylene is difluoroethylene.

[0016] Implementation Scheme 3: The stable composition according to Implementation Scheme 2, wherein the difluoroethylene comprises at least one compound selected from the group consisting of 1,1-difluoroethylene (HFO-1132a), (E)-1,2-difluoroethylene (HFO-E-1132) and (Z)-1,2-difluoroethylene (HFO-Z-1132).

[0017] Implementation Scheme 4: A stable composition according to any one of Implementation Schemes 1 to 3, wherein the stabilizer comprises a compound that is chemically inert relative to the at least one fluoroethylene.

[0018] Implementation Scheme 5: A stable composition according to any one of Implementation Schemes 1 to 4, wherein the stabilizer comprises at least one compound, preferably at least one refrigerant, wherein the boiling point of the at least one compound differs from the boiling point of the fluoroethylene by at least 5°C, preferably at least 10°C, and more preferably at least 20°C.

[0019] Implementation Scheme 6: A stable composition according to any one of Implementation Schemes 1 to 5, wherein the stabilizer comprises at least one compound, preferably at least one refrigerant, wherein the boiling point of the at least one compound differs from the boiling point of the fluoroethylene by at least 30°C, preferably at least 40°C, and more preferably at least 50°C.

[0020] Implementation Scheme 7: A stable composition according to any one of Implementation Schemes 1 to 4, 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, HC FO-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), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

[0021] Implementation Scheme 8: The stable composition according to Implementation Scheme 7, wherein the weight percentage ratio of the stabilizer to the fluoroethylene is 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.

[0022] Implementation Scheme 9: A stable composition according to any one of Implementation Schemes 1 to 5, wherein the at least one stabilizer is selected from the group consisting of polyol esters, polyalkylene glycols and polyvinyl ethers.

[0023] Implementation Scheme 10: The stable composition according to Implementation Scheme 9, wherein the amount of the stabilizer is from about 1% by weight to about 30% by weight based on the total weight of the stable composition.

[0024] Implementation Scheme 11: A stable composition according to any one of Implementation Schemes 1 to 5, wherein the at least one stabilizer is selected from the group consisting of: hydrocarbons, the hydrocarbons including at least one of cyclic monoterpenes; lipophilic organic compounds, the lipophilic organic compounds including tocopherols, such as α-tocopherol; and phenols, aromatic organic compounds having at least one chemical moiety -C6H4(OH), including benzene-1,4-diol.

[0025] Implementation Scheme 12: The stable composition according to Implementation Scheme 11, wherein the amount of the stabilizer is from 0.001% by weight to about 1% by weight based on the total weight of the stable composition.

[0026] Implementation Scheme 13: A stable composition according to any one of Implementation Schemes 1 to 12, wherein the fluoroethylene comprises HFO-E-1132, and the stable composition further comprises at least one additional compound selected from the group consisting of: acetylene, ethane, ethylene, propane, 1,2-dichloro-1,2-difluoroethane (HFC-132), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143), etc. 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.

[0027] Implementation Scheme 14: A stable composition according to any one of Implementation Schemes 1 to 12, wherein the fluoroethylene comprises HFO-Z-1132, and the stable 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.

[0028] Implementation Scheme 15: A stable composition according to any one of Implementation Schemes 1 to 12, wherein the fluoroethylene comprises HFO-1132a, and the stable 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.

[0029] Implementation Scheme 16: A stable composition according to any one of Implementation Schemes 1 to 15, wherein the stable composition comprises a refrigerant blend comprising the at least one fluoroethylene and at least one other refrigerant compound selected from the following: 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-1 233xf, 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), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

[0030] Implementation Scheme 17: A stable composition according to any one of Implementation Schemes 1 to 16, wherein the at least one stabilizer is selected from the group consisting of HCl, HF, HFC-142b, HFC-32, HCFO-1122, HCFO-1122a, HCFO-1131, HFC-152a, ethane, and combinations thereof.

[0031] Implementation Scheme 18: A stable composition according to any one of Implementation Schemes 1 to 17, wherein the storage and transport conditions include temperatures up to 54.5°C.

[0032] Implementation Scheme 19: A stable composition according to any one of Implementation Schemes 1 to 18, wherein the stable composition is free of or substantially free of Group A fluorinated substances.

[0033] Implementation Scheme 20: A stable composition according to any one of Implementation Schemes 1 to 18, wherein the degradation products of the stable composition are free of or substantially free of Group A fluorinated substances.

[0034] Implementation Scheme 21: A container comprising a stable composition according to any one of Implementation Schemes 1 to 20.

[0035] Implementation Scheme 22: The container according to Implementation Scheme 21, wherein the stable composition is miscible at temperatures up to 54.5°C and pressure ratings of about 145 psig or greater.

[0036] Implementation Scheme 23: A container according to any one of Implementation Schemes 21 to 22, wherein the container containing the stable composition is transported from a first location (e.g., a manufacturing facility) to a second location (e.g., a usage facility) remote from the first location.

[0037] Implementation Scheme 24: A container according to any one of Implementation Schemes 21 to 23, wherein the fluoroethylene is liquid at a temperature of about -60°C to about 54.5°C.

[0038] Implementation Scheme 25: A container according to any one of Implementation Schemes 21 to 24, wherein at a temperature of about 25°C, the concentration of oxygen and / or water in the gas phase and / or liquid phase of the container is in the range of about 3 vol ppm to less than about 3,000 vol ppm.

[0039] Implementation Scheme 26: A container according to any one of Implementation Schemes 21 to 25, wherein the container has a pressure rating of about 145 psig or greater.

[0040] Implementation Scheme 27: A method for stabilizing vinyl fluoride for storage and transportation, the method comprising mixing the vinyl fluoride with at least one stabilizer in a suitable container to form a liquid stable mixture, wherein the at least one stabilizer inhibits the vinyl fluoride from undergoing at least one of decomposition, disproportionation or polymerization under storage and transportation conditions.

[0041] Implementation Scheme 28: According to the method of Implementation Scheme 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-1 122a(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), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

[0042] Implementation Scheme 29: According to the method of Implementation Scheme 28, the weight percentage ratio of the stabilizer to the fluoroethylene is 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.

[0043] Implementation Scheme 30: The method according to Implementation Scheme 27, wherein the at least one stabilizer is selected from the group consisting of polyol esters, polyalkylene glycols and polyvinyl ethers.

[0044] Implementation Scheme 31: The method according to Implementation Scheme 30, wherein the amount of the stabilizer is from about 1% by weight to about 30% by weight based on the total weight of the stabilized composition.

[0045] Implementation Scheme 32: The method according to Implementation Scheme 27, wherein the at least one stabilizer is selected from the group consisting of: hydrocarbons, the hydrocarbons including at least one of cyclic monoterpenes; lipophilic organic compounds, the lipophilic organic compounds including tocopherols, such as α-tocopherol; and phenols, aromatic organic compounds having at least one chemical moiety -C6H4(OH), including benzene-1,4-diol.

[0046] Implementation Scheme 33: The method according to Implementation Scheme 32, wherein the amount of the stabilizer is from 0.001% by weight to about 1% by weight based on the total weight of the stabilized composition.

[0047] Implementation Scheme 34: The method according to any one of Implementation Schemes 27 to 32, wherein the fluoroethylene comprises HFO-E-1132, and the stable 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 (HF... C-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.

[0048] Implementation Scheme 35: The method according to any one of Implementation Schemes 27 to 32, wherein the fluoroethylene comprises HFO-Z-1132, and the stable 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.

[0049] Implementation Scheme 36: The method according to any one of Implementation Schemes 27 to 32, wherein the fluoroethylene comprises HFO-1132a, and the stable 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.

[0050] Implementation Scheme 37: The method according to any one of Implementation Schemes 27 to 36, wherein the stable composition comprises a refrigerant blend comprising the at least one fluoroethylene and at least one other refrigerant compound selected from the following: 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-12 33xf, 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), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

[0051] Implementation Scheme 38: The method according to Implementation Scheme 27, wherein the at least one stabilizer is selected from the group consisting of HCl, HF, HFC-142, HFC-32, HCFO-1122, HCFO-1122a, HCFO-1131, HFC-152a, ethane, and combinations thereof.

[0052] Implementation Scheme 39: The method according to any one of Implementation Schemes 27 to 38, wherein the stable composition is free of or substantially free of Group A fluorinated substances.

[0053] Implementation Scheme 40: The method according to any one of Implementation Schemes 27 to 38, wherein the degradation products of the stable composition are free of or substantially free of Group A fluorinated substances.

[0054] Implementation Scheme 41: A method for stably storing and / or transporting a composition containing vinyl fluoride, the method comprising performing the process according to any one of Implementation Schemes 27 to 40 to form a stable mixture stored in a liquid state in the container; and storing and / or transporting the container containing the stable mixture in liquid state.

[0055] The embodiments of the present invention can be used alone or in combination with each other, and different embodiments can be combined to form a part of the present invention. Attached Figure Description

[0056] Figure 1 This is a perspective view of a refrigerant distribution system according to one embodiment of the present disclosure.

[0057] Figure 2 This is a front view of a vertical ton tank according to an implementation plan.

[0058] Figure 3 This is a side view of a vertical ton tank according to one implementation plan.

[0059] Figure 4A This is a front view of the internal piping of a vertical tonnage tank according to one implementation scheme.

[0060] Figure 4B This is an unfolded side view of the internal piping of a vertical tonnage tank according to one implementation scheme.

[0061] Figure 5 A pipe connector for a vertical tonnage tank according to one embodiment is shown.

[0062] Figure 6 This is a view of the bottom portion of a vertical ton tank according to one implementation scheme.

[0063] Figure 7 This is an unfolded top view of the valve configuration of a vertical tonnage tank according to one implementation scheme.

[0064] Figure 8 This is an unfolded side view of the valve configuration of a vertical tonnage tank according to one implementation scheme.

[0065] Figure 9This is a view of a vertical ton tank with a bottom protective liner according to one embodiment.

[0066] Figure 10 A door, as part of the bottom protective liner of a vertical tonnage tank, is shown according to one embodiment. Detailed Implementation

[0067] In some embodiments, the present invention provides a stable composition comprising at least one vinyl fluoride and an effective amount of at least one stabilizer. Without wishing to be bound by any theory or interpretation, it is believed that vinyl fluoride compounds, particularly difluoroethylene compounds (such as HFO-E / Z-1132 and HFO-1132a), are prone to reactions such as decomposition, including but not limited to disproportionation, polymerization, etc., under certain conditions, particularly temperature and pressure conditions associated with packaging, handling, storage, and transportation. "Stable" means a composition in which the tendency of the vinyl fluoride compound to undergo reactions (such as decomposition, polymerization, disproportionation, etc.), particularly under certain conditions associated with packaging, storage, handling, and transportation, is suppressed or contained. "Suppressed," "inhibited," "contained," or "contained" means that the tendency of the vinyl fluoride compound to undergo reactions (such as decomposition, including but not limited to polymerization, disproportionation, etc.) relative to the tendency of a composition without a stabilizer has been eliminated or at least reduced to a degree to which the composition is safe for storage and transportation. "Effective amount" means an amount of at least one stabilizer compound sufficient to achieve the desired result of inhibiting the fluoroethylene compound from undergoing reactions such as decomposition, including but not limited to polymerization, disproportionation, etc., especially under certain conditions associated with storage, handling and transport.

[0068] The present invention enables the safe storage, transport and handling of compositions containing fluoroethylene, particularly compositions containing difluoroethylene, and more particularly compositions containing HFO-1132a, HFO-E-1132 or HFO-Z-1132, in the form of liquid mixtures containing stabilizers.

[0069] On the other hand, the present invention relates to a container for long-term storage of vinyl fluoride compositions, particularly compositions containing difluoroethylene (such as HFO-1132, HFO-E-1132, or HFO-Z-1132), preferably in the form of a liquid mixture just described. Typically, long-term storage will be carried out under varying temperature conditions, but the liquid mixture is preferably stored stably at temperatures up to about 54.5°C (130°F). During storage and shipment, the liquid mixture remains stable at temperatures up to about 54.5°C. Furthermore, at temperatures encountered during shipment or storage, no chemical interaction occurs between the vinyl fluoride and the stabilizer component of the mixture (liquid or vapor). Long-term storage means storing or transporting the liquid mixture for at least 6 hours.

