Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
  • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
  • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
  • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
  • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
  • C10M105/32—Esters
  • C10M105/38—Esters of polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
  • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
  • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
  • C10M107/34—Polyoxyalkylenes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
  • F25B1/00—Compression machines, plants or systems with non-reversible cycle
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
  • F25B13/00—Compression machines, plants or systems, with reversible cycle
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
  • C09K2205/122—Halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
  • C09K2205/126—Unsaturated fluorinated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/22—All components of a mixture being fluoro compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

• the present disclosure relates to a working medium, a composition for heat cycling, a heat cycling device, and a heat cycling method.
• chlorofluorocarbons such as chlorotrifluoromethane and dichlorodifluoromethane
• hydrochlorofluorocarbons such as chlorodifluoromethane
• CFCs and HCFCs are currently subject to regulation due to their impact on the stratospheric ozone layer.
• HFCs hydrofluorocarbons
• HFC-32 difluoromethane
• HFC-134a 1,1,1,2-tetrafluoroethane
• HFC-125 pentafluoroethane
• HFC-134a is non-flammable and is therefore widely used in car air conditioners, refrigeration equipment, etc.
• GWP global warming potential
• HFOs Hydrofluoroolefins
• HFCs Hydrofluoroolefins
• Patent Document 1 discloses a refrigerant composition in which (E)-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) is added to HFC-134a as a refrigerant using HFO.
• HFO-1234ze(E) has a GWP of less than 1 (AR5), making it a refrigerant with a low environmental impact.
• Patent Document 1 discloses that adding HFO-1234ze(E) to HFC-134a reduces the GWP and maintains the temperature glide.
• the refrigerant component described in Patent Document 1 contains 36 to 56% by weight of HFC-134a, assuming the total content of HFO-1234ze(E) and HFC-134a to be 100% by weight.
• the refrigerant composition containing the refrigerant component has a high GWP of 469 to 728, and it is desired to reduce the environmental load.
• the flammability of HFO-1234ze(E) is classified as slightly flammable (2L category) according to the standards of the American Society of Heating, Refrigeration and Air-Conditioning Engineers (ASHRAE), and therefore it is desirable to reduce the flammability.
• Patent Document 1 states that it is preferable to contain 44 to 64% by weight of HFO-1234ze(E). In this case, the specific heat ratio is likely to be high, and the discharge temperature of the thermal cycle device tends to be high.
• One aspect of the present disclosure has been made in consideration of the above-mentioned conventional circumstances, and aims to provide a working fluid in which the GWP and specific heat ratio are reduced, the increase in flammability is suppressed, and the dew point-boiling point temperature difference is suppressed, thereby suppressing the increase in temperature glide, as well as a heat cycle composition, a heat cycle device, and a heat cycle method that use this working fluid.
• ⁇ 2> The working fluid according to ⁇ 1>, wherein a total content of the (E)-1,3,3,3-tetrafluoropropene, the (Z) 1-chloro-2,3,3,3-tetrafluoropropene, and the 1,1,1,2-tetrafluoroethane is 90.0 mass% or more based on a total amount of the working fluid.
• ⁇ 3> The working fluid according to ⁇ 1> or ⁇ 2>, wherein the content of the (E)-1,3,3,3-tetrafluoropropene is 80.0 to 90.0 mass% based on the total amount of the working fluid.
• ⁇ 4> The working fluid according to any one of ⁇ 1> to ⁇ 3>, wherein an air concentration in a gas phase of the working fluid at 25° C. is 3.5 vol% or less.
• ⁇ 5> With respect to the total amount of the working medium, The working fluid according to ⁇ 4>, wherein the content of the (E)-1,3,3,3-tetrafluoropropene is 86.5% by mass or less, and the content of the 1,1,1,2-tetrafluoroethane is 14.0% by mass or less.
• ⁇ 6> A composition for use in a heat cycle, comprising the working fluid according to any one of ⁇ 1> to ⁇ 5> and a refrigerating machine oil.
• composition for heat cycle use according to ⁇ 6> wherein the refrigeration oil is at least one selected from the group consisting of polyalkylene glycol oil, polyol ester oil, polyvinyl ether oil, hydrocarbon-based synthetic oil, and mineral oil.
• the refrigerating machine oil has a kinetic viscosity at 40° C. of 700 mm 2 /s or less.
• a working fluid according to any one of ⁇ 1> to ⁇ 5> A compressor that compresses the vapor of the working medium; a condenser for cooling and liquefying the vapor of the working medium discharged from the compressor; a pressure reducing device that reduces the pressure of the working medium discharged from the condenser; an evaporator for heating the working medium discharged from the pressure reducing device;
• a thermal cycler comprising: ⁇ 10> A working fluid according to ⁇ 3>, A compressor that compresses the vapor of the working medium; a condenser for cooling and liquefying the vapor of the working medium discharged from the compressor; a pressure reducing device that reduces the pressure of the working medium discharged from the condenser; an evaporator for heating the working medium discharged from the pressure reducing device;
• the evaporator is a heat cycle device in which the evaporation temperature of the working medium is controlled to be in the range of -40 to 7°C.
• the heat cycle device according to ⁇ 10>, wherein the evaporator controls an evaporation temperature of the working medium to be in the range of ⁇ 25 to 7° C.
• the heat cycle device according to ⁇ 11>, wherein the evaporator controls an evaporation temperature of the working medium to be ⁇ 15 to 7° C.
• the thermal cycle apparatus according to any one of ⁇ 9> to ⁇ 12>, wherein at least a part of a surface of a component constituting the thermal cycle apparatus that comes into contact with the working medium contains at least one selected from the group consisting of copper and copper alloys.
• ⁇ 14> The heat cycle device according to ⁇ 13>, wherein the part is at least one selected from the group consisting of the compressor, the condenser, the evaporator, and a refrigerant pipe.
• ⁇ 15> Compressing the vapor of the working fluid according to any one of ⁇ 1> to ⁇ 5>, Cooling the vapor of the working medium to liquefy it; depressurizing the liquefied working medium; The working medium having a reduced pressure is heated.
• ⁇ 16> Compressing the vapor of the working fluid according to ⁇ 3>, Cooling the vapor of the working medium to liquefy it; depressurizing the liquefied working medium; The reduced pressure working medium is heated at an evaporation temperature of -40 to 7°C.
• a working fluid in which the GWP and specific heat ratio are reduced, the increase in flammability is suppressed, and the dew point-boiling point temperature difference is suppressed, thereby suppressing the increase in temperature glide, as well as a heat cycle composition, a heat cycle device, and a heat cycle method that use this working fluid.
• FIG. 1 is a schematic diagram illustrating an example of a refrigeration cycle device. This is a cycle diagram in which the state change of the working medium in a refrigeration cycle device is depicted on a pressure-enthalpy diagram. This is a cycle diagram showing the state change of the working medium in a refrigeration cycle device on a temperature-entropy diagram.
• a numerical range indicated using “to” means a range that includes the numerical values before and after “to” as the minimum and maximum values, respectively.
• the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in the present disclosure.
