WO2023100746A1 - 作動媒体 - Google Patents

作動媒体 Download PDF

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Publication number
WO2023100746A1
WO2023100746A1 PCT/JP2022/043431 JP2022043431W WO2023100746A1 WO 2023100746 A1 WO2023100746 A1 WO 2023100746A1 JP 2022043431 W JP2022043431 W JP 2022043431W WO 2023100746 A1 WO2023100746 A1 WO 2023100746A1
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WIPO (PCT)
Prior art keywords
propane
content
hfo
mass
working medium
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PCT/JP2022/043431
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English (en)
French (fr)
Japanese (ja)
Inventor
洋輝 速水
正人 福島
秀一 岡本
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AGC Inc
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Asahi Glass Co Ltd
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Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2023564924A priority Critical patent/JPWO2023100746A1/ja
Priority to CN202280079909.3A priority patent/CN118355089A/zh
Priority to EP22901179.6A priority patent/EP4442787A4/en
Publication of WO2023100746A1 publication Critical patent/WO2023100746A1/ja
Priority to US18/675,264 priority patent/US20240318060A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/106—Carbon dioxide
    • 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
    • C09K2205/32—The mixture being azeotropic

Definitions

  • the present disclosure relates to working media.
  • CFCs chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • HFC-32 difluoromethane
  • HFC-125 pentafluoroethane
  • HFC-125 hydrofluorocarbons
  • R410A a quasi-azeotropic mixture of HFC-32 and HFC-125 at a mass ratio of 1:1
  • HFCs may cause global warming.
  • R410A Due to its high refrigeration capacity, R410A has been widely used in ordinary air conditioning equipment such as so-called packaged air conditioners and room air conditioners. However, R410A has a high global warming potential (GWP) of 2088. Therefore, development of low GWP refrigerants is required. At this time, there is a demand for the development of a refrigerant on the premise of simply replacing R410A and continuing to use the devices that have been used as they are.
  • GWP global warming potential
  • HFO hydrofluoroolefins
  • HFO-1123 1,1,2-trifluoroethylene
  • HFO-1132 E-1,2-difluoroethylene
  • Techniques are disclosed. For HFO-1123 and HFO-1132(E), it is effective to combine other media such as HFC and HFO to form a working medium for the purpose of enhancing the cycle performance of these components.
  • propane which has a low GWP and excellent performance as a refrigerant
  • propane which has a low GWP and excellent performance as a refrigerant
  • development of a working medium containing propane is desired.
  • One aspect of the present disclosure has been made in view of the above-described conventional circumstances, and an object thereof is to provide a working medium containing propane and having excellent performance as a refrigerant.
  • Concrete means for achieving the above object are as follows. ⁇ 1> with propane; at least one of 1,1,2-trifluoroethylene and (E)-1,2-difluoroethylene; 2,3,3,3-tetrafluoro-1-propene, (E)-1,3,3,3-tetrafluoropropene, difluoromethane, CO 2 , CF 3 I, (Z)-1-chloro-2 , 3,3,3-tetrafluoropropene, (E)-1-chloro-2,3,3,3-tetrafluoropropene, (E)-1-chloro-3,3,3-trifluoropropene, ( E)-1,1,1,4,4,4-hexafluoro-2-butene, (Z)-1,2,3,3,3-pentafluoropropene, and (E)-1,2,3 , and at least one third component selected from the group consisting of 3,3-pentafluoropropene, A working medium having a heat of
  • ⁇ 2> containing propane, 1,1,2-trifluoroethylene, and 2,3,3,3-tetrafluoro-1-propene
  • the mass ratio of the propane content to the 1,1,2-trifluoroethylene content is 5:95 to 29:71
  • the content of 2,3,3,3-tetrafluoro-1-propene is the total content of propane, 1,1,2-trifluoroethylene, and 2,3,3,3-tetrafluoro-1-propene 10.5 to 25.0% by mass with respect to
  • the total content of propane, 1,1,2-trifluoroethylene, and 2,3,3,3-tetrafluoro-1-propene is 80% by mass or more relative to the total amount of the working medium, ⁇ 1>
  • the working medium according to .