[0070] In one embodiment, the present invention relates to a container that stably stores a composition comprising HFO-E-1132, preferably pure HFO-E-1132, the container being maintained at a temperature up to about 54.5°C and having a pressure rating of about 1000 psig or greater, preferably about 1500 psig or greater, more preferably about 2000 psig or greater, the container being configured for storage and / or shipment via conventional routes, such as by rail, road, waterway, etc.

[0071] In one embodiment, the present invention relates to a container that stably stores a composition comprising HFO-E-1132, preferably a blend comprising HFO-E-1132, the container being maintained at a temperature up to about 54.5°C and having a pressure rating of 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 for storage and / or shipment via conventional routes, such as by rail, road, waterway, etc.

[0072] In one embodiment, the present invention relates to a container that stably stores a composition comprising pure or blended HFO-Z-1132, the container being maintained at a temperature up to about 54.5°C and having a pressure rating of about 145 psig or greater, preferably about 240 psig or greater, or more preferably about 500 psig or greater, the container being configured for storage and / or shipment via conventional routes such as by rail, road, waterway, etc.

[0073] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, conditions A or B satisfy one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0074] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If in a claim, it will not include protection for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claim.

[0075] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect one or more essential and novel features of the invention protected by the claims, particularly the mode of action for achieving the desired results of any of the methods of the invention. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0076] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the specification should be interpreted as also using the terms “consistently consisting of” or “comprises of” to describe such inventions.

[0077] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. The description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0078] As used herein, the term "ethylene fluoride" describes a compound comprising two carbon atoms linked by a double bond and also comprising at least one fluorine atom, optionally at least one hydrogen atom, and optionally at least one chlorine atom. In one embodiment, ethylene fluoride has the formula CR1R2=CR3R4, wherein R1 is fluorine and R2, R3, and R4 are independently selected from hydrogen, fluorine, and chlorine. In one embodiment, ethylene fluoride is hydrofluoroethylene. In one embodiment, ethylene fluoride is difluoroethylene. In one embodiment, difluoroethylene comprises (Z)-1,2-difluoroethylene (HFO-Z-1132). In one embodiment, difluoroethylene comprises (E)-1,2-difluoroethylene (HFO-E-1132). In one embodiment, difluoroethylene is both HFO-Z-1132 and HFO-E-1132. In one embodiment, difluoroethylene comprises 1,1-difluoroethylene (HFO-1132a).

[0079] In one embodiment, the vinyl fluoride component of the stable composition comprises HFO-1132(E), HFO-1132(Z), and / or HFO-1132a. In another embodiment, the vinyl fluoride comprises HFO-1132(E), HFO-1132(Z), and / or HFO-1132a having a purity greater than 99% by weight, greater than 99.5% by weight, and in some cases, greater than 99.5% by weight to 99.98% by weight.

[0080] In some embodiments, the vinyl fluoride component of the stable composition or method is formed, purified, and / or obtained by methods known in the art. For example, in some embodiments, the vinyl fluoride component is (E)-1,2-difluoroethylene or Z-1,2-difluoroethylene formed and / or purified by the method described in U.S. Patent Application Publication 2021 / 0107850, the entire disclosure of which is hereby incorporated by reference. In some embodiments, the vinyl fluoride component is (E)-1,2-difluoroethylene or Z-1,2-difluoroethylene formed and / or purified by methods described in the following documents: U.S. Provisional Applications 63 / 541,445, 63 / 541,320, 63 / 541,333, or 63 / 541,353, filed September 29, 2023, the entire disclosure of each of which is hereby incorporated by reference. In other embodiments, the vinyl fluoride component is 1,1-difluoroethylene formed and / or purified by the method described in U.S. Patent 7,294,747, the entire disclosure of which is hereby incorporated by reference. Those skilled in the art will understand that the present invention is not limited to vinyl fluoride components produced by one of the methods described above, but covers such components produced by any method known in the art.

[0081] In some embodiments, the stabilized composition comprises at least one fluoroethylene component, a stabilizer, and at least one additional compound. In some embodiments, the at least one additional compound comprises at least one fluoroolefin. In some embodiments, the at least one additional compound comprises at least two additional compounds. In another embodiment, the at least one additional compound comprises a hydrocarbon, such as propane and butane.

[0082] As used herein, the term fluoroolefin describes a compound comprising a carbon atom, a fluorine atom, and optionally a hydrogen atom. In one embodiment, the fluoroolefin in the composition of the present invention comprises a compound having 2 to 12 carbon atoms. In another embodiment, the fluoroolefin comprises a compound having 3 to 10 carbon atoms, and in yet another embodiment, the fluoroolefin comprises a compound having 3 to 7 carbon atoms.

[0083] Many compounds in the compositions of this invention exist as different configurational isomers or stereoisomers. When no specific isomer is specified, this invention is intended to include all isomers of a single configuration, a single stereoisomer, or any combination thereof. For example, F11E is intended to represent any combination or mixture of two isomers of 1,1,1,4,4,4-hexafluorobut-2-ene in any ratio, including the E-isomer, the Z-isomer, or any ratio of two isomers of 1,2-difluoroethylene. As another example, HFO-1132a is intended to represent any combination or mixture of two isomers of 1,2-difluoroethylene in any ratio, including the E-isomer, the Z-isomer, or any ratio of two isomers of 1,2-difluoroethylene.

[0084] In one embodiment, 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), and 1,1,2-trifluoroethane (HF). C-143), 1-chloro-1,2-difluoroethylene (HCFO-1122a), trifluoroethylene (HFO-1123), 1-chloro-2-fluoroethylene (HCFO-1131), (E)-1,2-difluoroethylene ((E)-HFO-1132), (Z)-1,2-difluoroethylene ((Z)-HFO-1132), 1,1-difluoroethylene (HFO-1132a), difluoromethane (HFC-32), HFC-134, HFC-152a, HCFO-1243ze(E), HFO-1234yf, and combinations thereof. Based on the total weight of the refrigerant portion of the stable composition, the amount of at least one additional compound may be in the range of about 1 ppm to about 2000 ppm, about 10 ppm to about 1000 ppm, about 100 ppm to about 500 ppm, about 50 ppm to about 200 ppm, about 10 ppm to about 100 ppm, greater than about 0.1% or any value, range or subrange thereof.

[0085] In some specific embodiments, the fluoroethylene component is 1,1-difluoroethylene (HFO-1132a), and 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 greater than 0% by weight based on the total weight of the refrigerant portion, and in some cases about 0.01% by weight. In some embodiments, the total amount of additional compounds, based on the total weight of the refrigerant portion of the composition, is between greater than 0 wt% and 0.3 wt%, between greater than 0 wt% and 0.1 wt%, between greater than 0 wt% and 0.02 wt%, or between greater than 0 wt% and about 0.01 wt%.

[0086] In some specific embodiments, the fluoroethylene component is (E)-1,2-difluoroethylene ((E)-HFO-1132), and 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-1... 123), 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 greater than 0.5% by weight and, in some cases, about 0.01% by weight, based on the total weight of the refrigerant portion of the composition. In some embodiments, the total amount of the additional compound, based on the total weight of the refrigerant portion of the composition, is between greater than 0.5% by weight and 0.3%, between greater than 0.5% by weight and 0.1% by weight, between greater than 0.5% by weight and 0.02% by weight, or between greater than 0.5% by weight and about 0.01% by weight, including all intermediate values ​​and ranges.

[0087] In some specific embodiments, the fluoroethylene component is (Z)-1,2-difluoroethylene ((Z)-HFO-1132), and 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, CO2, 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(Z), HFO-1243ze(E), HFO-1243ze(Z), HCFO-1233zd(E), HFC-134, HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf and HCFO-1224yd(Z), and combinations thereof, based on the total weight of the refrigerant portion, are greater than 0% by weight and, in some cases, approximately 0.01% by weight. In some embodiments, based on the total weight of the refrigerant portion of the composition, the total amount of the additional compound is between greater than 0 wt% and 0.3 wt%, between greater than 0 wt% and 0.1 wt%, between greater than 0 wt% and 0.02 wt%, or between greater than 0 wt% and about 0.01 wt%, including all intermediate values ​​and ranges.

[0088] In some embodiments, the stabilized composition comprises a stabilizer and a refrigerant blend, the refrigerant blend comprising at least one fluoroethylene and at least one other compound. Such a composition may also contain any of the additional compounds listed above. The at least one fluoroethylene is preferably difluoroethylene selected from HFO-Z-1132, HFO-E-1132, and HFO-1132a.

[0089] In one embodiment, at least one other compound in the refrigerant blend may be selected from fluoroolefins, hydrofluorocarbons, hydrocarbons, dimethyl ethers, CF3I, ammonia, carbon dioxide (CO2), and mixtures thereof, meaning a mixture of any of the additional compounds listed in this paragraph. The amount of another refrigerant compound may range from about 1% to about 90% by weight, from about 5% to about 75% by weight, and in some cases from about 10% to about 50% by weight, including all intervening values ​​and ranges.

[0090] In one embodiment, at least one other compound of the refrigerant blend may be 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), HFO-1234yf, HFC-143, HFC-143a, HFC-134, CFC-12, HFO-1243zf, HFO-1224yd(Z), HFO-1233xf, HCFO-1131a, HCFO-11 22a(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), HFC-227ea, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, ethane, propane, butane, and combinations thereof.

[0091] In one embodiment, at least one other compound of the refrigerant blend may be selected from CO2, 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-1234y e(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-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, ethane, propane, butane, and combinations thereof.

[0092] In some embodiments, at least one other compound includes a fluoroolefin, such as any of the fluoroolefins listed above. The amount of the other fluoroolefin may be from about 1% to about 90% by weight, from about 5% to about 75% by weight, and in some cases from about 10% to about 50% by weight, including all intervening values ​​and ranges.

[0093] In one embodiment, 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. Particularly available are hydrofluorocarbons having 1 to 7 carbon atoms and a normal boiling point of about -90°C to about 80°C. The hydrofluorocarbons are commercially available products from various sources or can be prepared by methods known in the art. Representative hydrofluorocarbons 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), and fluoroethane (CH3... CH2F, HFC-161), 1,1,1,2,2,3,3-heptafluoropropane (CF3CF2CHF2, HFC-227ca), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea), 1,1,2,2,3,3,-hexafluoropropane (CHF2CF2CHF2, HFC-236ca), 1,1,1,2,2,3-hexafluoropropane (CF3CF3CH2F, HFC-236cb), 1,1,1,2,3,3-hexafluoropropane (CF3CHFCHF2, HFC-236ea), 1,1 1,3,3,3-Hexafluoropropane (CF3CH2CF3, HFC-236fa), 1,1,2,2,3-Pentafluoropropane (CHF2CF2CH2F, HFC-245ca), 1,1,1,2,2-Pentafluoropropane (CF3CF2CH3, HFC-245cb), 1,1,2,3,3-Pentafluoropropane (CHF2CHFCHF2, HFC-245ea), 1,1,1,2,3-Pentafluoropropane (CF3CHFCH2F, HFC-245eb), 1,1,1,3,3-Pentafluoropropane (CF3CH2CHF2, HFC-245) fa), 1,2,2,3-tetrafluoropropane (CH2FCF2CH2F, HFC-254ca), 1,1,2,2-tetrafluoropropane (CHF2CF2CH3, HFC-254cb), 1,1,2,3-tetrafluoropropane (CHF2CHFCH2F, HFC-254ea), 1,1,1,2-tetrafluoropropane (CF3CHFCH3, HFC-254eb), 1,1,3,3-tetrafluoropropane (CHF2CH2CHF2, HFC-254fa), 1,1,1,3-tetrafluoropropane (CF3CH2CH2F, HFC-254fb), 1,1,1-Trifluoropropane (CF3CH2CH3, HFC-263fb), 2,2-Difluoropropane (CH3CF2CH3, HFC-272ca), 1,2-Difluoropropane (CH2FCHFCH3, HFC-272ea), 1,3-Difluoropropane (CH2FCH2CH2F, HFC-272fa), 1,1-Difluoropropane (CHF2CH2CH3, HFC-272fb), 2-Fluoropropane (CH3CHFCH3, HFC-281ea), 1-Fluoropropane (CH2FCH2CH3, HFC-281fa), 1,1,2,2,3,3,4,4-Octafluorobutane (CH F2CF2CF2CHF2 (HFC-338pcc), 1,1,1,2,2,4,4,4-octafluorobutane (CF3CH2CF2CF3 (HFC-338mf), 1,1,1,3,3-pentafluorobutane (CF3CH2CHF2 (HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF3CHFCHFCF2CF3 (HFC-43-10mee)), and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetrafluoroheptane (CF3CF2CHFCHFCF2CF2CF3 (HFC-63-14mee)).