• the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.
• the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
• pressure refers to absolute pressure, which is 101.3 kPa at atmospheric pressure.
• the saturated vapor pressure means the pressure of saturated vapor, and means the pressure at the intersection of the isotherm and the saturated vapor line in a pressure-enthalpy diagram.
• the saturated liquid pressure means the pressure of a saturated liquid, and means the pressure at the intersection of an isotherm and a saturated liquid line in a pressure-enthalpy diagram.
• the working fluid of the present disclosure contains (E)-1,3,3,3-tetrafluoropropene, (Z) 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), and 1,1,1,2-tetrafluoroethane, in which the content of the 1,1,1,2-tetrafluoroethane is 14.5% by mass or less relative to the total content of the (E)-1,3,3,3-tetrafluoropropene, the (Z) 1-chloro-2,3,3,3-tetrafluoropropene, and the 1,1,1,2-tetrafluoroethane, the content of the (Z) 1-chloro-2,3,3,3-tetrafluoropropene is 10.0% by mass or less relative to the total content, and the content of the (E)-1,3,3,3-tetrafluoropropene is 75.5% by mass or more relative to the total content.
• HFO 1-chloro-2,3,
• the working medium means a medium that carries heat, and is a concept that includes a refrigerant composition and a heat transfer medium composition.
• the refrigerant composition is a medium that mainly serves to cool the heat source, but may also be used as a medium that simultaneously serves to heat the heat source.
• the heat transfer medium composition is a medium that mainly serves to heat the heat source, but may also be used as a medium that simultaneously serves to cool the heat source.
• the working fluid of the present disclosure is preferably used in a heat cycle. Specifically, the working fluid of the present disclosure is preferably used in a heat cycle device in which a series of changes occur, such as a change in state by utilizing heat absorption and heat release, and then returning to the initial state.
• the GWP is lowered because HFC-134a, which has a high GWP of 1, contains HFO-1234ze (E), which has a GWP of 1, and HCFO-1224yd (Z), which has a GWP of less than 1. Furthermore, the specific heat ratio of HFC-134a is 1.1195, and that of HFO-1234ze(E) is 1.1014. In contrast, the specific heat ratio of HCFO-1224yd(Z) is low at 1.0983. Therefore, by adding HCFO-1224yd(Z) to HFC-134a and HFO-1234ze(E), the specific heat ratio can be lowered, and the discharge temperature of the thermal cycle device can be reduced.
• HFO-1224yd(Z) which has a flammability category of 1
• HFO-1234ze(E) which has a flammability category of 2L (ASHRAE standard) and is slightly flammable
• the boiling point of HFC-134a is ⁇ 26.074° C.
• the boiling point of HFO-1234ze(E) is ⁇ 18.973° C.
• the boiling point of HCFO-1224yd(Z) is 14.617° C. Therefore, the temperature glide is maintained by setting the content of HCFO-1224yd(Z) to 10.0 mass% or less with respect to the total content of the specific components.
• the content of HFC-134a is set to 14.5 mass% or less of the total content of the specific components
• the content of HFO-1234ze(E) is set to 75.5 mass% or more of the total content of the specific components.
• the content of HFC-134a is 14.5 mass% or less, based on the total content of the specific components, and from the viewpoint of reducing the GWP and the specific heat ratio, it is preferably 14.0 mass% or less, more preferably 12.0 mass% or less, and even more preferably 10.0 mass% or less. Since the working fluid of the present disclosure contains HFC-134a, the content of HFC-134a is more than 0 mass% based on the total content of the specific components. From the viewpoint of reducing flammability and balancing each performance, the content of HFC-134a may be 3.0 mass% or more, or may be 5.0 mass% or more, based on the total content of the specific components.
• the content of HCFO-1224yd(Z) is 10.0% by mass or less, based on the total content of the specific components, and from the viewpoint of suppressing the dew point-boiling point temperature difference, it is preferably 9.0% by mass or less, more preferably 8.0% by mass or less, and even more preferably 7.0% by mass or less. Since the working fluid of the present disclosure contains HCFO-1224yd(Z), the content of HCFO-1224yd(Z) is more than 0 mass% with respect to the total content of the specific components.
• the content of HCFO-1224yd(Z) may be 3.0 mass% or more, or may be 5.0 mass% or more with respect to the total content of the specific components.
• the content of HFO-1234ze(E) is 75.5 mass% or more, preferably 80.0 mass% or more, more preferably 81.0 mass% or more, and even more preferably 82.0 mass% or more, based on the total content of the specific components. Furthermore, from the viewpoint of reducing the amount of heat of combustion due to low combustibility, the content of HFO-1234ze(E) is preferably 90.0 mass% or less, more preferably 87.0 mass% or less, and even more preferably 85.0 mass% or less, relative to the total content of the specific components.
• the content of HFO-1234ze(E) is preferably 80.0 to 90.0 mass% relative to the total amount of the working fluid, more preferably 80.0 to 85.0 mass%, and even more preferably 82.0 to 85.0 mass%.
• the content of HFO-1234ze(E) relative to the total amount of the working fluid is within the above range, the combustion heat of the working fluid is reduced, and in a heat cycle device or heat cycle method, when the reduced pressure working fluid is heated at an evaporation temperature of -40 to 7°C, the discharge temperature tends to be lowered.
• the mass ratio of the content of HCFO-1224yd(Z) to the content of HFO-1234ze(E) is preferably 1.0:99.0 to 13.3:86.7, and more preferably 1.0:99.0 to 11.6:88.4.
• the mass ratio of the content of HFC-134a to the content of HFO-1234ze(E) is preferably 1.0:99.0 to 16.1:83.9, and more preferably 1.0:99.0 to 14.5:85.5.
• the total content of the specific components is preferably 90.0 mass% or more, more preferably 95.0 mass% or more, even more preferably 99.0 mass% or more, particularly preferably 99.5 mass% or more, and may be 100 mass% based on the total amount of the working fluid.
• the total content of the specific components is preferably 99.0 mass% or more, more preferably 99.5 mass% or more, and may be 100 mass% based on the total amount of the working medium.
• the working fluid of the present disclosure may contain other working fluid components other than the specific components.
• the other components include HFOs other than HFO-1234ze(E), HCFOs other than HCFO-1224yd(Z), HFCs other than HFC-134a, hydrocarbons, chlorofluoroolefins (CFOs), etc.
• the other components are preferably components that have little impact on the ozone layer and little impact on global warming.
• the other working fluid components may be used alone or in combination of two or more.
• HCFO hydroochlorofluoroolefin
• HFOs include (Z)-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), trifluoroethylene (HFO-1123), 1,1-difluoroethylene (HFO-1132a), (Z)-1,2-difluoroethylene (HFO-1132(Z)), (E)-1,2-difluoroethylene (HFO-1132(E)), 2-fluoropropene (HFO-1261yf), 1,1,2-trifluoropropene (HFO-1243yc), 3,3,3-trifluoropropene (HFO- 1243zf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 2,4,4,4-tetrafluorobutene (HFO-1354yf), (Z)-1,1,1,4,4,4
• HCFOs include (E) 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), 2-chloro-1,1,3,3-tetrafluoropropene (HCFO-1224xc), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoro Examples of chlorofluoropropene include ethylene (HCFO-1122a), (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), (Z)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).