  • ⁇ 3> containing propane, 1,1,2-trifluoroethylene, and difluoromethane;
  • the mass ratio of the propane content to the 1,1,2-trifluoroethylene content is 18:82 to 22:78,
  • ⁇ 4> containing propane, 1,1,2-trifluoroethylene, and difluoromethane;
  • the mass ratio of the propane content to the 1,1,2-trifluoroethylene content is 5:95 to 23:77,
  • ⁇ 5> containing propane, 1,1,2-trifluoroethylene, and difluoromethane;
  • the mass ratio of the propane content to the 1,1,2-trifluoroethylene content is 18.9:81.1 to 23:77,
  • ⁇ 6> containing propane, 1,1,2-trifluoroethylene, and (E)-1,3,3,3-tetrafluoropropene
  • the propane content is 25.0% by mass or less with respect to the total content of propane and 1,1,2-trifluoroethylene
  • (E)-1,3,3,3-tetrafluoropropene content is the sum of propane, 1,1,2-trifluoroethylene
  • the working medium according to ⁇ 1> wherein the total content is 78.5% by mass or more relative to the total amount of the working medium.
  • ⁇ 7> containing propane, 1,1,2-trifluoroethylene, and (E)-1,3,3,3-tetrafluoropropene
  • the propane content is 10% by mass or less with respect to the total content of propane and 1,1,2-trifluoroethylene
  • (E)-1,3,3,3-tetrafluoropropene content is the sum of propane, 1,1,2-trifluoroethylene
  • (E)-1,3,3,3-tetrafluoropropene The working medium according to ⁇ 1>, wherein the content is 15.0% by mass or less.
  • ⁇ 8> containing propane, 1,1,2-trifluoroethylene, and (E)-1,3,3,3-tetrafluoropropene
  • the propane content is 20.0% by mass or less with respect to the total content of propane and 1,1,2-trifluoroethylene
  • (E)-1,3,3,3-tetrafluoropropene content is the sum of propane, 1,1,2-trifluoroethylene
  • the working medium according to ⁇ 1> having a content of 9.0% by mass or less.
  • ⁇ 9> containing propane, 1,1,2-trifluoroethylene, and CO2 ,
  • the content of 1,1,2-trifluoroethylene with respect to the total content of propane, 1,1,2-trifluoroethylene, and CO 2 is X 1 % by mass, and the content of CO 2 with respect to the above total content is Y
  • X 1 and Y 1 satisfy the following formula (1),
  • ⁇ 11> containing propane, 1,1,2-trifluoroethylene, and CF 3 I
  • X 2 and Y 2 satisfy the following formula (2A)
  • the working medium according to ⁇ 1> which contains propane, (E)-1,2-difluoroethylene, and a third component, and has a combustion heat quantity of less than 15.250 MJ/kg.
  • ⁇ 14> containing propane, (E)-1,2-difluoroethylene, and a third component,
  • ⁇ 15> containing propane, 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoro-1-propene, and difluoromethane;
  • the content of difluoromethane with respect to the total content of propane, 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoro-1-propene, and difluoromethane is A mass%, with respect to the total content
  • the content of 2,3,3,3-tetrafluoro-1-propene is B% by mass
  • the content of propane with respect to the above total content is C% by mass
  • 1,1,2-trifluoroethylene with respect to the above total content
  • the content of difluoromethane with respect to the total content of propane, 1,1,2-trifluoroethylene, (E)-1,3,3,3-tetrafluoropropene, and difluoromethane is E mass%, the above total content
  • the content of difluoromethane with respect to the total content of propane, 1,1,2-trifluoroethylene, CO 2 and difluoromethane is J mass%
  • the content of CO 2 with respect to the above total content is K mass%
  • the above total When the content of propane with respect to the content is L mass%, and the content of 1,1,2-trifluoroethylene with respect to the total content is M mass%
  • J, K, L, and M are represented by the following formula ( The working medium according to ⁇ 1>, which satisfies 5A) to (5D).