[0094] In one embodiment, examples of suitable hydrofluorocarbons include at least one member selected from: HFC-32, HFC-125, HFC-134a, HFC-152a, HFC-236fa, and HFC-227ea. The amount of hydrofluorocarbon may range from about 1% by weight to about 90% by weight, from about 5% by weight to about 75% by weight, and in some cases from about 10% by weight to about 50% by weight, including all intermediate values ​​and ranges.

[0095] In another embodiment, at least one other compound comprises one or more hydrocarbons. The hydrocarbons of the present invention include compounds having only carbon and hydrogen atoms. Compounds having 3 to 7 carbon atoms are particularly available. Hydrocarbons are commercially available from numerous chemical suppliers. Representative 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.

[0096] In another embodiment, at least one other compound comprises a hydrocarbon containing a heteroatom, such as dimethyl ether (DME, CH3OCH3). DME is commercially available. The amount of hydrocarbon may range from about 1% to about 90% by weight, from about 5% to about 75% by weight, and in some cases from about 10% to about 50% by weight, including all intervening values ​​and ranges.

[0097] In another embodiment, at least one other compound comprises trifluoroiodomethane (CF3I), which is commercially available from various sources or can be prepared by methods known in the art. The amount of CF3I can range from about 1 wt% to about 90 wt%, from about 5 wt% to about 75 wt%, and in some cases from about 10 wt% to about 50 wt%, including all intervening values ​​and ranges.

[0098] In another embodiment, at least one other compound comprises carbon dioxide (CO2), which is commercially available from various sources or can be prepared by methods known in the art. The amount of CO2 may range from about 1% by weight to about 90% by weight, from about 5% by weight to about 75% by weight, and in some cases from about 10% by weight to about 50% by weight, including all intervening values ​​and ranges.

[0099] In another embodiment, at least one other compound comprises at least one member selected from HFC-23, HFC-41, HFC-134a, HCFC-22, CFC-12, HCC-40 and 143a, in an amount ranging from about 1 wt% to about 90 wt%, from about 5 wt% to about 75 wt%, and in some cases from about 10 wt% to about 50 wt%, including all intervening values ​​and ranges.

[0100] In another embodiment, at least one other compound includes at least one member selected from water, air (N2 / O2 78 / 21 ratio), air (N2 / O2 > 78 / 21 ratio), O2, N2, Ar, CO2, CH4, and He.

[0101] If desired, the refrigerant portion of the blend composition may further include at least one additional member selected from HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113. The amount of the additional member may be greater than 0% by weight to about 5% by weight, about 0% by weight to about 2% by weight, and in some cases about 0% by weight to about 0.5% by weight. In one specific embodiment, the aforementioned amount of the additional member is blended with at least one of HFO-1132(E), HFO-1132(Z), and HFO-1132a. In another specific embodiment, the aforementioned additional member is blended with at least one of HFO-1132(E), HFO-1132(Z) and HFO-1132a, and at least one hydrofluorocarbon selected from HFC-32, HFC-125, HFC-134, HFC-134a, HFC-152a, 236fa and HFC-227ea, and in some cases combined with carbon dioxide.

[0102] In some embodiments, the fluoroethylene component is 1,1-difluoroethylene in the refrigerant blend composition as described in International Publication WO2020 / 035690A1 or International Publication WO2020 / 135569A1, the entire contents of which are hereby incorporated by reference. The stable composition also contains a stabilizer according to the invention.

[0103] In some embodiments, the fluoroethylene component is (Z)-1,2-difluoroethylene or (E)-1,2-difluoroethylene in the refrigerant blend compositions described in U.S. Patent 8,961,812, U.S. Provisional Application 63 / 541,360, filed September 29, 2023, U.S. Provisional Application 63 / 541,379, filed September 29, 2023, or U.S. Provisional Application 63 / 541,415, filed September 29, 2023, the entire disclosure of each of which is hereby incorporated by reference, and the stabilized composition further comprises a stabilizer according to the invention.

[0104] In some embodiments, the fluoroethylene component is (E)-1,2-difluoroethylene in the refrigerant blend compositions described in U.S. Patent 8,961,812, U.S. Provisional Application 63 / 541,360, filed September 29, 2023, U.S. Provisional Application 63 / 541,379, filed September 29, 2023, or U.S. Provisional Application 63 / 541,415, filed September 29, 2023, the entire disclosure of each of these patents being incorporated herein by reference. The stabilized composition also comprises a stabilizer according to the invention, and the stabilized composition comprises less than about 0.1% by weight (1,000 ppm) of HFO-Z-1132, preferably less than about 100 ppm of HFO-Z-1132.

[0105] In some embodiments, the refrigerant portion of the stable composition comprises a refrigerant blend comprising at least one fluoroethylene and at least one other refrigerant compound selected from: 2,3,3,3-tetrafluoropropylene (HFO-1234yf), difluoromethane (HFC-32), 1,3,3,3-tetrafluoropropylene (HFO-1234ze(E)), and 1,1-difluoroethane (HFC-152a). In some embodiments, the refrigerant blend further comprises at least one refrigerant compound selected from: trifluoroethylene (HFO-1123), trifluoroiodomethane (CF3I), carbon dioxide (R-744, CO2), 1,1,1,2-tetrafluoroethane (HFC-134a), and 1,1,2,2-tetrafluoroethane (HFC-134).

[0106] In some embodiments, the refrigerant blend constituting the refrigerant portion of the composition comprises about 1% to about 96% by weight of vinyl fluoride and about 4% to about 99% by weight of at least one other refrigerant compound, alternatively about 1% to about 20% by weight of vinyl fluoride and about 80% to about 99% by weight of at least one other refrigerant compound, alternatively about 2% to about 14% by weight of vinyl fluoride and about 86% to about 98% by weight of at least one other refrigerant compound, alternatively about 20% or more by weight of vinyl fluoride and up to about 80% by weight of at least one other refrigerant compound, alternatively about 72% to about 96% by weight of vinyl fluoride and about 4% to about 28% by weight of at least one other refrigerant compound, or any value, range or subrange therebetween.

[0107] In some specific embodiments, the refrigerant blend constituting the refrigerant portion of the stable composition comprises 2% to 35% by weight of vinyl fluoride, 2% to 96% by weight of a second refrigerant compound (such as, for example, HFC-152a), and 2% to 96% by weight of a third refrigerant compound (such as, for example, HFO-1234ze(E)), such as, for example, 4% to 10% by weight of vinyl fluoride, 2% to 30% by weight of the second refrigerant compound, and 60% to 94% by weight of the third refrigerant compound.

[0108] In some specific embodiments, the refrigerant blend constituting the refrigerant portion of the stable composition comprises about 1% to about 35% fluoroethylene, about 1% to about 40% fluorocarbons, a second refrigerant compound (such as, for example, HFC-32), and about 40% to about 98% fluorocarbons (such as, for example, HFO-1234yf).

[0109] Vinyl fluoride (or a refrigerant blend containing vinyl fluoride) and a stabilizer can be mixed together as liquids to form a homogeneous liquid mixture in which the compounds are completely miscible with each other. The liquid mixture can be prepared in one vessel and then transferred to another vessel for storage or shipment. The liquid mixture is preferably miscible under the temperature and pressure conditions of the storage and transport containers, i.e., temperatures up to 54.5°C and pressure ratings of about 145 psig or greater.

[0110] In one embodiment, the stabilizer is a compound compatible with at least one of vinyl fluoride, preferably difluoroethylene, and more preferably HFO-1132(E), HFO-1132(Z), and HFO-1132a, and a composition comprising a blend of vinyl fluoride, preferably difluoroethylene, and more preferably HFO-1132(E), HFO-1132(Z), and HFO-1132a. More specifically, in one embodiment, the stabilizer comprises an inert compound, meaning a compound compatible with vinyl fluoride but chemically inert to vinyl fluoride. Preferably, the inert compound is present in an amount sufficient to dilute the concentration of vinyl fluoride to a level that allows for safe and stable storage, handling, and transportation of vinyl fluoride, wherein the reaction risk of vinyl fluoride (such as undesirable decomposition, polymerization, disproportionation, etc.) is minimized.

[0111] In one embodiment, the stabilizer comprises one or more refrigerants having a boiling point different from that of the vinyl fluoride component, preferably with a boiling point difference of at least 5°C, or at least 10°C, or at least 20°C, or at least 30°C, or at least 40°C, or at least 50°C between the stabilizer and the vinyl fluoride component. In one embodiment, the stabilizer comprises a refrigerant whose boiling point differs from that of HFO-Z-1132 by preferably at least 5°C, or at least 10°C, or at least 20°C, or at least 30°C, or at least 40°C, or at least 50°C. In one embodiment, the stabilizer comprises a refrigerant whose boiling point differs from that of HFO-E-1132 by preferably at least 5°C, or at least 10°C, or at least 20°C, or at least 30°C, or at least 40°C, or at least 50°C. In one embodiment, the stabilizer comprises one or more refrigerants whose boiling point differs from that of HFO-1132a by preferably at least 5°C, or at least 10°C, or at least 20°C, or at least 30°C, or at least 40°C, or at least 50°C.

[0112] In one embodiment, the stabilizer comprises one or more compounds selected from the following: 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(Z), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

[0113] In one embodiment, the stabilizer comprises one or more compounds selected from the following: CO2, 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-1234y e(E), HFO-1234ye(Z), HFO-1234zc, HFO-1243yc, HFO-1243zc, HFO-1243ye(E), HFO-1243ye(Z), HFO-1243ze(E), HFO-1243ze(Z), HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

[0114] In one embodiment, the stabilizer includes one or more lubricants. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol. ® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ether (PVE).

[0115] Any suitable effective amount of stabilizer can be used in the aforementioned compositions containing at least one vinyl fluoride to form the stable compositions of the present invention. As stated above, the phrase "effective amount" refers to the amount of stabilizer of the present invention that, when added to a composition containing at least one vinyl fluoride, produces a composition in which the vinyl fluoride will not undergo reactions (such as decomposition, including but not limited to polymerization, disproportionation, etc.), particularly under certain conditions associated with storage, handling, and transportation, or at least reduces its tendency to undergo such reactions. Such conditions include temperatures up to about 54.5°C, as commonly encountered during storage and transportation.

[0116] Although any suitable effective amount may be used, in one embodiment where the stabilizer is one of the refrigerants discussed above, the weight percentage ratio of the stabilizer to vinyl fluoride, particularly difluoroethylene and more particularly HFO-1132(E), HFO-1132(Z) or HFO-1132a is 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.

[0117] In one embodiment, where the stabilizer includes one or more lubricants such as POE, PVE, or PAG, the stabilized composition (i.e., a liquid mixture of the stabilizer and a refrigerant portion containing at least one fluoroethylene) comprises about 1% to about 30% by weight of the stabilizer.