• HFCs include difluoromethane (HFC-32), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2,2-pentafluoroethane (HFC-125), pentafluoropropane, hexafluoropropane, 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), pentafluorobutane, and heptafluorocyclopentane.
• HFC-32 difluoromethane
• HFC-161 1,1-difluoroethane
• HFC-143a 1,1,1-trifluoroethane
• HFC-134 1,1,2,2-tetrafluoroethane
• HFC-125 1,1,1,2,2-pentaflu
• hydrocarbon examples include propylene, propane, cyclopropane, butane, isobutane, pentane, and isopentane.
• CFO examples include 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb), 1,2-dichloro-1,2-difluoroethylene (CFO-1112), and the like.
• the total content of the other working medium components is preferably less than 10 mass%, more preferably less than 5 mass%, even more preferably less than 1 mass%, particularly preferably less than 0.5 mass%, and may be 0 mass%, based on the total amount of the working medium.
• the water content in the working medium is preferably 20 ppm by mass or less, and particularly preferably 15 ppm by mass or less, relative to the total amount of the working medium. If the water content is 20 ppm by mass or less, freezing in capillary tubes, which are an example of pressure reducing devices in thermal cycle equipment, hydrolysis of the working medium and refrigeration oil, material deterioration due to acid components generated in the equipment, generation of contaminants, etc. are suppressed.
• the air content in the gas phase of the working fluid at 25°C is preferably 3.5% by volume or less, more preferably 2.5% by volume or less, even more preferably 2.0% by volume or less, and particularly preferably 1.5% by volume or less, as the air concentration measured by gas chromatography. If the air content is 3.5% by volume or less, browning and rusting of the copper surface, which is the surface that comes into contact with the working fluid in the thermal cycle device, is suppressed. This is presumably due to the suppression of decomposition of the working fluid or refrigeration oil caused by the reaction of oxygen in the air with the working fluid or refrigeration oil.
• copper and copper alloys are widely used in components constituting heat cycle devices such as refrigeration and air conditioning equipment, etc.
• Such components include compressors, condensers, evaporators, refrigerant piping, etc.
• refrigerant piping requires flexibility and strength, it is often made entirely of copper or copper alloy. If the surface of copper or copper alloy discolors and deteriorates, there is a concern that the flexibility and strength of the refrigerant piping will decrease.
• Condensers and evaporators are often made entirely of copper or copper alloys, which have high thermal conductivity, from the viewpoint of heat transfer.
• grooves may be formed on the surfaces of condensers and evaporators to improve heat transfer. If the surfaces of copper or copper alloys turn brown and rust occurs, there is a risk of a decrease in the heat transfer of the condensers and evaporators.
• copper or copper alloy is used for the windings and connecting piping in the compressor. If the surface of the windings discolors and changes, there is a concern that the insulation or conductivity will decrease. As a result, the performance and reliability of the compressor will decrease, and there is a risk that the working medium, the composition for heat cycle, etc. will leak from the compressor. If the working medium, the composition for heat cycle, etc. leaks, the refrigerant composition in the heat cycle device may change. From this viewpoint, it is preferable that the heat cycler suppresses browning and rusting of the copper and copper alloy surfaces.
• the content of HFO-1234ze(E) is preferably 86.5% by mass or less, and more preferably 85.0% by mass or less, based on the total amount of the working fluid.
• the content of HFC-134a is preferably 14.0% by mass or less, more preferably 12.0% by mass or less, and even more preferably 10.0% by mass or less, based on the total amount of the working fluid.
• the content of HFO-1234ze(E) is preferably 86.5% by mass or less and the content of HFC-134a is 14.0% by mass or less, more preferably the content of HFO-1234ze(E) is 85.0% by mass or less and the content of HFC-134a is 12.0% by mass or less, and even more preferably the content of HFO-1234ze(E) is 85.0% by mass or less and the content of HFC-134a is 10.0% by mass or less, relative to the total amount of the working fluid.
• Another embodiment of the working fluid of the present disclosure may be a working fluid comprising HFO-1234ze(E), HCFO-1224yd(Z) and HFC-134a, from the viewpoint of suppressing browning and rusting of the surface of copper and copper alloys, in which the air concentration at 25° C. in the gas phase part of the working fluid is 3.5 vol% or less, and the content of HFO-1234ze(E) is 86.5 mass% or less and the content of HFC-134a is 14.0 mass% or less, relative to the total amount of the working fluid.
• the content of HFO-1234ze(E) is preferably 85.0 mass% or less and the content of HFC-134a is 12.0 mass% or less, relative to the total amount of the working fluid, and more preferably the content of HFO-1234ze(E) is 85.0 mass% or less and the content of HFC-134a is 10.0 mass% or less.
• the working fluid may contain unavoidable components such as impurities produced as by-products during the production of the specific components, etc., and solvents used during production.
• the total content of these unavoidable components is preferably 1.5 mass% or less, more preferably 1.0 mass% or less, even more preferably 0.7 mass% or less, and particularly preferably 0.5 mass% or less, relative to the total amount of the working fluid.
• the total content of the unavoidable components may be 50.0 mass ppm or more, or may be 100.0 mass ppm or more.
• the unavoidable components include 1,1,2,2,3-pentafluoro-1,3-dichloropropane (HCFC-225cb), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,3,3,3-tetrafluoropropane (HFC-254fb), 1,1,2,3-tetrafluorobutane (HFC-374pee), CFO-1214ya, HCFO-1224yd(E), (Z)2- Chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe(Z)), (E)-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe(E)), HCFO-1233xf, HFO-1234yf, HFO-1234ze(Z), HFO-1354yf, HCFO-1233zd(E), HCFO-1233zd(Z), HCFO-1233xc, C Examples of such fluorocarbons
• the GWP of the working fluid is preferably 190 or less, more preferably 150 or less.
• GWP is the 100-year value of the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (2013) (AR5). If not stated in AR5, it is adopted from Scientific Assessment of Ozone Depletion 2018, J. Phys. Chem. A 2018, 122, 4593-4600, and EPA Greenhouse Gas Reporting Program: Addition of Global Warming Potentials 2014.
• the GWP of a mixture is the weighted average of the composition mass. When considering the GWP of a mixture, any mixture with a GWP of 1 or less is calculated as 1.
• the specific heat ratio of the working fluid is preferably 1.104 or less, and more preferably 1.103 or less. The lower the specific heat ratio, the more preferable it is, but it may be 1.100 or more, or may be 1.101 or more.
• the specific heat ratio is expressed as the ratio (C P /C V ) of the specific heat at constant pressure (C P ) of a gas to the specific heat at constant volume (C V ) of a gas.
• the specific heat at constant pressure and the specific heat at constant volume are values under standard conditions of 25° C. and atmospheric pressure, and are calculated using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (REFPROP 10.0).