  • the working medium according to ⁇ 1> containing propane, 1,1,2-trifluoroethylene, CF 3 I, and difluoromethane.
  • ⁇ 19> containing propane, 1,1,2-trifluoroethylene, and 2,3,3,3-tetrafluoro-1-propene,
  • the content of 2,3,3,3-tetrafluoro-1-propene is the total content of propane, 1,1,2-trifluoroethylene, and 2,3,3,3-tetrafluoro-1-propene 25.0 to 70.0% by mass with respect to
  • the propane content is 9.0% by mass or less with respect to the total content
  • the working medium according to ⁇ 1> wherein the total content is 78.5% by mass or more relative to the total amount of the working medium.
  • a working medium containing propane and having excellent performance as a refrigerant is provided.
  • FIG. 1 is a ternary diagram of the ternary system of propane, HFO-1123 and HFO-1234yf.
  • FIG. 2 shows a ternary diagram of the ternary system of propane, HFO-1123 and HFO-1234ze(E).
  • FIG. 3 is a ternary diagram of the ternary system of propane, HFO-1123 and HFC-32.
  • FIG. 4 is a ternary diagram of the ternary system of propane, HFO-1123 and CO 2 .
  • FIG. 5 is a ternary diagram of the propane, HFO-1123 and CF 3 I ternary system.
  • FIG. 6 is a ternary diagram of the ternary system of propane, HFO-1123 and HFO-1132(E).
  • FIG. 1 is a ternary diagram of the ternary system of propane, HFO-1123 and HFO-1234yf.
  • FIG. 2 shows a ternary diagram of the ternary system of propane, HFO-1123 and HFO-1234ze(
  • FIG. 7 is a ternary diagram of the ternary system of propane, HFO-1132(E) and HFO-1234yf.
  • FIG. 8 is a ternary diagram of the ternary system of propane, HFO-1132(E) and HFO-1234ze(E).
  • FIG. 9 is a ternary diagram of the ternary system of propane, HFO-1132(E) and HFC-32.
  • FIG. 10 is a ternary diagram of the ternary system of propane, HFO-1132(E) and CO 2 .
  • FIG. 11 is a ternary diagram of the ternary system of propane, HFO-1132(E) and CF 3 I.
  • FIG. 12 is a schematic configuration diagram showing an example of a refrigeration cycle system.
  • FIG. 13 is a cycle diagram showing changes in the state of the working medium in the refrigeration cycle system on a pressure-enthalpy diagram.
  • FIG. 14 is a cycle diagram showing changes in the state of the working medium in the refrigeration cycle system on
  • a numerical range indicated using “to” means a range including the numerical values before and after “to” as the minimum and maximum values, respectively.
  • upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step.
  • upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
  • the amount of each component in the composition is the total amount of the multiple substances present in the composition unless otherwise specified. means. In the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.
  • the working medium of the present disclosure comprises propane, at least one of HFO-1123 and HFO-1132 (E), and 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), (E)-1 , 3,3,3-tetrafluoropropene (HFO-1234ze(E)), HFC-32, CO 2 , CF 3 I, (Z)-1-chloro-2,3,3,3-tetrafluoropropene ( HCFO-1224yd(Z)), (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)), (E)-1-chloro-3,3,3- Trifluoropropene (HFO-1233zd(E)), (E)-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz(E)), (Z)-1,2 , 3,3,3-pentafluoropropene (HFO-1234y
  • the working medium means a medium that carries heat, and is a concept that includes refrigerant compositions and heat medium compositions.
  • the refrigerant composition is a medium mainly responsible for cooling the heat source, but may also be used as a medium responsible for heating at the same time.
  • the heat transfer medium composition is a medium mainly responsible for heating, but may also be used as a medium responsible for cooling the heat source at the same time.