[0118] In one embodiment, the stabilizer comprises one or more of the following: a hydrocarbon, said hydrocarbon comprising at least one of cyclic monoterpenes; a lipophilic organic compound, said lipophilic organic compound comprising tocopherol, such as α-tocopherol; or a phenol, an aromatic organic compound having at least one chemical moiety -C6H4(OH), including benzene-1,4-diol. Specific examples of stabilizers include at least one member selected from: D-limonene, α-terpinene, α-tocopherol, butylated hydroxytoluene (BHT), 4-methoxyphenol, and benzene-1,4-diol. Other examples of stabilizers include at least one member selected from: D-limonene, terpinene, pinene, p-cymene, terpineol, myrcene, farnesene, 4-methoxyphenol, butylated hydroxytoluene, butylated hydroxyanisole, and tert-butylhydroquinone. In this embodiment, the stable composition (i.e., a liquid mixture of a stabilizer and a refrigerant portion containing at least one fluoroethylene) comprises at least 10 ppm (i.e., 0.001 wt%) of stabilizer. The higher the proportion of stabilizer present in the liquid mixture, the greater the safety margin against the reaction of fluoroethylene. Preferably, the liquid mixture will not contain more than 1 wt% stabilizer based on the total weight of the mixture. In one embodiment, based on the total weight of the liquid mixture, the liquid mixture contains approximately 0.001 wt% to approximately 1 wt%, approximately 0.005 wt% to approximately 1 wt%, approximately 0.008 wt% to approximately 1 wt%, approximately 0.01 wt% to approximately 1 wt%, approximately 0.02 wt% to approximately 1 wt%, approximately 0.05 wt% to approximately 1 wt%, approximately 0.08 wt% to approximately 1 wt%, approximately 0.1 wt% to approximately 1 wt%, approximately 0.2 wt% to approximately 1 wt%, approximately 0.3 wt% to approximately 1 wt%, and approximately 0.4 wt% to approximately 1 wt%. About 0.5 wt% to about 1 wt%, about 0.6 wt% to about 1 wt%, about 0.7 wt% to about 1 wt%, about 0.8 wt% to about 1 wt%, about 0.9 wt% to about 1 wt%, about 0.001 wt% to about 0.09 wt%, about 0.001 wt% to about 0.05 wt%, about 0.001 wt% to about 0.01 wt%, about 0.001 wt% to about 0.1 wt%, about 0.005 wt% to about 0.01 wt%, or about 0.005 wt% to about 0.1 wt%, and all values ​​and ranges therein.

[0119] In one embodiment, the stabilizer content in the stabilized composition may be greater than the vinyl fluoride content. The relatively high concentration of stabilizer in the liquid mixture essentially dilutes the vinyl fluoride, making it less susceptible to the decomposition reaction described herein.

[0120] In one embodiment, the composition comprises HFO-Z-1132 and a stabilizer, wherein the stabilizer comprises one or more compounds, preferably a refrigerant compound, having a boiling point that differs from the boiling point of HFO-Z-1132 by at least about 5°C, or at least about 10°C, or at least about 20°C, or at least about 30°C, or at least about 40°C, or at least about 50°C. In one embodiment, the composition comprises HFO-Z-1132 having a boiling point of -26°C at atmospheric pressure (760 mm Hg, 101.3 kPa, absolute pressure) and a stabilizer comprising a refrigerant compound having a boiling point of -80°C to 40°C at atmospheric pressure.

[0121] In one embodiment, the composition comprises HFO-E-1132 and a stabilizer, wherein the stabilizer comprises one or more compounds, preferably a refrigerant compound, having a boiling point that differs from the boiling point of HFO-E-1132 by at least about 5°C, or at least about 10°C, or at least about 20°C, or at least about 30°C, or at least about 40°C, or at least about 50°C. In one embodiment, the composition comprises HFO-E-1132 having a boiling point of -52°C at atmospheric pressure and a stabilizer comprising a refrigerant compound having a boiling point of -80°C to 40°C at atmospheric pressure.

[0122] In one embodiment, the composition comprises HFO-1132a and a stabilizer, wherein the stabilizer comprises one or more compounds, preferably a refrigerant compound, having a boiling point that differs from the boiling point of HFO-1132a by at least about 5°C, or at least about 10°C, or at least about 20°C, or at least about 30°C, or at least about 40°C, or at least about 50°C. In one embodiment, the composition comprises HFO-1132a having a boiling point of -84°C at atmospheric pressure and a stabilizer comprising a refrigerant compound having a boiling point of -90°C to 40°C at atmospheric pressure.

[0123] In another embodiment, the aforementioned stable composition of the present invention is substantially free of at least one of dimethyl ether, CF3I, ammonia, and carbon dioxide. In a preferred aspect of this embodiment, the aforementioned stable composition is substantially free of CF3I. In this document, “substantially free” means that the composition contains less than about 10%, typically less than about 5%, and in some cases 0% of dimethyl ether, CF3I, ammonia, and carbon dioxide.

[0124] The stable compositions of the present invention can be prepared by any convenient method of combining the desired amounts of the individual components. A preferred method is to weigh the desired amounts of the components and then combine them in a suitable vessel. Stirring may be used if desired.

[0125] In some embodiments, the stabilizer is a component incorporated into, used for, or otherwise present in a method for forming vinyl fluoride (e.g., E / Z-HFO-1132 or HFO-1132a) or for purifying vinyl fluoride, and remains present in the reaction product mixture and is retained with the vinyl fluoride after any separation process to act as a stabilizer for the vinyl fluoride during packaging, storage, transportation, and handling. For example, in one embodiment, the stabilizer may be a reactant, reagent, catalyst, solvent, etc., used in a method for forming and / or purifying vinyl fluoride.

[0126] Examples of such reactants / reagents include, but are not limited to, hydrogen chloride (HCl).

[0127] For example, in one embodiment, the solvent may be an ionic liquid stabilizer, which is retained in the reaction product mixture and recovered from the reaction product mixture along with vinyl fluoride. The ionic liquid stabilizer may be selected from organic salts that are liquid at room temperature (about 25°C), those salts comprising cations selected from the group consisting of: pyridinium, pyridinium, pyrimidineonium, pyrazinium, imidazolineonium, pyrazolium, thiazolineonium, oxazoliumonium, and triazoliumonium, and mixtures thereof; and anions selected from the group consisting of: [BF4]-, [PF6]-, [SbF6]-, [CF3SO3]-, [HCF2CF2SO3]-, [CF3HFCCF2SO3]-, [HCClFCF2S3]-, [(CF3SO2)2N]-, [(CF3CF2SO2)2N]-, [(CF3SO2)3C]-, [CF3CO2]-, and F-, and mixtures thereof. In some embodiments, the ionic liquid stabilizer is selected from the group consisting of: emim BF4 (1-ethyl-3-methylimidazolium tetrafluoroborate); bmim BF4 (1-butyl-3-methylimidazolium tetrafluoroborate); emim PF6 (1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF6 (1-butyl-3-methylimidazolium hexafluorophosphate), all of which are purchased from Fluka (Sigma-Aldrich).

[0128] In some embodiments, the stabilizer may be formed in a method for preparing and / or purifying vinyl fluoride (e.g., E / Z-HFO-1132 or HFO-1132a). For example, the stabilizer may be formed as an intermediate, by-product, or byproduct during the method for forming vinyl fluoride. The stabilizer may be recovered from the method as an intermediate, by-product, or byproduct, separated from the reaction product, and purified if necessary, and subsequently blended with vinyl fluoride to act as a stabilizer for vinyl fluoride during packaging, storage, transportation, and handling. Alternatively, the stabilizer as an intermediate, by-product, or byproduct may be retained in the method and included with vinyl fluoride in the reaction product (and purified if necessary) as a stable composition for packaging, storage, transportation, and handling.

[0129] Examples of such intermediate / byproduct compounds include, but are not limited to, HCl, HF, HFC-142, HFC-32, HCFO-1122, HCFO-1122a, HCFO-1131, HFC-152a, ethane, and combinations thereof.

[0130] For example, in some embodiments, where HCl is required as a stabilizer, HCl can be used in the method to form vinyl fluoride, or it can be formed as a byproduct of the reaction, and excess HCl is not washed away from the reaction product mixture but is retained with the vinyl fluoride to act as a stabilizer during packaging, storage, handling, and / or transportation. The HCl can then be washed away from the stabilized composition to prepare refrigerant compositions for various applications. Any CO2 present can also be washed away as needed.

[0131] According to one embodiment, some stable compositions of the present invention are free of or substantially free of Group A fluorinated substances, such as trifluoroacetic acid (TFA). In one embodiment, as used herein, “Group A fluorinated substance” includes any substance that satisfies the following criteria: (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached thereto); as well as(ii) It complies with the persistence criteria in soil / sediments and water as set out in Annex XIII (Section 1.1.1) of the EU REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, accessed 2 May 2023), and the publication of that criterion is cited in Annex XV Restriction Report of 22 March 2023, the publication of which is incorporated herein by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed 2 May 2023).

[0132] In another implementation, as used herein, “Group A fluorinated substances” include those with a Henry’s Law constant ≤250 Pa*m 3 / mol and Any substance containing at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached to it).

[0133] In the implementation plan, Group A fluorinated substances include, but are not limited to, TFA.

[0134] As used herein, the phrase "free of" relating to the presence of Group A fluorinated substances in the stable compositions of the present invention means that the amount of such substances in the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector (by analyzing a gas or liquid sample), and / or ion chromatography (by analyzing a water sample after bubbling a hot fluid through water). Such methods are well known to those skilled in the art. As used herein, the phrase "substantially free" regarding the presence of Group A fluorinated substances in the stable compositions of the present invention means, when measured by gas chromatography (GC), such as gas chromatography with a flame ionization or electron capture detector, or GC coupled with a mass detector (gas chromatography / mass spectrometry (GC / MS) method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS), or by high performance liquid chromatography (HPLC) or high performance liquid chromatography-mass spectrometry (HPLC-MS), the amount of such substances in the composition is >0 wt% and ≤5 wt%, or >0 wt% and ≤4 wt%, or >0 wt% and ≤3 wt%, or >0 wt% and ≤2 wt%, or >0 wt% and ≤1 wt%, and all values ​​and ranges therebetween. TFA analytical standards are available for gas chromatography or ion chromatography and are available from, for example, Sigma Aldrich.

[0135] In one embodiment, the degradation products of some stable compositions according to the invention are free from or substantially free from Group A fluorinated substances, such as TFA. As used herein, the phrase “free from” in relation to the formation of Group A fluorinated substances from the degradation products of the compositions of the invention means that the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. As used herein, the phrase “substantially free” regarding the formation of Group A fluorinated substances from the compositions of the present invention means, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, all values ​​and ranges in between, of such substances generated in the environmental compartments of air, soil / sediment, and water during the tropospheric degradation of the composition.

[0136] In one embodiment, the stable composition according to the invention comprises at least one fluoroethylene, such as HFO-E-1132, HFO-Z-1132, or HFO-1132a; and at least one other refrigerant selected from: CO2, 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-113 1a, 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-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, ethane, propane, Butane and combinations thereof; and at least one stabilizer selected from the following: CO2, 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-1243yc, HFO-1243zc, HFO-1243ye(E), HFO-1243ye(Z), HFO-1243ze(E), HFO-1243ze(Z), HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof; wherein the degradation products of stable compositions are free of or substantially free of Group A fluorinated substances, such as TFA.

[0137] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132 and HFC-32, wherein HFC-32 acts as a stabilizer.

[0138] In one embodiment, the stable composition according to the invention comprises HFO-E-1132 and HFC-32, wherein HFC-32 acts as a stabilizer.

[0139] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, HFO-E-1132 and HFC-32, wherein HFC-32 acts as a stabilizer.

[0140] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, HFO-E-1132 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0141] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0142] In one embodiment, the stable composition according to the invention comprises HFO-E-1132 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0143] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, CF3I and HFC-32, wherein HFC-32 acts as a stabilizer.

[0144] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, HFO-E-1132, CF3I and HFC-32, wherein HFC-32 acts as a stabilizer.

[0145] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, HFO-E-1132, CF3I and HFC-134, wherein HFC-134 acts as a stabilizer.

[0146] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, CF3I and HFC-134, wherein HFC-134 acts as a stabilizer.

[0147] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, CO2 and HFC-32, wherein HFC-32 acts as a stabilizer.

[0148] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, HFO-E-1132, CO2 and HFC-32, wherein HFC-32 acts as a stabilizer.

[0149] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, HFO-E-1132, CO2 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0150] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, CO2 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0151] In one embodiment, the stable composition according to the invention comprises HFO-E-1132, CO2 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0152] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, CF3I, CO2 and HFC-32, wherein HFC-32 acts as a stabilizer.

[0153] In one embodiment, the stable composition according to the invention comprises HFO-E-1132, CF3I, CO2 and HFC-32, wherein HFC-32 acts as a stabilizer.

[0154] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, HFO-E-1132, CF3I, CO2 and HFC-32, wherein HFC-32 acts as a stabilizer.

