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US-20260126221-A1 - COMPOSITIONS COMPRISING FLUOROOLEFINS AND NATURAL REFRIGERANTS AND USES THEREOF

US20260126221A1US 20260126221 A1US20260126221 A1US 20260126221A1US-20260126221-A1

Abstract

Refrigerant blends of HFOs and HCs, having HFOs as the main component, provide better cooling capacity than incumbent HFOs and maintain low flammability. Refrigerant blends of HFOs and HCs, having HCs as the main component, allow for larger HC charge at reduced flammability. Such compositions include (i) at least one compound selected from HFO-1234ze(E), HFO-1234ze(Z), HFO-1336mzz(E), HFO-1336mzz(Z), HCFO-1233zd(E), HCFO-1233zd(Z), CFO-1112, and combinations thereof, (ii) at least one other compound selected from HC-290, HC-1270, R-600, R-600a, R-601, R-601a, R-744, R-717, and combinations thereof, and optionally (iii) at least one other compound selected from HFC-134, HFC-134a, HFC-125, HFC-32, HFC-152a, and combinations thereof. These compositions are useful as refrigerants in air conditioning, heat pumps, refrigeration, and/or chillers.

Inventors

  • Joshua Hughes
  • Sheng Peng
  • Luke David Simoni

Assignees

  • THE CHEMOURS COMPANY FC, LLC

Dates

Publication Date
20260507
Application Date
20251218

Claims (20)