  • the working medium of the present disclosure includes propane together with at least one of HFO-1123 and HFO-1132(E), HFO-1234yf, HFO-1234ze(E), HFC-32, CO 2 , CF 3 I, HCFO-1224yd ( Z), HCFO-1224yd (E), HFO-1233zd (E), HFO-1336mzz (E), HFO-1225ye (Z), and at least one selected from the group consisting of HFO-1225ye (E)
  • propane can be effectively used as a refrigerant.
  • HFO-1234yf, HFO-1234ze (E), HFC-32, CO 2 , CF 3 I, HCFO-1224yd (Z), HCFO-1224yd (E), HFO-1233zd (E), HFO-1336mzz ( E), HFO-1225ye (Z), and at least one selected from the group consisting of HFO-1225ye (E)" is also referred to as a third component.
  • the third component preferably has a boiling point of 0°C or less, more preferably -5°C or less, and comes out at -10°C. is more preferred, and -15°C or lower is particularly preferred.
  • the lower limit of the boiling point is not particularly limited, and is -80°C, for example.
  • the working medium of the present disclosure comprises propane, at least one of HFO-1123 and HFO-1132(E), HFO-1234yf, HFO-1234ze(E), HFC-32, CO 2 and CF and at least one selected from the group consisting of 3I .
  • the working medium of the present disclosure consists of propane, at least one of HFO-1123 and HFO-1132(E), and HFO-1234yf, HFO-1234ze(E), and HFC-32. It is further preferable to contain at least one selected from the group.
  • the working fluid of the present disclosure preferably contains HFO-1123 because of its slow burning rate and low heat of combustion.
  • HFO-1123 does not have isomers, it does not cause isomerization reaction during use of the working medium, and has excellent stability. That is, the working medium of the present disclosure includes propane, HFO-1123, HFO-1234yf, HFO-1234ze (E), HFC-32, CO 2 , CF 3 I, HCFO-1224yd (Z), HCFO-1224yd ( E), HFO-1233zd (E), HFO-1336mzz (E), HFO-1225ye (Z), and at least one selected from the group consisting of HFO-1225ye (E).
  • the working medium of the present disclosure includes at least one selected from the group consisting of propane, HFO-1123, HFO-1234yf, HFO-1234ze(E), HFC-32, CO 2 and CF 3 I. , is more preferred. Further, the working medium of the present disclosure further contains propane, HFO-1123, and at least one selected from the group consisting of HFO-1234yf, HFO-1234ze(E), and HFC-32. preferable.
  • the content of propane in the working medium of the present disclosure is not particularly limited as long as the amount of combustion heat of the working medium as a whole is within the range of less than 19.000 MJ/kg.
  • the content of propane is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, relative to the total amount of the working medium. , more preferably 5.0% by mass or more.
  • the propane content may be 40.0% by mass or less relative to the total amount of the working medium.
  • the content of propane is preferably 1.0 to 30.0% by mass with respect to the total amount of the working medium from the viewpoint of making the combustion heat amount of the working medium as a whole less than 19.000 MJ / kg. 0 to 25.0% by mass, and even more preferably 1.0 to 23.0% by mass.
  • the content of at least one of HFO-1123 and HFO-1132 (E) in the working medium of the present disclosure is particularly limited as long as the amount of heat of combustion of the working medium as a whole is within the range of less than 19.000 MJ / kg. not to be From the viewpoint of improving the performance of the working medium as a refrigerant, the content of at least one of HFO-1123 and HFO-1132 (E) is preferably 20.0% by mass or more with respect to the total amount of the working medium, It is more preferably 30.0% by mass or more, further preferably 40.0% by mass or more, particularly preferably 50.0% by mass or more, and most preferably 55.0% by mass or more. preferable.
  • the content of at least one of HFO-1123 and HFO-1132(E) may be 90.0% by mass or less, or may be 85% by mass or less, relative to the total amount of the working medium.