[0155] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, HFO-E-1132, CF3I, CO2 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0156] In one embodiment, the stable composition according to the invention comprises HFO-Z-1132, CF3I, CO2 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0157] In one embodiment, the stable composition according to the invention comprises HFO-E-1132, CF3I, CO2 and HFC-134, wherein HFC-134 acts as a stabilizer.

[0158] In some embodiments, for any of the aforementioned stable compositions comprising HFO-E-1132 or both HFO-E-1132 and HFO-Z-1132, the amount of HFO-Z-1132 is less than about 0.1% by weight, preferably less than about 100 ppm.

[0159] In some embodiments, the stabilizer and vinyl fluoride or vinyl fluoride blends may not need to be separated from each other before use (i.e., after storage and / or transportation), for example, when they are available as co-reactants in chemical processes (e.g., to produce refrigerants or refrigerant blends) or as components of working fluids or refrigerant blends. In such cases, the stabilizer does not affect the refrigeration performance or compatibility of the composition with refrigerant oils and components. Additionally, in such cases, the stabilized composition can be used in cooling systems and as a replacement for existing refrigerants with higher global warming potential.

[0160] For example, in some embodiments, after storage and / or transportation is completed (e.g., once the container containing the stable composition arrives at the second location as described herein), the formulation of the stable composition is altered by adding one or more other refrigerants to form a novel blend composition.

[0161] In embodiments where the stabilizer is intended to remain blended with vinyl fluoride or a vinyl fluoride blend after storage or transportation is completed and the composition is ready for use, the stabilized composition may also contain one or more optional components.

[0162] For example, in some embodiments, the aforementioned stable composition may also contain a tracer as an optional component. While any suitable tracer may be used, examples of suitable tracers include at least one member selected from the following: E-1336mzz, 1233zd, 1224yd, 1112, 1327, Z-1336mzz, 1336yf, 1336ze, and 263fb.

[0163] In one embodiment, the aforementioned stable composition further comprises at least one inhibitor as an optional component and is substantially free of oligomers, homopolymers or other polymer products derived from vinyl fluoride, as described in International Application Publication WO2023 / 287695A1, the entire disclosure of which is hereby incorporated by reference.

[0164] One embodiment of the invention relates to any of the aforementioned stable compositions, which further comprises at least one antioxidant as an optional component. While any suitable antioxidant may be used, examples of suitable antioxidants include at least one member selected from: butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, phenols, bisphenol methane derivatives, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and combinations thereof. Based on the total weight of the stable composition, the amount of antioxidant may range from about 0.01 ppm to about 5,000 ppm, from about 0.03 ppm to about 2,000 ppm by weight, and in some cases from about 0.05 ppm to about 1,000 ppm by weight.

[0165] In one embodiment, any of the aforementioned stable compositions of the present invention may further comprise at least one lubricant as an optional component. The lubricants of the present invention include those suitable for use with refrigeration or air conditioning equipment. Among these lubricants are those conventionally used in compression refrigeration equipment utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in Chapter 8, entitled "Lubricants in Refrigeration Systems," of the 1990 ASHRAE manual, *Refrigeration Systems and Applications*, pages 8.1 to 8.21, which are incorporated herein by reference. The lubricants of the present invention may include those commonly known as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils include alkanes (i.e., saturated hydrocarbons with straight and branched carbon chains), cycloalkanes (i.e., cyclic or cyclic saturated hydrocarbons, which may be alkanes), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention also include those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils contain alkyl aryl compounds (i.e., straight-chain and branched alkylalkylbenzenes), synthetic alkanes and cycloalkanes, organosilicones, and poly-α-olefins. A representative conventional lubricant of this invention is commercially available BVM 100 N (an alkane mineral oil sold by BVA Oils), available from Crompton Co. under the trademark Suniso. ® 3GS and Suniso ® 5GS commercially available cycloalkane mineral oil, can be branded as Sontex ® 372LT is a cycloalkanes mineral oil purchased from Pennzoil, and can be marketed under the trademark Calumet. ®RO-30 is a cycloalkanes mineral oil obtained from Calumet Lubricants, and can be marketed under the brand name Zerol. ® 75. Zerol ® 150 and Zerol ® 500 linear alkylbenzenes obtained commercially from Shrieve Chemicals and branched alkylbenzenes sold by Nippon Oil as HAB 22.

[0166] In another embodiment, the lubricants of the present invention include those designed for use with hydrofluorocarbon refrigerants and miscible with the refrigerants of the present invention under compression refrigeration and air conditioning equipment operating conditions. Such lubricants and their properties are discussed in “Synthetic Lubricants and High-Performance Fluids”, edited by RLShubkin, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol. ® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ether (PVE).

[0167] The lubricant of the present invention is selected by taking into account the given compressor requirements and the environment in which the lubricant will be exposed. The amount of lubricant can range from about 1% to about 50% by weight, from about 1% to about 20% by weight, and in some cases from about 1% to about 3% by weight. In one specific embodiment, the foregoing composition is combined with a PAG lubricant for use in an A / C system of a motor vehicle having an internal combustion engine. In another specific embodiment, the foregoing composition is combined with a POE lubricant for use in an A / C system of a motor vehicle having an electric or hybrid electric drive system.

[0168] In one embodiment of the invention, any of the foregoing compositions optionally further comprises an antioxidant as an optional component, which has a distinctive aroma even at levels of a few ppm. This aroma can be used for refrigerant leak detection in refrigerants and in blends based on HFO-1132, HFO-E-1132, and / or HFO-Z-1132.

[0169] In one embodiment of the invention, any of the aforementioned stable compositions may include at least one additive as an optional component that can improve the lifespan of the refrigerant and air conditioning system, as well as the durability of the compressor. In one aspect of the invention, any of the aforementioned stable compositions may include at least one member selected from acid scavengers, performance enhancers, and flame retardants as an optional component.

[0170] Acid scavengers may comprise siloxanes, activated aromatic compounds, or combinations thereof. Serrano et al. (paragraph 38 of US2011 / 0272624 A1, which is incorporated herein by reference) disclose that siloxanes may be any molecule having silanoxy functionality. Siloxanes may include alkylsiloxanes, arylsiloxanes, or siloxanes comprising a mixture of aryl and alkyl substituents. For example, a siloxane may be an alkylsiloxane, including dialkylsiloxanes or polydialkylsiloxanes. Preferred siloxanes comprise oxygen atoms bonded to two silicon atoms, i.e., groups having the structure SiOSi. For example, a siloxane may be a siloxane of formula IV: R1[Si(R2R3)4O]nSi(R2R3)R4, where n is 1 or greater. The n of a siloxane of formula IV is preferably 2 or greater, more preferably 3 or greater (e.g., about 4 or greater). The n of the siloxane of formula IV is preferably about 30 or less, more preferably about 12 or less, and most preferably about 7 or less. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, the R2 group is an aryl group or an alkyl group or a mixture thereof. Preferably, the R3 group is an aryl group or an alkyl group or a mixture thereof. Preferably, the R4 group is an aryl group or an alkyl group. Preferably, R1, R2, R3, R4, or any combination thereof are not hydrogen. The R2 groups in the molecule can be the same or different. Preferably, the R2 groups in the molecule are the same. The R2 groups in the molecule can be the same or different from the R3 groups. Preferably, the R2 groups and R3 groups in the molecule are the same. Preferred siloxanes include siloxanes of formula IV, wherein R1, R2, R3, R4, R5, or any combination thereof are methyl, ethyl, propyl, or butyl groups or any combination thereof. Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, dodecylpentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof.

[0171] The paragraph

[0039] from Serrano et al. is incorporated by reference, noting that in one aspect of the invention, the siloxane is an alkylsiloxane comprising about 1 to about 12 carbon atoms, such as hexamethyldisiloxane. The siloxane may also be a polymer, such as polydialkylsiloxane, wherein the alkyl group is methyl, ethyl, propyl, butyl, or any combination thereof. Suitable polydialkylsiloxanes have a molecular weight of about 100 to about 10,000. Highly preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may consist substantially of polydimethylsiloxane, hexamethyldisiloxane, or combinations thereof.

[0172] Activated aromatic compounds can be any aromatic molecule activated by Friedel-Crafts addition reactions, or mixtures thereof. An aromatic molecule activated by Friedel-Crafts addition reactions is defined as any aromatic molecule capable of undergoing an addition reaction with an inorganic acid. This is particularly true for aromatic molecules capable of undergoing an addition reaction with an inorganic acid during application environments (A / C systems) or the thermal stability test as described in ASHRAE 97:2007, "Sealed glass tube method for testing the chemical stability of materials used in refrigerant systems." Such molecules or compounds are typically activated by substituting a hydrogen atom of the aromatic ring with one of the following groups: -NH2, -NHR, -NRz, ADH, AD, -NHCOCH3, -NHCOR, 4OCH3, -OR, -CH3, 4C2H5, -R, or -C6H5, where R is a hydrocarbon (preferably a hydrocarbon containing about 1 to about 100 carbon atoms). Activated aromatic molecules can be alcohols or ethers, where the oxygen atom (i.e., the oxygen atom of the alcohol or ether group) is directly bonded to the aromatic group. The activated aromatic molecule can be an amine, wherein the nitrogen atom (i.e., the nitrogen atom of the amine group) is directly bonded to the aromatic group. For example, the activated aromatic molecule can have the formula ArXRn, where X is O (i.e., oxygen) or N (i.e., nitrogen); n: 1 when X: O; n: 2 when X: N; Ar is an aromatic group (i.e., a group, C6H5); R can be H or a carbon-containing group; and when n: 2, the R groups can be the same or different. For example, R can be H (i.e., hydrogen), Ar, an alkyl group, or any combination thereof. Exemplary activated aromatic molecules that can be used in compositions according to the teachings herein include diphenyl oxide (i.e., diphenyl ether), methyl phenyl ether (e.g., anisole), ethyl phenyl ether, butyl phenyl ether, or any combination thereof. A highly preferred aromatic molecule activated by Friedel-Crafts addition reactions is diphenyl ether.

[0173] The paragraph from Serrano et al.

[0045] , incorporated herein by reference, describes an acid scavenger (e.g., an activated aromatic compound, a siloxane, or both) that may be present at any concentration resulting in a relatively low total acid value, a relatively low total halide concentration, a relatively low total organic acid concentration, or any combination thereof. Preferably, based on the total weight of the composition, the acid scavenger is present at a concentration greater than about 0.0050% by weight, more preferably greater than about 0.05% by weight, and even more preferably greater than about 0.1% by weight (e.g., greater than about 0.5% by weight). Based on the total weight of the composition, the acid scavenger is preferably present at a concentration less than about 3% by weight, more preferably less than about 2.5% by weight, and most preferably greater than about 2% by weight (e.g., less than about 1.8% by weight).

[0174] Additional examples of acid scavengers that may be included in and preferably excluded from a composition include those described by Kaneko (U.S. Patent Application Serial No. 11 / 575,256, published as U.S. Patent Publication 2007 / 0290164, paragraph 42, expressly incorporated herein by reference), such as one or more of the following: phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, oxooxide, or epoxides such as epoxidized soybean oil, and those described by Singh et al. (U.S. Patent Application Serial No. 11 / 250,219, published as 20060116310, paragraphs 34-42, expressly incorporated herein by reference).

[0175] Preferred additives include U.S. Patents 5,152,926 and 4,755,316, which are incorporated herein by reference. In particular, preferred extreme pressure additives comprise mixtures of: (A) toluenetriazole or a substituted derivative thereof, (B) an amine (e.g., Jeffamine M-600), and (C) a third component which is (i) an ethoxylated phosphate ester (e.g., AntaraLP-700), or (ii) a phosphoethanol (e.g., ZELEC 3337), or (iii) zinc dialkyl dithiophosphate (e.g., Lubrizol 5139, 5604, 5178, or 5186), or (iv) mercaptobenzothiazole, or (v) a 2,5-dimercapto-1,3,4-thiadiazole derivative (e.g., Curvan 826) or mixtures thereof. Additional examples of additives that may be used are given in U.S. Patent 5,976,399 (Schnur, 5:12-6:51, which is incorporated herein by reference).