  1. 1 . A composition comprising: (i) HFO-1234ze(E); (ii) a hydrocarbon component selected from the group consisting of propane and isobutane; (iii) one or more additional compounds selected from the group consisting of: (a) one or more, two or more, three or more or four or more additional compounds selected from the group consisting of HFC-134a, HFC-134, HFO-1225zc, HFO-1234yf, HFC-245cb, HFC-236fa, HFO-1234zc, HFC-245fa, HCFC-124, CFC-114, trifluoropropyne, HFC-152a, HFO-1225ye(Z), HFO-1225ye(E), HCFO-1233xf, HFC-263fb, HFO-1243zf, HCFO-1233zd(E), HFO-1234ze(Z) and combinations thereof; (b) one or more, two or more, three or more of four or more additional compounds selected from the group consisting of HFO-1234yf, HFC-143a, HFC-152a, HFO-1243zf, HCFO-1233xf, HCFO-1233zd(E), HCFO-1233zd(Z), HCFO-1224yd, HCFO-1224zc, HCFO-1326mxz, CFC-113, HFC-32, HFC-23, trifluoropropyne and combinations thereof; and (c) one or more, two or more, three or more or four or more additional compounds selected from the group consisting of HFO-1234yf, HFC-143a, HFC-152a, HFO-1243zf, HCFO-1233xf, HCFO-1233zd(E), HCFO-1233zd(Z), HCFO-1224yd, HCFO-1224zc, HCFO-1326mxz, CFC-113, HFC-32, HFC-23, trifluoropropyne, HFC-125, HFC-143, HFC-134, HFC-263fb, CFC-114, CFC-114a, HCC-40, HCO-1140, HCFO-1113, CFC-13, CFC-12, HFC-227ca, HCFO-1131(E), HCFC-124, HCFC-124a, HFC-134a, HFC-227ea, CFC-217ca, CFC-217ba and combinations thereof; and (iv) one or more additional compounds selected from the group consisting of: (a) when the hydrocarbon component is propane, one or more additional compounds selected from the group consisting of butane, isobutane, propylene, pentane and isopentane, or one or more additional compounds selected from the group consisting of methane, ethane, butadiene, allene, butane, cyclobutane, acetylene, propyne and propylene; or (b) when the hydrocarbon component is isobutane, one or more additional compounds selected from the group consisting of butane, propane, propylene, pentane and isopentane, or one or more additional compounds selected from the group consisting of methane, ethane, butadiene, allene, methyl cyclopropane, 2-methylpropene, propane, propyne and propylene.
  2. 2 . The composition of claim 1 , wherein the composition comprises from about 2 to about 98 weight percent HFO-1234ze(E) and from about 2 to about 98 weight percent hydrocarbon component.
  3. 3 . The composition of claim 2 , wherein the hydrocarbon component is propane.
  4. 4 . The composition of claim 2 , wherein the hydrocarbon component is isobutane.
  5. 5 . The composition of claim 1 , wherein the composition further comprises HFC-134.
  6. 6 . The composition of claim 5 , wherein the composition comprises from about 2 to about 98 weight percent HFO-1234ze(E), from about 2 to about 98 weight percent HFC-134, and from about 2 to about 98 weight percent hydrocarbon component.
  7. 7 . The composition of claim 6 , wherein the hydrocarbon component is propane.
  8. 8 . The composition of claim 6 , wherein the hydrocarbon component is isobutane.
  9. 9 . The composition of claim 1 , wherein when the hydrocarbon component is propane, the propane component comprises 99.9 wt. % propane and 0.1 wt. % one or more additional compounds selected from the group consisting of isobutane, butane, methane, ethane and combinations thereof.
  10. 10 . The composition of claim 9 , wherein a total amount of methane and ethane is less than 100 ppm, based on the total weight of the propane component.
  11. 11 . The composition of claim 1 , wherein when the hydrocarbon component is propane, the propane component comprises 99.9 wt. % propane and 0.1 wt. % one or more additional compounds selected from the group consisting of isobutane, butane, propylene, methane, ethane and combinations thereof.
  12. 12 . The composition of claim 11 , wherein a total amount of methane and ethane is less than 100 ppm, based on the total weight of the propane component.
  13. 13 . The composition of claim 11 , wherein a total amount of propylene, methane and ethane is less than 100 ppm, based on the total weight of the propane component.
  14. 14 . The composition of claim 1 , wherein when the hydrocarbon component is propane, the propane component comprises 99.9 wt. % propane and 0.1 wt. % one or more additional compounds selected from the group consisting of isobutane, butane, propylene, butadiene, allene, propyne, methane, ethane and combinations thereof.
  15. 15 . The composition of claim 14 , wherein a total amount of propylene, methane and ethane is less than 100 ppm, based on the total weight of the propane component.
  16. 16 . The composition of claim 14 , wherein a total amount of butadiene, allene and propyne is less than 100 ppm, based on the total weight of the propane component.
  17. 17 . The composition of claim 1 , wherein when the hydrocarbon component is isobutane, the isobutane component comprises 99.9 wt. % isobutane and 0.1 wt. % one or more additional compounds selected from the group consisting of butane, 2-methylpropene, methyl cyclopropane, methane, ethane and combinations thereof.
  18. 18 . The composition of claim 17 , wherein a total amount of methane and ethane is less than 100 ppm, based on the total weight of the isobutane component.
  19. 19 . The composition of claim 17 , wherein a total amount of butane, 2-methylpropene, methyl cyclopropane, methane and ethane is less than 100 ppm, based on the total weight of the isobutane component.
  20. 20 . The composition of claim 19 , wherein when the hydrocarbon component is isobutane, the isobutane component comprises 99.9 wt. % isobutane and 0.1 wt. % one or more additional compounds selected from the group consisting of propane, butane, butadiene, propyne, allene, propylene, methane, ethane and combinations thereof.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a Continuation-in-Part of International PCT Application No. PCT/US2025/034101 filed Jun. 18, 2025, which claims the benefit of U.S. Patent Application No. 63/662,898, filed Jun. 21, 2024, and U.S. Patent Application No. 63/676,102, filed Jul. 26, 2024, the disclosures of which are all incorporated herein by reference in their entireties. FIELD The present invention is directed to fluoroolefin refrigerant compositions, methods and systems using the same, and systems containing the E-HFO-1234ze refrigerant compositions. BACKGROUND The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for ozone depleting chlorofluorocarbons (CFCs), such as CFC-11 and CFC-12, and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, foam blowing agents and propellants. These new compounds, such as HFC-refrigerants, HFC-134a and HFC-125 being the most widely used at this time, have zero ozone depletion potential (ODP) and thus are not affected by the current regulatory phase-out as a result of the Montreal Protocol. In addition to ozone depleting concerns, global warming is another environmental concern in many applications. HFC refrigerants such as HFC-134a and HFC-125 respectively have global warming potentials (GWP) of 1,430 and 3,500 according to the UN's IPCC Fourth Assessment Report (AR4). This regulatory landscape is continuously evolving, taking into consideration properties beyond just ODP and GWP. More particularly, there is a need for refrigerants composition that not only meet low ODP standards and have lower (<500 GWP or <300 GWP) or low (<150 GWP) global warming potentials, but that also exhibit low or no flammability, provide superior performance in a variety of applications and which meet the standards of evolving regulations. There is a need in this art for new refrigerant compositions that meet evolving regulations as well as provide heat transfer and refrigerant characteristics that meet or exceed the effectiveness of conventional refrigerant and refrigerant blends. Fluoroolefins, and more particularly hydrofluoroolefins (HFOs), have been replacing saturated CFCs, HCFCs, and HFCs in a variety of applications for several years. HFOs have low ODP and low GWP as compared to ozone depleting CFCs (e.g., trichlorofluoromethane (CFC-11) and CFC-12 (dichlorodifluoromethane)) and high GWP HFCs (e.g., pentafluoroethane (HFC-125) and 1,1,1,2-tetrafluoroethane (HFC-134a), while maintaining their nonflammable or mildly flammable properties. For example, E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze), like 2,3,3,3-tetrafluoropropene (HFO-1234yf), has zero ozone depletion and very low global warming potential, and has thus been identified as a potential useful refrigerant. For example, U.S. Pat. No. 7,862,742 discloses compositions comprising E-HFC-1234ze and HFO-1234yf. U.S. Pat. No. 9,302,962 discloses methods for making E-HFO-1234ze. The disclosures of U.S. Pat. Nos. 7,862,742 and 9,302,962 are hereby incorporated by reference in their entireties. E-HFO-1234ze, which, in addition to zero ozone depletion and very low global warming potential, has a boiling point of −19.0° C. and possesses physical properties that make it an attractive option for refrigeration, air conditioning, and heat pump applications. However, HFOs often bear higher costs than CFCs and HFCs, due to more complex manufacturing processes. So-called natural thermal management fluids, also typically referred to as A3 refrigerants, such as HC-290 (propane), HC-1270 (propylene), R-600 (butane), R-600a (isobutane), exhibit acceptable performance and are cost effective. However, the high flammability of A3 refrigerants limits their charge size. In 2019, the International Electrotechnical Commission (IEC) 60336-2-89 standard was updated to increase the charge limit for A3 refrigerants, including HC-290 and R-600a, to 500 grams, at the international level. The present invention provides refrigerant compositions that have HFO and HC blends with HFOs as the main component, at reduced costs relative to HFO blends, while have better cooling capacity and maintaining low flammability, while also meeting the evolving regulatory landscape. The present invention also provides compositions having HC and HFO blends having HCs as the main component, which allow for large HC charge at reduced flammability, while also meeting the evolving regulatory landscape. SUMMARY The present disclosure relates to compositions comprising at least one compound selected from (i) trans-1,3,3,3-tetrafluoropropene (E-HFO-1234ze or HFO-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (Z-HFO-1234ze or HFO-1234ze(Z)), trans-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz or HFO-1336mzz(E)), cis-1,1,1,4,4,4-