  • the content of at least one of HFO-1123 and HFO-1132(E) means the content of one component when the working medium contains HFO-1123 or HFO-1132(E), When the medium contains HFO-1123 and HFO-1132(E), it means the total content of each component.
  • the third component may be used singly or in combination of two or more.
  • the content of the main component in the third component is not particularly limited as long as the amount of combustion heat of the working medium as a whole is within the range of less than 19.000 MJ / kg. do not have.
  • the content of the main component in the third component is preferably 1.0% by mass or more with respect to the total amount of the working medium, and 5.0% by mass. It is more preferably 10.0% by mass or more, and more preferably 10.0% by mass or more.
  • the content of the main component in the third component is preferably 35.0% by mass or less with respect to the total amount of the working medium, and 30.0% by mass. It is more preferably 25.0% by mass or more, and more preferably 25.0% by mass or more.
  • the main component in the third component means the component when the working medium contains only one component as the third component, and when the working medium contains a plurality of components as the third component. , means the component with the highest content among the third components.
  • the total content of propane, at least one of HFO-1123 and HFO-1132 (E), and the main component in the third component is the total amount of the working medium from the viewpoint of reducing GWP It is preferably 80% by mass or more, more preferably 85% by mass or more.
  • the upper limit of the total content is not particularly limited, and may be 100% by mass.
  • the total content may be less than 95% by mass or less than 90% by mass with respect to the total amount of the working medium. That is, the working medium of the present disclosure may contain propane, at least one of HFO-1123 and HFO-1132(E), and components other than the third component, and the third component may include a plurality of good too.
  • the content of HFC-32 is 22.0% by mass or less with respect to the total amount of the working medium from the viewpoint of making the GWP of the entire working medium 150 or less. It may be present, may be 19.0% by mass or less, or may be 15.0% by mass or less.
  • the content of HFC-32 may be 1.0% by mass or more relative to the total amount of the working medium.
  • the content of CO2 may be 15.0% by mass or less with respect to the total amount of the working medium, and may be 10.0% by mass. % or less, or 8.0% by mass or less.
  • the content of CO 2 may be 1.0% by weight or more, relative to the total amount of working medium.
  • the content of HFO-1234yf is preferably 30.0% by mass or less with respect to the total amount of the working medium from the viewpoint of reducing temperature glide and pressure loss. It is preferably 25.0% by mass or less, and more preferably 25.0% by mass or less. From the viewpoint of lowering the condensation pressure, the content of HFO-1234yf is preferably 10.5% by mass or more, more preferably 15.0% by mass or more, relative to the total amount of the working medium.
  • the working medium of the present disclosure contains HCFO-1224yd(Z), HCFO-1224yd(E), HFO-1233zd(E), HFO-1336mzz(E), HFO-1225ye(Z), or HFO-1225ye(E)
  • the content of each component may be 15.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less with respect to the total amount of the working medium. good too.
  • the content of each component may be 1.0% by mass or more relative to the total amount of the working medium.
  • combustion heat quantity per mass is defined by the American Society of Heating, Refrigeration and Air-conditioning Engineers (ASHRAE) Standard 34 as an index for determining the combustibility of refrigerants.
  • ASHRAE American Society of Heating, Refrigeration and Air-conditioning Engineers
  • This standard defines a substance with a calorific value of 19.000 MJ/kg or more as one of the indicators of a "highly flammable" refrigerant.
  • the amount of combustion heat is represented by the difference between the sum of the enthalpy of formation of the products in the combustion reaction formula and the enthalpy of formation of the compounds in the reaction system.
  • the enthalpy of formation is described in handbooks of chemistry, international standards (see Reference A), various handbooks, and the like.
  • the enthalpy of formation of a novel compound can be determined by Benson's group additivity rule (see reference B) or by a computational chemical method.
  • concept of the combustion reaction formula for compounds containing halogen is specified in international standards (see references A and C).
  • Reference A ANSI/ASHRAE Standard 34 (2016), Designation and Safety Classification of Refrigerants.