• the heat of combustion of the working medium is preferably 9.850 MJ/kg or less, more preferably 9.830 MJ/kg or less, and even more preferably 9.800 MJ/kg or less.
• There is no particular lower limit to the heat of combustion of the working medium and it may be 9.260 MJ/kg or more, 9.280 MJ/kg or more, or 9.300 MJ/kg or more.
• the heat of combustion per mass (MJ/kg) is defined by the American Society of Heating, Refrigeration and Air-conditioning Engineers (ASHRAE) standard 34 as an index for determining the flammability of a refrigerant.
• the amount of heat of combustion is expressed as the difference between the sum of the enthalpies of formation of the products in the combustion reaction formula and the enthalpies of formation of the compounds in the reaction system.
• the enthalpies of formation are described in the Chemistry Handbook, International Standards (see Reference A), various handbooks, etc.
• the formation enthalpy of a new compound can be determined by Benson's group additivity rule (see Reference B) or a computational chemistry method.
• the combustion heat of the working medium is a theoretical value calculated under the following assumptions, which is obtained by converting the value of the combustion heat obtained by completely combusting 1 mole of the working medium with oxygen stoichiometrically into the value of the combustion heat per kg of the working medium.
• the product and reactant compounds are assumed to be gases.
• the combustion products are HF(g), CO2 (g), COF2 (g) and H2O (g), with the addition of Cl2 (g), N2 (g) or I2 (g) if chlorine, nitrogen or iodine are part of the molecular structure of the substance.
• each compound contained in the working fluid is decomposed into the atoms constituting each compound, and a virtual substance containing each atom is set in consideration of the molar ratio in the working fluid.
• the combustion heat is calculated using the combustion reaction formula of the virtual substance.
• C q H r F s corresponds to the virtual substance.
• a combustion reaction formula is defined by the magnitude of the number of H atoms (r) and the number of F atoms (s) in a substance, and the following formula is used as the combustion reaction formula when the number of H atoms (r) ⁇ the number of F atoms (s).
• the working fluid of the present disclosure contains HCFO-1224yd(Z), it also contains Cl 2 (g) as a combustion product. However, since Cl 2 has a standard enthalpy of formation of zero, it does not affect the value of the heat of combustion.
• the cycle performance which is a property required when applying a working fluid to a heat cycle device, can be evaluated by the coefficient of performance (also referred to as "COP” in this disclosure) and the capacity per unit volume (the suction volume of the compressor) (also referred to as "CAP" in this disclosure).
• the capacity is the refrigeration capacity.
• the evaluation items when the working fluid is applied to a refrigeration cycle device further include the temperature gradient in the evaporator and condenser (also referred to as "temperature glide” in this disclosure), the discharge temperature, the condensation pressure, and the evaporation pressure. Specifically, using a reference refrigeration cycle under the conditions shown below, each item is evaluated, for example, by the method described below.
• Evaporation temperature 0°C (however, in the case of a non-azeotropic mixture, the evaporation temperature is calculated as the average temperature of the evaporation start temperature and the evaporation completion temperature, and therefore the evaporation temperature is calculated as (evaporation start temperature + evaporation completion temperature)/2.) Condensation temperature: 45° C.
• the condensation temperature is calculated as the average temperature of the condensation start temperature and the condensation end temperature, and therefore the condensation temperature is calculated as (condensation start temperature + condensation end temperature)/2.
• the COP of the working fluid disclosed herein is preferably 0.995 or more, more preferably 0.996 or more, and even more preferably 0.997 or more, relative to the COP of HFC-134a, which is set to 1.00.
• the CAP of the working fluid of the present disclosure is, as a relative value assuming that the CAP of HFC-134a is 1.00, preferably 0.685 or more, more preferably 0.690 or more, and still more preferably 0.700 or more.
• the CAP and COP are determined by the method described below.
• Temperature glide is an index that measures the difference in composition between the liquid and gas phases of a mixture working medium. Temperature glide is defined as the property of a heat exchanger, for example, where the start and end temperatures of evaporation in an evaporator or condensation in a condenser are different.
• evaporation glide the property of an evaporator where the start and end temperatures of evaporation are different is referred to as "evaporation glide.”
• condensation glide the property of a condenser where the start and end temperatures of condensation are different is referred to as “condensation glide.”
• Evaporation glide and condensation glide are collectively referred to as "temperature glide.” In azeotropic mixtures, the temperature glide is zero, and in pseudo-azeotropic mixtures, the temperature glide is very close to zero.
• the inlet temperature at the evaporator will drop, which increases the possibility of frost formation, which is a problem.
• the working medium flowing through the heat exchanger it is common for the working medium flowing through the heat exchanger to flow in a countercurrent manner to the heat source fluid, such as water or air, in order to improve heat exchange efficiency. Since the temperature difference between the heat source fluids is small under stable operating conditions, it is difficult to obtain an energy-efficient heat cycle device when using a non-azeotropic mixture of media with a large temperature glide. For this reason, when using a mixture as a working medium, a working medium with an appropriate temperature glide is desired.
• non-azeotropic mixed media have the problem that their composition changes when they are filled from the pressure vessel into the refrigeration and air conditioning equipment. Furthermore, if a refrigerant leaks from the refrigeration and air conditioning equipment, there is a very high possibility that the refrigerant composition inside the refrigeration and air conditioning equipment will change, making it difficult to restore the refrigerant composition to its initial state. On the other hand, if an azeotropic or pseudo-azeotropic mixed medium is used, the above problems can be avoided.
• the evaporation glide of the working medium disclosed herein is preferably 3.0°C or less, and more preferably 2.7°C or less.
• the condensation glide of the working medium disclosed herein is preferably 3.0°C or less, and more preferably 2.8°C or less.
• the working fluid of the present disclosure has a dew point-boiling point temperature difference, which is the difference between the dew point and the boiling point, of preferably 4.00° C. or less, and more preferably 3.50° C. or less.
• the lower limit of the dew point-boiling point temperature difference is not particularly limited, and may be 0.50° C. or more, or may be 1.00° C. or more.
• the dew point and boiling point in the dew point-boiling point temperature difference are values at atmospheric pressure (101.3 kPa).
• the compression ratio is expressed as condensation pressure Pc (MPa)/evaporation pressure Pe (MPa) in the refrigeration cycle.
• the compression ratio becomes smaller as the condensing pressure in the refrigeration cycle becomes smaller and as the evaporating pressure becomes higher.
• the smaller the compression ratio the higher the volumetric efficiency of the compressor, so the amount of refrigerant circulating increases and the equipment performance improves.
• the Pc of the working fluid of the present disclosure is preferably 0.65 or more, more preferably 0.68 or more, and even more preferably 0.70 or more, relative to the Pc of HFC-134a being 1.00.
• the Pc may be 1.00 or less, or 0.95 or less.
• the Pe of the working medium of the present disclosure is preferably 0.50 or more, more preferably 0.55 or more, and even more preferably 0.60 or more, relative to the Pe of HFC-134a, which is 1.00. There is no particular upper limit to the Pe, but it may be 1.00 or less, or 0.95 or less.