[0176] Acid value was measured in mg KOH / g according to ASTM D664-01. Total halide ion concentration, fluoride ion concentration, and total organic acid concentration were measured by ion chromatography. The chemical stability of the refrigerant system was measured according to ASHRAE 97:2007 (RA2017), "Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems." The viscosity of the lubricant was tested at 40°C according to ASTM D-7042.

[0177] Mouli et al. (WO 2008 / 027595 and WO 2009 / 042847) proposed the use of alkylsilanes as stabilizers in compositions containing vinyl fluoride. Phosphates, phosphites, epoxides, and phenolic additives have also been used in some compositions. These are described, for example, by Kaneko (US Patent Application Publication 2007 / 0290164) and Singh et al. (US Patent Application Publication 2006 / 0116310). All of the foregoing applications are expressly incorporated herein by reference.

[0178] Preferred flame suppressants include those described in Canadian Patent 2,557,873 entitled “Compositions containing fluorine-substituted olefins”, and those with fluorinated products (such as HFC-125) and / or Krytox described in International Publication WO2009 / 018117A1 entitled “Compositions comprising fluoroolefins and uses thereof”. ® The lubricant is introduced together with this international publication for reference, which is also incorporated herein by reference.

[0179] In other embodiments, one or more of these optional components do not need to be blended with the stabilizer and vinyl fluoride components for storage and transport. Instead, optional components may be added to the composition, for example, as components of a working fluid or refrigerant blend, after storage or transport has been completed and the composition is required to be used.

[0180] Alternatively, in some embodiments, it is desirable to separate the stabilizer from the vinyl fluoride or vinyl fluoride blend before use (i.e., after storage or transportation) so that the vinyl fluoride or vinyl fluoride blend can be utilized, for example, as a working fluid or as a component of a refrigerant blend.

[0181] After storage, transportation, and handling, the stabilizer can be removed from the stable composition by any method known in the art. For example, methods for separating the stabilizer from the stable composition include, but are not limited to, washing, distillation, fractionation, adsorption, and combinations thereof.

[0182] For example, in some embodiments, after storage and / or transportation are completed (e.g., once the container containing the stable composition arrives at the second location as described herein), the formulation of the stable composition is altered by removing the stabilizer (e.g., by distillation) to obtain a blend containing HFO-1132a, HFO-1132(E) or HFO-1132(Z) and one or more other refrigerants, or to obtain pure HFO-1132a, HFO-1132(E) or HFO-1132(Z), which can then be used to prepare new blends.

[0183] In some embodiments, after storage or transportation is completed, the stabilizer has been removed, and the composition is required to be used, one or more of the optional components or one or more blend components (such as those discussed above) may be added to the composition.

[0184] The composition, whether with the stabilizer retained along with vinyl fluoride or after the stabilizer has been removed, can be blended as a heat transfer medium (such as a heat transfer fluid and refrigerant used in refrigeration systems, refrigerators, air conditioning systems, heat pumps, coolers, etc.). The composition is particularly suitable for mobile air conditioning systems and is used as a component in the preparation of refrigerant blends for stationary heat transfer systems. A heat transfer medium (also referred to herein as a heat transfer fluid, heat transfer composition, or heat transfer fluid composition) is a working fluid used to carry heat from a heat source to a radiator. A refrigerant is a compound or mixture of compounds used as a heat transfer fluid in a cycle, wherein the fluid undergoes a phase change from liquid to gas (or vapor) and back to liquid.

[0185] Storage, transportation and handling and use

[0186] In some embodiments, the stabilizer is preferably liquid at a temperature of about -80°C to about 40°C. The stabilizer is preferably liquid at temperatures typically encountered during the storage, transport, and handling of the stable composition, i.e., at temperatures up to 54.5°C.

[0187] In some embodiments, vinyl fluoride is preferably liquid at a temperature of about -60°C to about 54.5°C. Vinyl fluoride is preferably liquid at temperatures typically encountered during the storage, transport, and handling of stable compositions, i.e., at temperatures up to 54.5°C.

[0188] Preferably, the stabilizer and vinyl fluoride remain blended in the liquid phase during packaging, storage, transportation and handling.

[0189] One embodiment of the invention relates to storing any of the foregoing compositions preferably in a liquid phase in a sealed container, wherein at a temperature of about 25°C, the concentrations of oxygen and / or water in the gas and / or liquid phases are in the range of about 3 volume ppm to at least about 3,000 volume ppm, about 5 volume ppm to at least about 1,000 volume ppm, and in some cases about 5 volume ppm to at least about 500 volume ppm.

[0190] In one embodiment, the container for storing any foreign stable composition has a pressure rating of about 145 psig or greater, or about 240 psig or greater, or 500 psig or greater, preferably about 1000 psig or greater, and the container is configured for storage and / or shipment via conventional routes such as rail, road, waterway, etc.

[0191] In one embodiment, the present invention relates to, for example Figure 1 The dispensing system 100 shown is for any of the aforementioned vinyl fluoride compositions. In Figure 1 In one example, a delivery vessel 110 containing any of the aforementioned vinyl fluoropolymer compositions 115 can be transported from a first location to a second location. The delivery vessel 110 can be transported using any suitable mode of transport.

[0192] In one embodiment, as discussed above, a polymer inhibitor material may be introduced into the dispensing system 100. The polymer inhibitor material reduces (or eliminates) the formation of unwanted polymer materials. The polymer inhibitor material may be introduced in response to the detection that the oxidant concentration exceeds a threshold. While any suitable polymer inhibitor may be used, examples of suitable inhibitors are disclosed in International Application Publication WO 2019 / 213004A1, the disclosure of which is hereby incorporated by reference.

[0193] At least a portion of the refrigerant composition 115 is transferred from the delivery vessel 110 to the delivery vessel 130 at the second location via a distribution line 111, which optionally includes a transfer pump 112.

[0194] In one embodiment, the dispensing system 100 includes means for separating the stabilizer portion of the vinyl fluoride composition from the refrigerant portion. The stabilizer can be removed from the stabilized composition by any method known in the art, either before reaching, within, or after exiting the dispensing vessel 130. For example, a compressor can be used to preferentially separate the stabilizer portion of the composition from the refrigerant portion. Other methods for separating the stabilizer from the stabilized composition include, but are not limited to, washing, distillation, fractionation, adsorption, and combinations thereof.

[0195] The vinyl fluoride composition 115 may be sampled by the monitoring system 120 during and / or after transfer to the dispensing vessel 130. More specifically, the composition 115 may be sampled by the monitoring system 120 before or after the stabilizer has been separated from it. The monitoring system 120 may include a dispensing sensor 125 configured to sample the vinyl fluoride composition 115, for example, within the dispensing vessel 130. The monitoring system 120 receives at least one dispensing parameter of the refrigerant composition 115 from the dispensing sensor 125. In one embodiment, the monitoring system 120 employs an embedded device to detect the presence of the dispensing parameter. The embedded device may be located at any one or more suitable locations within the dispensing system. For example, an embedded GC / MS device is used to detect the presence of an oxidant. Although Figure 1 Sensor 125 on dispenser 130 is shown, but in other embodiments, sensor 125 on dispenser 130 may be omitted.

[0196] At least one distribution parameter may include temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, and combinations thereof. NAG comprises atmospheric air accumulated in the gaseous phase of the refrigerant (typically consisting of 78% nitrogen, 21% oxygen, and approximately 1% argon), where air has relatively low solubility in the liquid phase of the refrigerant. While reducing the total amount of NAG contained within the refrigerant (dissolved in the liquid refrigerant) may be desirable, it is generally more desirable to preferentially reduce the oxygen-containing portion of NAG over the nitrogen portion. In some cases, the oxygen-containing portion can increase the tendency for refrigerant decomposition or the formation of undesirable polymeric materials.

[0197] The monitoring system 120 determines whether at least one dispensing parameter is below at least one predetermined dispensing threshold. If at least one dispensing parameter is below at least one predetermined dispensing threshold, the refrigerant composition 115 is suitable for further dispensing.

[0198] In some embodiments, at least one predetermined allocation threshold includes a temperature not exceeding 100°C, a moisture content of 10 ppm by weight according to AHRI 700 (2016), a NAG concentration of less than 1.5 vol% according to AHRI 700 (2016) at 25°C, and combinations thereof. In other embodiments, at least one predetermined allocation threshold includes a temperature not exceeding 120°C, a moisture content of 10 ppm by weight according to AHRI 700 (2016), a NAG concentration of less than 0.9 vol% according to AHRI 700 (2016) at 25°C, and combinations thereof. In yet another embodiment, a predetermined allocation threshold includes a temperature not exceeding 100°C, a moisture content of 10 ppm by weight according to AHRI 700 (2016), a NAG concentration of less than 0.9 vol% according to AHRI 700 (2016) at 25°C, and combinations thereof.

[0199] The distribution system 100 can transfer at least a portion of the refrigerant composition 115 to the end user. The distribution line 111 is connected to the distribution vessel 130 via a distribution valve 151. The operation of the distribution valve 151 can be regulated by a monitoring system 120 based on user input, data from one or more sensors, other data, and combinations thereof. The distribution valve 151 can be used to regulate the flow of the refrigerant composition 115. The pressure within the distribution line can be regulated by one or more distribution pumps 152.

[0200] In one embodiment, one or more distribution sensors 125 are configured to sample the vinyl fluorinated refrigerant composition 115 within the distribution line 111. A monitoring system 120 receives at least one distribution parameter (e.g., temperature, moisture concentration, NAG concentration, acidity, and combinations thereof) of the vinyl fluorinated refrigerant composition 115 from the one or more distribution sensors 125. The monitoring system 120 determines whether at least one distribution parameter is below at least one predetermined threshold. If at least one distribution parameter is below at least one predetermined threshold, the refrigerant composition 115 is suitable for delivery to the end user. Although Figure 1 Sensor 125 on dispensing line 111 is shown, but in other embodiments, sensor 125 on dispensing line 111 may be omitted.

[0201] Rack system 160 can be used to deliver refrigerant composition 115 to one or more end-user refrigerant systems 175. Rack system 160 allows refrigerant composition 115 to be delivered to multiple end-user refrigerant systems 175 simultaneously. One or more distribution sensors 125 are configured to sample the refrigerant composition 115 within distribution line 111. 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 one or more distribution sensors 125 and determines whether the at least one distribution parameter is below at least one predetermined distribution threshold. If the at least one distribution parameter is below at least one rack line predetermined threshold, the refrigerant composition 115 is provided to the end user.

[0202] Distribution line 111 may include multiple distribution line branches 170. Each distribution line branch 170 may be configured to independently deliver refrigerant composition 115 to an end user. Distribution line branch 170 may also include a distribution line branch valve 171 capable of regulating the flow of refrigerant composition 115 within the distribution line branch 170. The distribution line branch may also include one or more distribution line sensors 125 configured to sample the refrigerant composition 115 within the distribution line branch 170. Monitoring system 120 receives at least one distribution line parameter of refrigerant composition 115 (e.g., temperature, moisture concentration, NAG concentration, acidity, and combinations thereof) from one or more distribution line sensors 125 and determines whether at least one distribution line parameter is below at least one predetermined distribution line threshold. If at least one distribution line parameter is below at least one predetermined distribution line threshold, refrigerant composition 115 is provided to the end user via rack transfer valve 173. The distribution line branch 170 may also include a backflow prevention device 174 to prevent the refrigerant composition 115 from flowing back and to prevent the possible introduction of external materials.

[0203] In some implementations, the rack transfer valve 173 may include a nozzle portion configured to be in disengaged fluid communication with the end-user system refrigerant system 175.

[0204] If monitoring system 120 determines that at least one distribution line parameter is higher than at least one predetermined distribution line threshold, it may be necessary to adjust one or more properties of the refrigerant composition 115 to form an acceptable refrigerant composition that meets the desired specifications. In some embodiments, monitoring system 120 may close one or more valves 151, 171, 173 to stop the distribution of refrigerant composition 115. In some embodiments, distribution line branch 170 may be disconnected from end-user system refrigerant system 175 to prevent unacceptable refrigerant compositions from being transferred to end-user system refrigerant system 175.

[0205] The distribution line branch 170 can then be detachably connected to the recovery system 180. Unacceptable refrigerant compositions in the distribution line branch 170 can then be purged. The recovery system 180 includes a recovery line 181 configured to be selectively or detachably connected to the distribution line branch 170, thereby allowing unacceptable refrigerant compositions to be transferred to one or more recovery containers 182.