  • Reference B S.M. Benson, Thermo chemical kinetics, 2nd Ed. , Wiley Interscience, New York (1976).
  • Reference C ISO 817 (2014), Refrigerant: Designation and Safety Classification. In this standard, the heat of combustion is considered positive for exothermic reactions.
  • the combustion heat quantity of the working medium is obtained by converting the value of the combustion heat quantity obtained by stoichiometrically burning 1 mol of the working medium with oxygen completely into the value of the combustion heat quantity per 1 kg of the working medium. It is a theoretical value calculated under the following assumptions.
  • the compounds of the product and reaction systems are assumed to be gases.
  • the products of combustion are HF (g), CO2 (g), COF2 (g) and H2O (g).
  • nitrogen and iodine are part of the molecular structure of the substance, N 2 (g) or I 2 (g) are added as combustion products.
  • each compound contained in the working medium is decomposed into atoms constituting each compound, and a virtual substance containing each atom is set in consideration of the molar ratio in the working medium.
  • the combustion heat quantity is calculated using the combustion reaction formula of the virtual substance.
  • CqHrFs in the following formula corresponds to a virtual substance.
  • the combustion reaction formula is defined by the number of H atoms (r) and the number of F atoms (s) in a substance, and when the number of H atoms (r) ⁇ the number of F atoms (s), the combustion reaction formula is , the following formula is used:
  • the content of each component contained in the working fluid is within a specific range, so that the combustion heat quantity is low and the heat cycle performance is excellent.
  • HFO-1123 or HFO-1132(E) When HFO-1123 or HFO-1132(E) is combined with propane, the latent heat of vaporization tends to increase, and the pressure loss becomes smaller than when HFO-1123 or HFO-1132(E) is used alone. . Further, by combining propane, at least one of HFO-1123 and HFO-1132(E), and a third component, cycle performance such as discharge temperature, condensing pressure, CAP, and temperature glide is improved.
  • the first aspect of the working medium of the present disclosure contains propane, HFO-1123, and HFO-1234yf from the viewpoint of improving the performance of the working medium as a refrigerant, and the propane content and HFO-1123
  • the mass ratio with the content (propane: HFO-1123) is 5: 95 to 29: 71
  • the content of HFO-1234yf is relative to the total content of propane, HFO-1123, and HFO-1234yf 10.5 to 25.0% by mass
  • the total content of propane, HFO-1123, and HFO-1234yf is preferably 80% by mass or more relative to the total amount of the working medium.
  • the condensation pressure is lowered.
  • the ratio of the propane content to the total content of propane and HFO-1123 is 29% by mass or less, the combustion heat quantity decreases.
  • the mass ratio of the propane content and the HFO-1123 content is preferably 10:90 to 29:71, more preferably 15:85 to 29:71.
  • 20:80 to 29:71 are more preferred
  • 22:78 to 29:71 are particularly preferred
  • 22:78 to 27:73 are very preferred.
  • the content of HFO-1234yf is preferably 12% by mass or more with respect to the total content of propane, HFO-1123, and HFO-1234yf, and 15% by mass. It is more preferable to be above.
  • the GWP is lowered.
  • the total content of propane, HFO-1123 and HFO-1234yf is more preferably 85% by mass or more.
  • the upper limit of the total content is not particularly limited, and may be 100% by mass.
  • the total content may be less than 95% by mass or less than 90% by mass with respect to the total amount of the working medium.
  • a second embodiment of the working medium of the present disclosure contains propane, HFO-1123, and HFC-32, and the mass ratio of the propane content to the HFO-1123 content (propane:HFO-1123) is 18:82 to 22:78, and the content of HFC-32 is 5.5 to 19.5% by mass with respect to the total content of propane, HFO-1123, and HFC-32 preferable.
  • the discharge temperature and condensation pressure are lowered.
  • the proportion of the propane content in the total content of propane and HFO-1123 is 22% by mass or less, the combustion heat quantity is lowered, the CAP is improved, and the temperature glide and pressure loss are reduced.