• the Pe of the working fluid of the present disclosure is preferably 0.0250 MPa or more, more preferably 0.0600 MPa or more, and even more preferably 0.1013 MPa or more.
• Pe there is no particular upper limit for Pe, but it may be 1.0000 MPa or less, or 0.5000 MPa or less.
• the working medium of the present disclosure is suitable for use in a heat cycle device.
• the heat cycle device may be a heat pump system that uses the hot heat obtained in a condenser, or a refrigeration cycle system that uses the cold heat obtained in an evaporator.
• thermal cycle devices include refrigeration and freezing equipment, air conditioning equipment, heating and hot water equipment, power generation systems, heat transport devices, and secondary cooling machines.
• thermal cycle devices are preferably used as air conditioning equipment, which is often installed outdoors, because they can stably and safely demonstrate thermal cycle performance even in higher temperature operating environments.
• Thermal cycle devices are also preferably used as refrigeration and freezing equipment.
• air-conditioning equipment examples include room air conditioners, packaged air conditioners (packaged air conditioners for stores, packaged air conditioners for buildings, packaged air conditioners for facilities, etc.), gas engine heat pumps, train air conditioners, and automobile air conditioners.
• the automotive air conditioner is preferably an air conditioner for a gasoline vehicle, an air conditioner for a hybrid vehicle, an air conditioner for an electric vehicle, or an air conditioner for a hydrogen vehicle, and more preferably an air conditioner for an electric vehicle.
• refrigeration and freezing equipment include showcases (refrigerated showcases, freezer showcases, etc.), refrigerators, freezers, water chillers, freezing and refrigeration units, freezers for refrigerated and freezer warehouses, turbo freezers, screw freezers, vending machines, and ice makers.
• heating and hot water equipment include heat pump water heaters, heat pump hot water heaters, heat pump hot air heaters, steam hot air generating heat pumps, and exhaust heat recovery heat pumps.
• the preferred power generation system is a Rankine cycle system.
• a specific example of a power generation system is one in which the working medium is heated in an evaporator using geothermal energy, solar heat, or medium- to high-temperature waste heat of about 50 to 200°C, and the working medium that has become high-temperature, high-pressure steam is adiabatically expanded in an expander, and the work generated by this adiabatic expansion drives a generator to generate electricity.
• a latent heat transport device As the heat transport device, a latent heat transport device is preferred.
• latent heat transport devices include heat pipes and two-phase closed thermosiphon devices that transport latent heat by utilizing phenomena such as evaporation, boiling, and condensation of the working medium enclosed within the device.
• Heat pipes are used in relatively small cooling devices, such as cooling devices for heat-generating parts of semiconductor elements and electronic devices.
• Two-phase closed thermosiphon devices do not require a wig and have a simple structure, so they are widely used in gas-gas type heat exchangers, for promoting snow melting and preventing freezing on roads, etc.
• composition for heat cycle contains the working fluid according to the present disclosure and a refrigerating machine oil.
• the working fluid of the present disclosure can be mixed with a refrigerating machine oil to be used as a composition for heat cycle when applied to a heat cycle device.
• the composition for heat cycle of the present disclosure may further contain known additives such as stabilizers and leak detection substances.
• the refrigerating machine oil As the refrigerating machine oil, a known refrigerating machine oil used in a heat cycle device can be used.
• the refrigeration oil is preferably one that has sufficient compatibility with the working fluid under low temperature conditions while ensuring lubricity and hermeticity of the compressor.
• the kinetic viscosity of the refrigeration oil at 40°C is preferably 700 mm2/s or less, more preferably 400 mm2/s or less, and more preferably 300 mm2/s or less.
• the kinetic viscosity at 100°C is preferably 100 mm2/s or less, more preferably 70 mm2/s or less, and even more preferably 50 mm2/s or less.
• refrigeration oils include oxygen-containing synthetic oils (ester-based refrigeration oils, ether-based refrigeration oils, etc.), hydrocarbon-based synthetic oils (alkylbenzene oils, etc.), fluorine-based refrigeration oils, mineral-based refrigeration oils, silicone oils, and hydrocarbon-based synthetic oils. Refrigeration oils may be used alone or in combination of two or more types.
• ester-based refrigeration oils include dibasic acid ester oils, polyol ester oils, complex ester oils, and polyol carbonate ester oils.
• Preferred dibasic acid ester oils are esters of dibasic acids having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) with monohydric alcohols having 1 to 15 carbon atoms and linear or branched alkyl groups (methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc.).
• Preferred dibasic acid ester oils are ditridecyl glutarate, di(2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, or di(3-ethylhexyl) sebacate.
• esters of diols ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, neopentyl glycol, 1,7-heptanediol, 1,12-dodecanediol, etc.
• polyols having 3 to 20 hydroxyl groups trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, glycerin, sorbitol, sorbitan, sorbitol glycerin condensates, etc.
• fatty acids having 6 to 20 carbon atoms straight-chain or branched fatty acids such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecano
• the polyol ester oil is preferably an ester of a hindered alcohol (neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, etc.), and more preferably trimethylolpropane tripelargonate, pentaerythritol-2-ethylhexanoate, or pentaerythritol tetrapelargonate.
• a hindered alcohol neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, etc.
• Complex ester oils are esters of fatty acids and dibasic acids with monohydric alcohols and polyols.
• the fatty acids, dibasic acids, monohydric alcohols, and polyols that can be used are the same as those described above.
• Polyol carbonate ester oil is an ester of carbonic acid and a polyol.
• polyols include the same diols and polyols as described above.
• the polyol carbonate ester oil may be a ring-opening polymer of a cyclic alkylene carbonate.
• Ether-based refrigeration oils include polyvinyl ether oil and polyoxyalkylene oil.
• Polyvinyl ether oils include polymers obtained by polymerizing vinyl ether monomers such as alkyl vinyl ethers, and copolymers obtained by copolymerizing vinyl ether monomers with hydrocarbon monomers having olefinic double bonds.
• the vinyl ether monomer may be one type or two or more types.
• Hydrocarbon monomers having an olefinic double bond include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, ⁇ -methylstyrene, various alkyl-substituted styrenes, etc. Hydrocarbon monomers having an olefinic double bond may be of one type or two or more types.
• the polyvinyl ether oil may be either a block copolymer or a random copolymer.
• polyoxyalkylene oil examples include polyoxyalkylene monools; polyoxyalkylene polyols; alkyl ethers of polyoxyalkylene monools or polyoxyalkylene polyols; esters of polyoxyalkylene monools or polyoxyalkylene polyols; and polyoxyalkylene oils.
• the alkyl ether or ester of polyoxyalkylene monool or polyoxyalkylene polyol is preferred.
• Also as the polyoxyalkylene oil, the polyalkylene glycol oil is preferred.
• the alkyl ether of polyalkylene glycol which is called polyglycol oil and in which the terminal hydroxyl group of polyalkylene glycol is capped with an alkyl group such as a methyl group, is preferred.