[0206] One or more recovery containers 182 may store unacceptable refrigerant compositions until they are processed by a processing unit 190 having one or more processing modules. The processing modules may alter the composition of the unacceptable refrigerant composition to bring its properties back to desired specifications.

[0207] The recovery system 180 may further include one or more recovery system sensors 183 that can sample the characteristics of unacceptable refrigerant compositions in one or more recovery vessels 182 and / or after processing by one or more processing modules. The monitoring system 120 may receive one or more recovery parameters from the one or more recovery sensors 183. In some embodiments, recovery parameters may include temperature, moisture concentration, non-condensable material concentration (e.g., oxygen concentration), insoluble particle concentration, color, and / or acidity (e.g., total acid value). The monitoring system 120 may then direct the unacceptable refrigerant composition to one or more processing modules of the processing unit 190 based on the received parameters.

[0208] In one embodiment, the processing unit 190 includes a dehydration module 191. The dehydration module 191 can be used to remove water from an unacceptable refrigerant composition. For example, the dehydration module 191 can contact the unacceptable refrigerant composition with a desiccant such as a molecular sieve. Dehydration can result in a reduction in the concentration of one or more impurities to less than one or more predetermined thresholds for the unacceptable refrigerant composition. In some embodiments, the moisture concentration can be varied to obtain a moisture content of less than 20 ppm by weight according to AHRI 700 (2016). In one embodiment, the moisture concentration can be varied to obtain a moisture content of less than 10 ppm by weight according to AHRI 700 (2016).

[0209] In one embodiment, the processing unit 190 includes an inert gas purging module 192. The inert gas purging module 192 can contact an unacceptable refrigerant composition with an inert gas such as nitrogen, argon, or xenon to displace dissolved reactive gases in the unacceptable refrigerant composition. In one embodiment, the inert gas may include dry nitrogen. Inert gas purging can result in the concentration of one or more components being altered to below one or more predetermined thresholds in the unacceptable refrigerant composition. In one embodiment, the concentration of non-condensable material can be altered to obtain a concentration of less than 1.5% by volume at 25°C according to AHRI 700 (2016).

[0210] In one embodiment, processing unit 190 includes NAG reduction unit 193. NAG reduction unit 193 can contact an unacceptable refrigerant composition with a reducing agent, such as metal powder, which can react with oxygen or other oxidizable components of the unacceptable refrigerant composition. In one embodiment, the reducing agent may include iron powder. The treatment by NAG reduction unit 193 can result in a reduction of the concentration of one or more components of the unacceptable refrigerant composition to less than one or more predetermined threshold values ​​for the unacceptable refrigerant composition. In one embodiment, the concentration of non-condensable material can be varied to obtain a NAG (and other oxidizing agents) concentration of less than 1.5 vol% at 25°C according to AHRI 700 (2016).

[0211] In another embodiment, the condenser is used in conjunction with a cooling medium that is cold enough to condense the refrigerant and allows NAG to pass through with minimal refrigerant loss. The compressor can be used in conjunction with the condenser to increase pressure and enhance the condensation of the refrigerant at higher temperatures.

[0212] In another embodiment, a membrane selective for NAG is used. Specifically, the membrane is positioned such that NAG can pass through and then be removed while the refrigerant does not permeate, thereby separating the NAG from the refrigerant.

[0213] In one embodiment, the processing unit 190 includes a filtration module 194. The filtration module 194 can separate one or more insoluble particles from an unacceptable refrigerant composition 115. For example, the filtration module 194 can separate multiple insoluble particles from the unacceptable refrigerant composition by filtration. In some embodiments, the unacceptable refrigerant composition 115 is filtered through a sieve with a mesh size of at least 0.01 micrometers, at least 0.03 micrometers, at least 0.05 micrometers, at least 0.08 micrometers, at least 0.1 micrometers, or at least 0.15 micrometers. In one embodiment, the unacceptable refrigerant composition is filtered through a 0.1 micrometer sieve. Filtration can result in the concentration of one or more components being altered to be below one or more predetermined thresholds of the unacceptable refrigerant composition. Another method for removing relatively large undesirable materials includes using physical sieves. Larger sieves, ranging from approximately 50 micrometers to as low as 10 micrometers, can be used to remove metals, particulate matter, and residues (e.g., fluoropolymer particles). In one embodiment, the concentration of one or more components can be altered to obtain an oil concentration of less than 0.5% by weight. In one embodiment, the concentration of one or more components may be altered, resulting in a reduction in dye concentration. In one embodiment, the color of an unacceptable refrigerant composition is changed to a Byk-Gardner color value less than 3, preferably less than 2, and most preferably equal to 1. Another embodiment of the invention uses a plurality of screens in a tandem configuration, such that the refrigerant flows through all the screens, thereby removing different particles and contaminants at each screen or filter.

[0214] Another method for removing unwanted contaminant types of materials, particularly polymer-type residues (plasticizers, stabilizers, and other materials), involves using vapor transfer and refrigerant recovery, where the unwanted polymer-type materials remain in the liquid bottom. In this method, the polymers or other higher molecular weight materials are at concentrations still soluble in the refrigerant (or refrigerant blends), thus physical screening is ineffective. Vapor transfer delivers refrigerant in vapor form from one cylinder to a different cylinder, leaving the unwanted, heavier polymer materials in the original cylinder. Vapor transfer and refrigerant recovery can be used in combination with VTT (described below). Heating blankets or external cylinder heating can also be applied to the cylinders to facilitate vapor transfer.

[0215] Dryers can also be used to reduce moisture content and in combination with any of the methods described above.

[0216] The stable compositions described herein can be stored, transported, or handled in a variety of containers, including barrels, cylinders, cans, or other suitable storage vessels. Containers can be made of any suitable material, including but not limited to stainless steel, aluminum, or composite materials.

[0217] Containers for storing the aforementioned compositions can be constructed of any suitable material and design capable of sealing the composition within while maintaining a liquid phase. Examples of suitable containers include pressure vessels, such as tanks, filling cylinders, and second filling cylinders. Containers can be constructed of any suitable material that does not react with the stable composition, such as carbon steel, manganese steel, or chromium-molybdenum steel, as well as other low-alloy steels, stainless steel, and in some cases, aluminum alloys. Containers may include a puncture-resistant top or valve suitable for dispensing flammable substances. Some examples of suitable containers may be found in… https: / / hcc.worthingtonindustries.com / docs / default-source / default-document-library / Found in wi_refrigerant_portfolio_brochure_digital.pdf .

[0218] Containers storing any of the aforementioned compositions may be transported from a first location to a second location located away from the first location. For example, the first location may be a manufacturing facility for forming a stable composition, and the second location may be a use facility—an intermediate use facility, such as a facility for separating stabilizers or for blending the stable composition with one or more other refrigerants to prepare new blends—or a final use facility. Containers may be transported via any suitable mode of transport, such as by sea, road, and / or rail.

[0219] In one embodiment, the present invention relates to a container capable of dispensing, blending, transporting, transferring, storing, recovering, and using a refrigerant. In the exemplary embodiments described herein, the container is a vertical cylinder of 500L to 1000L, or more specifically 750L to 950L, or more specifically 850L to 950L, designed to hold, transfer, or transport flammable compositions. Due to its vertical orientation, it is suitable for facilitating the handling of the refrigerant. It should be noted that any vertical cylinder designed for flammable refrigerants can also be conveniently used for non-flammable refrigerants. The vertical tonne tank has specific design parameters that make it uniquely compatible with the other processes mentioned above in the combinations described below. One or more vertical tonne tanks may be used in different roles in the refrigeration distribution system 100, including as a delivery vessel 110, a dispensing vessel 130, and / or a recovery vessel 182.

[0220] In one implementation scheme, such as Figures 2-10As shown, the container is a vertical tonnage container (VTT) cylinder. VTT cylinders are designed so that the pressure vessel is vertically oriented, meaning the cylinder is upright (vertical) during use, transport, and storage. Since floor space (m²) can be limited, this particular orientation is suitable for a smaller physical footprint at potential distribution locations. Furthermore, the vertical orientation design itself is advantageously suited for the practical transport of VTT cylinders. VTT cylinders can be easily loaded onto forklifts without any loss of gravity or unusual positioning as is the case with horizontal tonnage containers. The base of the VTT cylinder is also designed to improve product transport. The bottom of the VTT cylinder has an integrated pallet with openings for forklift teeth. Therefore, the VTT cylinder can be safely and conveniently used to physically move flammable refrigerants from one location to another.

[0221] According to embodiments of the invention, pressure, flammability, and volume will comply with appropriate design specifications. For example, in the United States, VTT cylinders will comply with ASME design construction and rated pressure, while in the EU, VTT cylinders will comply with ADR, and in Japan, VTT cylinders will comply with HPGL.

[0222] Figure 2 and Figure 3 Front and side views of an embodiment of a vertical ton tank (VTT) with immersion tubes are shown. Immersion tubes 62 and 65 are shown as having 1 / 2-inch and 1-inch connections at the top and bottom of the tank, respectively. Attachments of immersion tubes 62 and 65 to the top flange 60 and the bottom flange 61 are also depicted.

[0223] Although process refrigerant can be delivered from a VTT to another VTT or a separate storage container, it is desirable to be able to access the VTT to see what residues remain there. Therefore, the VTT is designed to include two flanges, designated (top flange 60) and (bottom flange 61). The bottom and top flanges facilitate opening the VTT tank and allowing for visual inspection or easy examination via a sizing process such as an endoscope. The flanges also facilitate the easy removal of any debris that may have accumulated from impurities. The flanges are shown in... Figure 2 and Figure 3 middle.

[0224] As can be seen from the figure, the bottom flange has larger and smaller discharge pipes from the flange. Figure 5 The location and orientation of the discharge pipe are shown. Details of the smaller pipe are given in elements 83, 84, and 85 (smaller flanges), which connect to ½-inch pipe 64 and then lead to the connector. Details of the larger pipe are given in elements 87, 88, and 89, which connect to 1-inch pipe 63. Figure 5 and Figure 6These are unfolded top and side views of the bottom portion of (VTT). These figures show the components and how they are constructed into the main bottom flange in more detail.

[0225]

[0226]

[0227] Another design element is the addition of a PTFE gasket as shown in the diagram, which ensures no additional contamination from the gasket. PTFE gaskets have been found to be harmless to HFO-type products, therefore they need to be used in conjunction with this design.

[0228] The tank also includes a dry bulk coupler (DBC), which limits the amount of refrigerant that may be released during refrigerant transfer. The dry bulk coupler has a specific locking mechanism that stops product transfer until the unlocking mechanism engages. After the unlocking mechanism engages, the product is transferred. This mechanism reduces the release of flammable products to less than 1 gram, which is highly desirable in this VTT design. The combination of the DBC and this process contributes to ease of product transfer, increases safety, and limits any unintentional exposure to refrigerant and / or contaminants. These are elements 122, 124, and 125 in the attached figures. The adapter from the metal conduit to the DBC is element 123. DBCs are commonly branded as Denver Gardner TODO, Econosto valves, and Dixon valves.

[0229] In one embodiment, the VTT has a bottom bushing that latches into place to protect the bottom valve associated with the VTT. The bushing prevents forklift teeth from potentially colliding with the lower valve and / or flange, thus protecting the product. Additionally, the bottom bushing may be zipper-locked to aid in anti-counterfeiting detection. Any damage to the certified zipper lock can indicate that the product has been potentially tampered with. Figure 5 It describes how the bushing is assembled onto the valve. Figure 6 A protective door is shown, which further protects the valve when the tank is not externally connected.

[0230] In one embodiment, the container for storing, transporting, and handling any of the aforementioned compositions may be as described in U.S. Patent Application Publication 2022 / 0136748, the entire disclosure of which is incorporated herein by reference.

[0231] In one embodiment, the container for storing, transporting, and handling any of the aforementioned compositions may be selected from DOT4B240ET12-20M1031, DOT-3A2200, DOT-3AA2200, DOT-3AX2200, DOT-3AAX2200, DOT-3T2200, and DOT-39 cylinders. In one embodiment, the container for storing, transporting, and handling any of the aforementioned compositions containing HFO-Z-1132 is a DOT4B240ET12-20M1031 cylinder. In one embodiment, the container for storing, transporting, and handling any of the aforementioned compositions containing HFO-E-1132 or HFO-1132a is one of DOT-3A2200, DOT-3AA2200, DOT-3AX2200, DOT-3AAX2200, DOT-3T2200, or DOT-39 cylinders.