  • the mass ratio of the propane content and the HFO-1123 content is preferably 19:81 to 21:79, and 19.5:80.5 to 20.5:79. 5 is more preferred.
  • the content of HFC-32 is preferably 6.0% by mass or more with respect to the total content of propane, HFO-1123, and HFC-32, and 8.0 mass % or more is more preferable. From the viewpoint of further lowering the discharge temperature and condensation pressure, the content of HFC-32 is preferably 19.0% by mass or less with respect to the total content of propane, HFO-1123, and HFC-32. 0% by mass or less, and even more preferably 15.0% by mass or less.
  • the total content of propane, HFO-1123, and HFC-32 is preferably 80% by mass or more with respect to the total amount of the working medium, and 85% by mass. % or more is more preferable.
  • the upper limit of the total content is not particularly limited, and may be 100% by mass. Moreover, the total content may be less than 95% by mass or less than 90% by mass with respect to the total amount of the working medium.
  • a third aspect of the working medium of the present disclosure contains propane, HFO-1123, and HFC-32, and the mass ratio of the propane content to the HFO-1123 content (propane:HFO-1123) is 5:95 to 23:77, and the content of HFC-32 is 20.1 to 21.9% by mass with respect to the total content of propane, HFO-1123, and HFC-32 preferable.
  • the discharge temperature is lowered.
  • the ratio of the propane content to the total content of propane and HFO-1123 is 23% by mass or less, the CAP is improved.
  • the total content of propane, HFO-1123, and HFC-32 is preferably 80% by mass or more with respect to the total amount of the working medium, and 85% by mass. % or more is more preferable.
  • the upper limit of the total content is not particularly limited, and may be 100% by mass.
  • the total content may be less than 95% by mass or less than 90% by mass with respect to the total amount of the working medium.
  • a fourth aspect of the working medium of the present disclosure contains propane, HFO-1123, and HFC-32, and the mass ratio of the propane content to the HFO-1123 content (propane:HFO-1123) is 18.9:81.1 to 23:77, and the content of HFC-32 is 12.5 to 21.5% by mass with respect to the total content of propane, HFO-1123, and HFC-32 is preferably
  • the discharge temperature is lowered.
  • the ratio of the propane content to the total content of propane and HFO-1123 is 23% by mass or less, the CAP is improved.
  • the content of HFC-32 should be 15.0 to 21.5% by mass with respect to the total content of propane, HFO-1123, and HFC-32. is preferred, and 18.0 to 21.5% by mass is more preferred.
  • the total content of propane, HFO-1123, and HFC-32 is preferably 80% by mass or more with respect to the total amount of the working medium, and 85% by mass. % or more is preferable.
  • the upper limit of the total content is not particularly limited, and may be 100% by mass.
  • the total content may be less than 95% by mass or less than 90% by mass with respect to the total amount of the working medium.
  • a fifth aspect of the working medium of the present disclosure contains propane, HFO-1123, and HFO-1234ze(E), and the content of propane is 25% relative to the total content of propane and HFO-1123. .0% by mass or less, and the content of HFO-1234ze (E) is 11.0 to 25.0% by mass with respect to the total content of propane, HFO-1123, and HFO-1234ze (E) , the total content is preferably 78.5% by mass or more with respect to the total amount of the working medium.
  • the amount of combustion heat can be reduced.
  • the propane content is more preferably 20.0% by mass or less, and even more preferably 15.0% by mass or less.
  • the lower limit of the propane content is not particularly limited, but from the viewpoint of latent heat of vaporization, it is preferably 2.0% by mass, more preferably 3.0% by mass, and 4.0% by mass. is more preferable, and 5.0% by mass is particularly preferable.
  • the condensation pressure decreases. and can achieve 1.12 or less.
  • the content of HFO-1234ze (E) is 25.0% by mass or less with respect to the total content of propane, HFO-1123, and HFO-1234ze (E)
  • the temperature glide becomes small, A temperature glide of less than °C can be achieved.