• Polyoxyalkylene monools and polyoxyalkylene polyols can be produced, for example, by a method of ring-opening addition polymerization of an alkylene oxide having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, etc.) with an initiator such as water or a hydroxyl group-containing compound in the presence of a catalyst such as an alkali hydroxide.
• the oxyalkylene units in the polyalkylene chain may be the same in one molecule, or may contain two or more types of oxyalkylene units. It is preferable that one molecule contains at least an oxypropylene unit.
• initiators used in the reaction include water; monohydric alcohols such as methanol and butanol; and polyhydric alcohols such as ethylene glycol, propylene glycol, pentaerythritol, and glycerol.
• fluorine-based refrigeration oils include compounds in which the hydrogen atoms of synthetic oils (such as mineral oils, poly- ⁇ -olefins, alkylbenzenes, and alkylnaphthalenes described below) are replaced with fluorine atoms, fluorine-containing oils, perfluoropolyether oils, and fluorinated silicone oils.
• synthetic oils such as mineral oils, poly- ⁇ -olefins, alkylbenzenes, and alkylnaphthalenes described below
• Mineral refrigeration oils include mineral oils (e.g., paraffinic mineral oils and naphthenic mineral oils) that are produced by refining refrigeration oil fractions obtained by atmospheric or reduced pressure distillation of crude oil through an appropriate combination of refining processes (solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, clay treatment, etc.).
• refining refrigeration oil fractions obtained by atmospheric or reduced pressure distillation of crude oil through an appropriate combination of refining processes (solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, clay treatment, etc.).
• Examples of synthetic hydrocarbon oils include poly- ⁇ -olefins, alkylbenzenes, and alkylnaphthalenes.
• the refrigeration oil is preferably at least one selected from the group consisting of polyalkylene glycol oil, polyol ester oil, polyvinyl ether oil, silicone oil, fluorine-containing oil, mineral oil, and hydrocarbon-based synthetic oil, and more preferably at least one selected from the group consisting of polyalkylene glycol oil, polyol ester oil, polyvinyl ether oil, hydrocarbon-based synthetic oil, and mineral oil.
• the refrigeration oil may further contain at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents, and antifoaming agents.
• the amount of refrigerating machine oil contained in the heat cycle composition may be within a range that does not significantly reduce the effects of the present disclosure, and is preferably 10 parts by mass or more and 100 parts by mass or less, and more preferably 20 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the working fluid.
• the heat cycle composition may contain, in addition to the working fluid and the refrigerating machine oil, at least one known additive selected from the group consisting of a tracer, a stabilizer, a polymerization inhibitor, and a leak detection substance.
• the tracer is preferably added in a detectable concentration to allow tracking of any dilution, contamination, or other changes to the working medium of the present disclosure.
• the working medium of the present disclosure may contain only one type of tracer, or two or more types.
• the tracer is not particularly limited and can be appropriately selected from among commonly used tracers. It is preferable to select as the tracer a compound that cannot become an impurity that is inevitably mixed into the working medium of the present disclosure.
• Preferred tracers include the following compounds: HC-40 (chloromethane, CH3Cl ) HFC-161 (fluoroethane , CH3CH2F ) HFC-245fa (1,1,1,3,3 - pentafluoropropane, CF3CH2CHF2 ) HFC-236fa (1,1,1,3,3,3 - hexafluoropropane, CF3CH2CF3 ) HFC-236ea (1,1,1,2,3,3 - hexafluoropropane, CF3CHFCHF2 ) HCFC-22 (chlorodifluoromethane, CHClF 2 ) HCFC-31 (Chlorofluoromethane, CH2ClF ) CFC-1113 (chlorotrifluoroethylene, CF 2 ⁇ CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF 3 OCHF 2 ) HFE-143a (tri
• the tracer content is preferably 10 to 1000 ppm by mass, more preferably 3 to 500 ppm by mass, even more preferably 5 to 300 ppm by mass, particularly preferably 75 to 250 ppm by mass, and most preferably 10 to 200 ppm by mass, relative to the total amount of the working medium.
• the stabilizer is a component that improves the stability of the heat cycle working fluid against heat and oxidation.
• examples of the stabilizer include conventionally known stabilizers, such as oxidation resistance improvers, heat resistance improvers, and metal deactivators.
• oxidation resistance improvers and heat resistance improvers examples include N,N'-diphenylphenylenediamine, p-octyldiphenylamine, p,p'-dioctyldiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, N-(p-dodecyl)phenyl-2-naphthylamine, di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothiazine, 6-(tert-butyl)phenol, 2,6-di-(tert-butyl)phenol, 4-methyl-2,6-di-(tert-butyl)phenol, and 4,4'-methylenebis(2,6-di-tert-butylphenol).
• the oxidation resistance improvers and heat resistance improvers may each be one type or two or more types.
• Metal deactivators include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimethylcaptothiadiazole, salicylidin-propylenediamine, pyrazole, benzotriazole, tolutriazole, 2-methylbenzamidazole, 3,5-dimethylpyrazole, methylenebis-benzotriazole, organic acids or their esters, primary, secondary or tertiary aliphatic amines, amine salts of organic or inorganic acids, heterocyclic nitrogen-containing compounds, amine salts of alkyl acid phosphates or their derivatives, etc.
• the amount of stabilizer contained may be within a range that does not significantly reduce the effects of the present disclosure, and is typically 0.01 to 5 mass%, preferably 0.05 to 3 mass%, more preferably 0.1 to 2 mass%, even more preferably 0.25 to 1.5 mass%, and particularly preferably 0.5 to 1 mass%, relative to 100 parts by mass of the working fluid.
• the polymerization inhibitor is not particularly limited and can be appropriately selected from among commonly used polymerization inhibitors.
• the polymerization inhibitor contained in the working fluid of the present disclosure may be one type or two or more types.
• polymerization inhibitors examples include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.
• the content of the polymerization inhibitor is not particularly limited, and is usually 0.01 to 5 mass% relative to the total amount of the working fluid, preferably 0.05 to 3 mass%, more preferably 0.1 to 2 mass%, even more preferably 0.25 to 1.5 mass%, and particularly preferably 0.5 to 1 mass%.
• Leak detection materials include ultraviolet fluorescent dyes, odorous gases, and odor masking agents.
• ultraviolet fluorescent dyes include conventionally known ultraviolet fluorescent dyes such as those described in U.S. Pat. No. 4,249,412, JP-T-10-502737, JP-T-2007-511645, JP-T-2008-500437, and JP-T-2008-531836.
• odor masking agents include conventionally known fragrances such as those described in JP-T-2008-500437 and JP-T-2008-531836.
• a solubilizer When using a leak detection substance, a solubilizer may be used to improve the solubility of the leak detection substance in the heat cycle working fluid.
• Solubilizers include those described in JP-T-2007-511645, JP-T-2008-500437, JP-T-2008-531836, etc.
• the amount of the leak detection substance contained may be within a range that does not significantly reduce the effect of the present disclosure, and is preferably 2 parts by mass or less, and more preferably 0.5 parts by mass or less, per 100 parts by mass of the working medium.