[0232] In some embodiments, the invention utilizes systems and methods for controlling and monitoring parameters of any of the aforementioned stable compositions, such as pressure, temperature, moisture concentration, non-absorbable gas (NAG) concentration, acidity, and combinations thereof, particularly during storage, transport, and handling, as described in U.S. Patent Application Publication 2022 / 0136748, the entire disclosure of which is incorporated herein by reference. Preferably, the storage container for any of the aforementioned compositions is an autoclave.

[0233] In one embodiment, the container for storing, transporting and handling any of the aforementioned compositions is a sealed container, wherein the NAG concentration in the gas phase and / or liquid phase is less than 1.5 by volume at a temperature of about 21°C.

[0234] While it may be desirable to reduce the total amount of NAG (dissolved in the liquid refrigerant) in stable vinyl fluoride refrigerants or refrigerant blends, it is generally preferred to reduce the oxygenated portion of NAG over nitrogen, as the oxygenated portion can, in some cases, increase the refrigerant's tendency to decompose or undergo unwanted reactions.

[0235] Embodiments of the present invention can be used alone or in combination with each other. Other features and advantages of the invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings which illustrate the principles of the invention by way of example.

Claims

1. A stabilized composition comprising at least one fluoroolefin and an effective amount of at least one stabilizing agent, wherein the at least one stabilizing agent inhibits the at least one fluoroolefin from undergoing at least one of decomposition, disproportionation, or polymerization under storage and transport conditions.

2. The stabilized composition of claim 1, wherein the fluoroolefin is difluoroethylene.

3. The stabilized composition of claim 2, wherein the difluoroethylene comprises at least one compound selected from the group consisting of 1,1-difluoroethylene (HFO-1132a), (E)-1,2-difluoroethylene (HFO-E-1132), and (Z)-1,2-difluoroethylene (HFO-Z-1132).

4. The stabilized composition of any one of claims 1 to 3, wherein the stabilizing agent comprises a compound that is chemically inert with respect to the at least one fluoroolefin.

5. The stabilized composition of any one of claims 1 to 4, wherein the stabilizing agent comprises at least one compound, preferably at least one refrigerant, having a boiling point that differs from the boiling point of the fluoroolefin by at least about 5°C, preferably at least about 10°C, more preferably at least 20°C.

6. The stabilized composition of any one of claims 1 to 5, wherein the stabilizing agent comprises at least one compound, preferably at least one refrigerant, having a boiling point that differs from the boiling point of the fluoroolefin by at least 30°C, preferably at least 40°C, more preferably at least 50°C.

7. The stabilized composition of any one of claims 1 to 4, wherein the at least one stabilizing agent 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(Z), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

8. The stabilized composition of claim 7, wherein the weight percent ratio of the stabilizing agent to the fluoroethene is 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.

9. The stabilized composition of any one of claims 1 to 6, wherein the at least one stabilizing agent is selected from the group consisting of polyol esters, polyalkylene glycols, and polyvinyl ethers.

10. The stabilized composition of claim 9, wherein the amount of the stabilizing agent is about 1 wt% to about 30 wt% based on the total weight of the stabilized composition.

11. The stabilized composition of any one of claims 1 to 6, wherein the at least one stabilizing agent is selected from the group consisting of hydrocarbons, including at least one of cyclic monoterpene; lipophilic organic compounds, including tocopherols such as alpha-tocopherol; and phenols, aromatic organic compounds having at least one chemical moiety -C6H4(OH), including benzene-1,4-diol.

12. The stabilized composition of claim 11, wherein the amount of the stabilizing agent is 0.001 wt% to about 1 wt% based on the total weight of the stabilized composition.

13. The stabilized composition of any one of claims 1-11, wherein the fluoroethene comprises HFO-E-1132, and the stabilized composition further comprises at least one additional compound selected from the group consisting of 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-difluoroethene (HCFO-1122a), trifluoroethene (HFO-1123), 1-chloro-2-fluoroethene (HCFO-1131), 1,2-difluoroethene (HFO-Z-1132), HFC-32, HFC-125, HFO-1141, HFC-161, CFO-1112(E), CFO-1112(Z), HFC-152a, and combinations thereof.

14. The stabilized composition of any one of claims 1-11, wherein the fluoroethene 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.

15. The stabilized composition of any one of claims 1-11, wherein the fluoroethene 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), tetrafluoroethene (HFO-1114), 1-chloro-2,2-difluoroethene (HCFO-1122), fluoroethene (HFO-1141), and combinations thereof.

16. The stabilized composition of any one of claims 1 to 14, wherein the stabilized composition comprises a refrigerant blend comprising the at least one fluoroolefin and at least one other refrigerant compound 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(Z), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

17. The stabilized composition of claim 1, wherein the at least one stabilizing agent is selected from the group consisting of HC1, HF, HFC-142, HFC-32, HCFO-1122, HCFO-1122a, HCFO-1131, HFC-152a, ethane, and combinations thereof.

18. The stabilized composition of any one of claims 1 to 3, wherein the storage and transport conditions comprise a temperature of up to 54.5 °C.

19. The stabilized composition of any one of claims 1 to 18, wherein the stabilized composition is free or substantially free of Group A fluorinated substances.

20. The stabilized composition of any one of claims 1 to 18, wherein degradation products of the stabilized composition are free or substantially free of Group A fluorinated substances.

21. A container comprising the stabilized composition of any one of claims 1 to 20.

22. The container of claim 21, wherein the stabilized composition is miscible at a temperature of up to 54.5 °C and a pressure rating of about 145 psig or greater.

23. The container of any one of claims 21-22, wherein the container comprising the stabilized composition is transported from a first location (e.g., a manufacturing facility) to a second location (e.g., a use facility) remote from the first location.

24. The container of any one of claims 21-23, wherein the fluoroethene is a liquid at a temperature of about -60 °C to about 54.5 °C.

25. The container of any one of claims 21-24, wherein the oxygen and / or water concentration in the gas and / or liquid phase in the container is in the range of about 3 vol ppm to less than about 3,000 vol ppm at a temperature of about 25 °C.

26. The container of any one of claims 21-25, wherein the container has a pressure rating of about 145 psig or greater.

27. A method for stabilizing fluoroethene for storage and transport, the method comprising mixing the fluoroethene with at least one stabilizing agent in a suitable container to form a stabilized mixture in a liquid state, wherein the at least one stabilizing agent inhibits the fluoroethene from undergoing at least one of decomposition, disproportionation, or polymerization under storage and transport conditions.

28. The method of claim 27, wherein the at least one stabilizing agent 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(Z), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

29. The method of claim 28, wherein the weight percent ratio of the stabilizing agent to the fluoroethene is 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.

30. The method of claim 27, wherein the at least one stabilizing agent is selected from the group consisting of polyol esters, polyalkylene glycols, and polyvinyl ethers.

31. The method of claim 30, wherein the amount of the stabilizing agent is about 1 wt% to about 30 wt% based on the total weight of the stabilized composition.

32. The method of claim 27, wherein the at least one stabilizing agent is selected from the group consisting of: hydrocarbons, including at least one of cyclic monoterpenes; lipophilic organic compounds, including tocopherols such as alpha-tocopherol; and phenols, aromatic organic compounds having at least one chemical moiety -C6H4(OH), including benzene- 1,4-diol.

33. The method of claim 32, wherein the amount of the stabilizing agent is 0.001 wt% to about 1 wt% based on the total weight of the stabilized composition.

34. The method of any one of claims 27 to 32, wherein the fluoroethene comprises HFO-E-1132, and the stabilized composition further comprises at least one additional compound selected from the group consisting of: 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), trifluoroethene (HFO-1123), 1-chloro-2-fluoroethene (HCFO-1131), 1,2-difluoroethene (HFO-Z-1132), HFC-32, HFC-125, HFO-1141, HFC-161, CFO-1112(E), CFO-1112(Z), HFC-152a, and combinations thereof.

35. The method of any one of claims 27 to 32, wherein the fluoroethene 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.

36. The method of any one of claims 27-32, wherein the fluoroethene 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), tetrafluoroethene (HFO-1114), 1-chloro-2,2-difluoroethene (HCFO-1122), fluoroethene (HFO-1141), and combinations thereof.

37. The method of any one of claims 27-36, wherein the stabilized composition comprises a refrigerant blend comprising the at least one fluoroethene and at least one other refrigerant compound 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(Z), HFC-227ca, HFO-1252zc, HFO-1252zf, HFO-1252ye(E), HFO-1252ye(Z), HFO-1252ze(E), HFO-1252ze(Z), HFO-1252yf, HFO-1234yf, ethane, propane, butane, and combinations thereof.

38. The method of claim 27, wherein the at least one stabilizing agent is selected from the group consisting of HC1, HF, HFC-142, HFC-32, HCFO-1122, HCFO-1122a, HCFO-1131, HFC-152a, ethane, and combinations thereof.

39. The method of any one of claims 27-38, wherein the stabilized composition is free or substantially free of Group A fluorinated substances.

40. The method of any one of claims 27-38, wherein the degradation products of the stable composition are free or substantially free of Group A fluoride species.

41. A method for the stable storage and / or transport of a composition comprising fluoroethene, the method comprising performing the method of any one of claims 27-40 to form a stable mixture stored in a liquid state in the container; and storing and / or transporting the container comprising the stable mixture in a liquid state.

42. A method for delivering a refrigerant to a refrigerant system, the method comprising: providing a stable composition comprising a stabilizing agent and the refrigerant, the refrigerant comprising fluoroethene; separating the stabilizing agent from the refrigerant, providing a distribution system arranged and disposed to deliver the refrigerant to the refrigerant system; transferring the refrigerant to the refrigerant system with the distribution system; and directing refrigerant to the refrigerant system or a recovery system based on the suitability of the refrigerant for use in the refrigerant system.

43. The method of claim 42, further comprising measuring at least one distribution parameter of the refrigerant and / or the stable composition with one or more sensors within the distribution system; wherein the distribution is responsive to a comparison of the at least one distribution parameter to at least one threshold parameter, and wherein the at least one distribution parameter is selected from the group consisting of refrigerant temperature, refrigerant moisture concentration, refrigerant non- absorbable gas concentration, refrigerant acidity, and combinations thereof.

44. The method of claim 43, wherein the at least one threshold parameter is selected from the group consisting of a refrigerant temperature of 100 °C, a refrigerant moisture concentration of 10 ppm by weight according to AHRI 700 (2016), a refrigerant non- absorbable gas concentration of 1.5 vol% at 25 °C according to AHRI 700 (2016), and combinations thereof.

45. A system for delivering a refrigerant to a refrigerant system, the system comprising: a compressor for separating a stabilizing agent from a refrigerant in a stable composition; a distribution system comprising a distribution vessel, a transfer line, at least one pump, a distribution line, and a distribution line branch arranged and disposed to transfer the refrigerant from the distribution vessel to the refrigerant system; a monitoring system comprising one or more sensors arranged and disposed to measure at least one distribution parameter within the distribution system; and a recovery system arranged and disposed to selectively receive refrigerant based on the suitability of the refrigerant for use in the refrigerant system responsive to a comparison of the at least one distribution parameter to at least one threshold parameter.

46. The system of claim 45, wherein the one or more sensors are arranged and disposed to measure a distribution parameter selected from the group consisting of refrigerant temperature, refrigerant moisture concentration, refrigerant non-absorbable gas concentration, refrigerant acidity, and combinations thereof.

47. The system of claim 45, wherein the recovery system receives refrigerant when one or more of the following threshold parameters is exceeded: (i) a refrigerant temperature measured with the one or more sensors exceeds 100°C; (ii) a refrigerant moisture concentration measured with the one or more sensors exceeds 10 ppm by weight refrigerant moisture concentration according to AHRI 700 (2016); or (iii) a non-absorbable gas concentration measured with the one or more sensors exceeds 1.5% by volume refrigerant non-absorbable gas concentration at 25°C according to AHRI 700 (2016).

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