• heat cycles to which the heat cycle composition can be applied are similar to those described for the working fluid.
• the heat cycle device of the present disclosure includes a working medium of the present disclosure, a compressor that compresses the vapor of the working medium, a condenser that cools and liquefies the vapor of the working medium discharged from the compressor, a pressure reduction device that reduces the pressure of the working medium discharged from the condenser, and an evaporator that heats the working medium discharged from the pressure reduction device.
• the working fluid applied to the heat cycle device may be used as a heat cycle composition.
• the heat cycle method of the present disclosure compresses the vapor of the working medium of the present disclosure, cools and liquefies the vapor of the working medium discharged from the compressor, depressurizes the liquefied working medium, and heats the depressurized working medium.
• the evaporator is operated at an evaporation temperature of the working medium I of -40 to 7°C.
• the evaporation temperature of the working medium in the evaporator may be automatically controlled.
• the decompressed working medium is heated at an evaporation temperature of ⁇ 40 to 7° C.
• the discharge temperature can be lowered while the evaporation pressure is secured.
• the evaporation temperature means the temperature at which the working medium absorbs heat and turns into vapor in the evaporation process of the heat cycle device.
• the condensation temperature means the temperature at which the vapor of the working medium releases heat and becomes liquid in the condensation process of the heat cycle device.
• the condensation temperature can be determined by measuring the temperature at least one of the condenser inlet and outlet.
• condensation temperature (condensation start temperature + condensation end temperature) / 2".
• the heat cycle device to which the working medium of the present disclosure is applied may be a heat pump device that uses the hot heat obtained in a condenser, or a refrigeration cycle device that uses the cold heat obtained in an evaporator.
• the heat cycle device of the present disclosure may be of the direct expansion type or the indirect expansion type. Examples of the indirect expansion type include the flooded evaporator type.
• the thermal cycle includes a series of cycles in which the working medium is (1) compressed in a gaseous state by a compressor, (2) cooled in a condenser to change to a high-pressure liquid state, (3) the pressure is reduced by an expansion valve, which is an example of a pressure reducing device, and (4) vaporized at a low temperature in an evaporator, and the heat is removed by the heat of vaporization.
• Compressors can be classified into turbo (centrifugal), reciprocating, rotary, twin-screw, single-screw, scroll compressors, etc. depending on the method of compressing the working medium in a gaseous state, and can be selected based on heat capacity, compression ratio, and size.
• the working medium of the present disclosure removes thermal energy from the load fluid in the evaporator, thereby cooling the load fluid to a lower temperature.
• FIG. 1 is a schematic diagram showing an example of a refrigeration cycle device of the present disclosure.
• the refrigeration cycle device 10 is a system generally comprising a compressor 11 that compresses working medium vapor A to produce high-temperature, high-pressure working medium vapor B, a condenser 12 that cools and liquefies the working medium vapor B discharged from the compressor 11 to produce low-temperature, high-pressure working medium C, an expansion valve 13 that expands the working medium C discharged from the condenser 12 to produce low-temperature, low-pressure working medium D, an evaporator 14 that heats the working medium D discharged from the expansion valve 13 to produce high-temperature, low-pressure working medium vapor A, a pump 15 that supplies a load fluid E to the evaporator 14, and a pump 16 that supplies a fluid F to the condenser 12.
• the working medium vapor A discharged from the evaporator 14 is compressed by the compressor 11 to produce high-temperature, high-pressure working medium vapor B (hereinafter referred to as the "AB process").
• the working fluid vapor B discharged from the compressor 11 is cooled by the fluid F in the condenser 12 and liquefied to become a low-temperature, high-pressure working fluid C. At this time, the fluid F is heated to become a fluid F', which is discharged from the condenser 12 (hereinafter referred to as the "BC process").
• the working medium C discharged from the condenser 12 is expanded in the expansion valve 13 to become a low-temperature, low-pressure working medium D (hereinafter referred to as the "CD process”).
• the working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to become high-temperature, low-pressure working medium vapor A. At this time, the load fluid E is cooled to become a load fluid E', which is discharged from the evaporator 14 (hereinafter referred to as the "DA process").
• the refrigeration cycle device 10 is a cycle system consisting of adiabatic isentropic changes, isenthalpic changes, and isobaric changes.
• the state change of the working medium is plotted on the pressure-enthalpy curve (curve) shown in Figure 2, it can be represented as a trapezoid with vertices A, B, C, and D.
• the AB process is a process in which adiabatic compression is performed in the compressor 11 to convert low-temperature, low-pressure working medium vapor A into high-temperature, high-pressure working medium vapor B, and is shown by line AB in Figure 2.
• the working medium vapor A is introduced into the compressor 11 in a superheated state, and the resulting working medium vapor B is also superheated vapor.
• the compressor intake gas density is the density ( ⁇ s) in state A in Figure 2.
• the compressor discharge temperature (discharge temperature) is the temperature (Tx) in state B in Figure 2, which is the maximum temperature in the refrigeration cycle.
• the compressor discharge pressure (discharge pressure) is the pressure (Px) in state B in Figure 2, which is the maximum pressure in the refrigeration cycle. Note that since the BC process is isobaric cooling, the discharge pressure has the same value as the condensation pressure. Therefore, for convenience, the condensation pressure is shown as Px in Figure 2.
• the discharge temperature (Td) is preferably lower than the discharge temperature of HFC-134a.
• the reduction effect (%) of the discharge temperature based on the discharge temperature of HFC-134a (- (discharge temperature of each working medium (°C) - discharge temperature of HFC-134a (°C)) / discharge temperature of HFC-134a (°C) x 100) is preferably 0.0% or more, more preferably 2.0% or more, and even more preferably 4.0% or more.
• the BC process is a process in which isobaric cooling is performed in the condenser 12 to convert high-temperature, high-pressure working medium vapor B into low-temperature, high-pressure working medium C, and is shown by line BC in Figure 2.
• the pressure at this time is the condensation pressure.
• the intersection T1 on the high enthalpy side is the condensation temperature
• the intersection T2 on the low enthalpy side is the condensation boiling point temperature.
• the temperature gradient is shown as the difference between T1 and T2 .
• the condensation temperature in the BC process is preferably 20° C. or higher, more preferably 30° C. or higher, and even more preferably 36° C. or higher. Furthermore, when the working medium I is applied, the condensation temperature in the BC process is preferably 90°C or less, more preferably 80°C or less, and even more preferably 66°C or less. If the condensation temperature is 90°C or less, it can be made below the critical temperature.
• the critical temperature is the end temperature on the high pressure/high temperature side of the saturated liquid line and the saturated vapor line. Above the critical point, there is no evaporation or liquefaction phenomenon, the liquid phase and the gas phase cannot be distinguished, and there is no phase change. If the temperature of the working medium is below the critical temperature, the working medium can be liquefied (condensed) and the refrigeration performance can be maintained.
• the CD process is a process in which isenthalpic expansion is performed in the expansion valve 13 to convert the low-temperature, high-pressure working medium C into a low-temperature, low-pressure working medium D, and is indicated by the line CD in Fig. 2. If the temperature of the low-temperature, high-pressure working medium C is indicated as T3 , then T2 - T3 is the degree of supercooling (SC) of the working medium in the cycles (i) to (iv).
• SC degree of supercooling
• the DA process is a process in which isobaric heating is performed in the evaporator 14 to return the low-temperature, low-pressure working medium D to high-temperature, low-pressure working medium vapor A, and is shown by the DA line in FIG. 2.
• the pressure at this time is the evaporation pressure.
• the intersection point T6 on the high-enthalpy side is the evaporation temperature.
• the temperature gradient in the evaporator when the working medium is a non-azeotropic mixture is shown as the difference between T6 and T4 .
• T7 - T6 is the degree of superheat (SH) of the working medium in the cycles (i) to (iv).
• T4 indicates the temperature of the working medium D.
• the evaporation temperature in the DA process is preferably -40°C or higher, more preferably -25°C or higher, and even more preferably -15°C or higher. If the evaporation temperature is -40°C or higher, the evaporation pressure can be 0.0295 MPa or higher, if it is -25°C or higher, the evaporation pressure can be 0.0645 MPa or higher, and if it is -15°C or higher, the evaporation pressure can be 0.101 MPa or higher.
• the evaporation temperature in the DA process is preferably 7°C or less, and more preferably 5°C or less. Setting the evaporation temperature to 7°C or less allows the discharge temperature to be reduced.
• the degree of superheat (SH) of the working medium is preferably 0 to 20°C from the viewpoint of reducing the discharge temperature.
• the CAP and COP of the working medium can be calculated from the following formulas (11), (12), (13), and (14), respectively, using the enthalpies hA, hB, hC, and hD, and the refrigerant mass circulation amount qmr in the working medium's states A (after evaporation, low temperature and low pressure), B (after compression, high temperature and high pressure), C (after condensation, low temperature and high pressure), and D (after expansion, low temperature and low pressure). There is no pressure loss in the piping and heat exchanger.
• the working medium vapor B' after the AB step is expressed by the following equation using hA, hB, and ⁇ , using the compressor efficiency ⁇ .
• hB' hA+(hB-hA)/ ⁇
• Thermodynamic properties required for calculating the cycle performance of the working fluid can be calculated based on the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (REFPROP 10.0), a generalized equation of state based on the corresponding state principle (Soave-Redlich-Kwong equation), and various thermodynamic relational equations.
• NIST National Institute of Science and Technology
• REFPROP 10.0 Reference Fluid Thermodynamic and Transport Properties Database
• the thermal cycle device of the present disclosure is filled with a working medium in a state where both the gas phase and the liquid phase coexist, and the air concentration of the gas phase in the thermal cycle device at a temperature of 25°C is preferably 3.5 vol.% or less, more preferably 2.5 vol.% or less, even more preferably 2.0 vol.% or less, and particularly preferably 1.5 vol.% or less.
• Examples 1 to 9, 16, and 17 are examples, and Examples 10 to 15, 18, and 19 are comparative examples.
• the working fluid was calculated for the items shown in Table 1. The method of calculating each item is as described above.
• the temperature (Td) is an absolute value
• the discharge temperature difference (Td134a difference) is a difference value based on the value of HFC-134a (Example 15)
• the CAP, COP, Pc, Pe, and discharge temperature reduction effect (Td Vs. HFC-134a) are relative values based on the value for HFC-134a (Example 15).
• the content of HFC-134a is 14.5 mass% or less relative to the total content of the specific components
• the content of HCFO-1224yd(Z) is 10.0 mass% or less relative to the total content of the specific components, so the GWP and specific heat ratio are reduced, a significant increase in flammability is suppressed, and the dew point boiling point temperature difference is suppressed, thereby suppressing an increase in temperature glide.
• the discharge temperature (Td) is reduced, and the effect of reducing the discharge temperature for HFC-134a is confirmed.
• examples 14 and 15 contain one of three specific components, so the values for GWP, specific heat ratio, and flammability are high.
• HFC-134a was more than 14.5% by mass, which resulted in a large dew point boiling point temperature difference, high temperature glide, and high GWP.
• Table 2 shows the saturated vapor pressure at temperature (Te') for the working fluids of Examples 1 to 19.
• the working fluid is a single medium or an azeotropic mixture medium
• the saturated liquid pressure and the saturated vapor pressure at the same temperature are substantially the same.
• the working fluid is a non-azeotropic medium
• the saturated liquid pressure and the saturated vapor pressure at the same temperature are different, and the saturated vapor pressure is lower than the saturated liquid pressure.
• the saturated vapor pressure estimated as the vapor pressure is 0.0295 MPa or more
• Te' is -25 to 7°C
• the saturated vapor pressure is 0.0645 MPa or more
• Te' is -15 to 7°C
• the saturated vapor pressure is 0.101 MPa or more.
• Example 7 For the working fluid of Example 7, the refrigeration cycle state was calculated when the condensation temperature, evaporation temperature, degree of superheat (SH), degree of subcooling (SC), and compressor efficiency were set to the conditions in Table 3, and the discharge temperature was obtained. In addition, for the working fluid of Example 13, the refrigeration cycle state was calculated when the condensation temperature, evaporation temperature, degree of superheat (SH), degree of subcooling (SC), and compressor efficiency were set to the conditions in Table 4, and the discharge temperature was obtained.
• Tables 3 and 4 also show the absolute value of the discharge temperature, the difference based on the discharge temperature of HFC-134a, and the reduction effect (%) of the discharge temperature based on the discharge temperature of HFC-134a (-(discharge temperature of each working medium (°C)-discharge temperature of HFC-134a (°C))/discharge temperature of HFC-134a (°C) ⁇ 100).
• the working medium of the present disclosure can have a small specific heat ratio, and therefore can suppress an increase in discharge temperature.
• the application of the working fluid of the present disclosure provides a significant benefit in terms of the reduction in discharge temperature.
• the air was filled in an amount such that the air concentration in the gas phase at 25° C. was as shown in Table 5.
• the HFO-1234ze(E), HCFO-1224yd(Z) and HFC-134a used had a purity of 99.5% by mass or more.
• the pressure vessel containing the working medium along with air of a specified concentration was then placed in a hot air circulating thermostatic chamber and left at a constant temperature of 150°C for five days.
• the pressure vessel was removed from the thermostatic chamber, and the appearances of the metal pieces made of SS400, Cu, and Al were visually observed.
• the SS400 metal pieces and the Al metal pieces no surface changes were observed even when the air concentration was changed in the range of 1.0 to 5.0 volume %.
• the Cu metal pieces surface changes were confirmed when the air concentration was changed in the range of 1.0 to 5.0 volume %. Therefore, the appearance of the Cu metal pieces after the above test was compared with that of the Cu metal pieces before the test, and the metal corrosion resistance was evaluated according to the following criteria. The results are shown in Table 5.
• B Part of the surface of the metal piece turned brown.
• C The entire surface of the metal piece turned brown and rust was generated.

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