  • the content of HFO-1234ze (E) is more preferably 12.0% by mass or more, more preferably 13.0% by mass or more, with respect to the total content, from the viewpoint of further lowering the condensation pressure.
  • HFO-1234ze (E) is more preferably 14.0% by mass or more, particularly preferably 15.0% by mass or more, and most preferably 15.0% by mass or more.
  • the content of HFO-1234ze (E) is more preferably 24.0% by mass or less, more preferably 23.0% by mass or less, relative to the total content, from the viewpoint of further reducing the temperature glide. 22.0% by mass or less is particularly preferable, and 21.0% by mass or less is most preferable.
  • the total content of propane, HFO-1123, and HFO-1234ze (E) is more preferably 85% by mass or more with respect to the total amount of the working medium, It is more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • a sixth aspect of the working medium of the present disclosure contains propane, HFO-1123, and HFO-1234ze(E), wherein the content of propane is 10% relative to the total content of propane and HFO-1123. % by mass or less, and the content of HFO-1234ze(E) is preferably 15.0% by mass or less with respect to the total content of propane, HFO-1123, and HFO-1234ze(E).
  • the amount of combustion heat can be reduced.
  • the propane content is more preferably 8.0% by mass or less, and even more preferably 6.0% by mass or less.
  • the lower limit of the propane content is not particularly limited, it is preferably 2.0% by mass from the viewpoint of the latent heat of vaporization.
  • the temperature glide is small. and a temperature glide of 5°C or less can be achieved.
  • the content of HFO-1234ze (E) is more preferably 14.0% by mass or less, more preferably 13.0% by mass or less, relative to the total content. It is more preferably 12.0% by mass or less, particularly preferably 11.0% by mass or less, and most preferably 11.0% by mass or less.
  • the content of HFO-1234ze(E) is not particularly limited, and is, for example, 1.0% by mass.
  • the total content of propane, HFO-1123, and HFO-1234ze (E) is 85% by mass or more with respect to the total amount of the working medium. is more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • a seventh aspect of the working medium of the present disclosure contains propane, HFO-1123, and HFO-1234ze(E), and the content of propane is 20% relative to the total content of propane and HFO-1123. 0% by mass or less, and the content of HFO-1234ze(E) is preferably 9.0% by mass or less with respect to the total content of propane, HFO-1123, and HFO-1234ze(E). .
  • the amount of combustion heat can be reduced.
  • the propane content is more preferably 15.0% by mass or less, and even more preferably 10.0% by mass or less.
  • the lower limit of the propane content is not particularly limited, it is preferably 2.0% by mass from the viewpoint of the latent heat of vaporization.
  • the temperature glide is small. and a temperature glide of 4°C or less can be achieved.
  • the content of HFO-1234ze (E) is more preferably 8.0% by mass or less, more preferably 7.0% by mass or less, relative to the total content. More preferably, it is particularly preferably 6.0% by mass or less.
  • the content of HFO-1234ze(E) is not particularly limited, and is, for example, 1.0% by mass.
  • the total content of propane, HFO-1123, and HFO-1234ze (E) is 85% by mass or more with respect to the total amount of the working medium. is more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • An eighth embodiment of the working medium of the present disclosure contains propane, HFO-1123 and CO2 , wherein the content of HFO-1123 with respect to the total content of propane, HFO-1123 and CO2 is X 1
  • X 1 and Y 1 satisfy the following formula (1)
  • propane the above total content is the total amount of the working medium It is preferably 78.5% by mass or more. ⁇ 0.00115X 1 3 +0.13537X 1 2 ⁇ 6.20662X 1 +151.14664 ⁇ Y 1 ⁇ 59 (1)
  • the temperature glide becomes small and a temperature glide of 7 ° C. or less is achieved. can.
  • Z 1 and Y 1 satisfy the following formula (1A) when the content of propane with respect to the total content is Z 1 % by mass.
  • Z 1 and Y 1 when Z 1 is 1.0 to 23.3, Z 1 and Y 1 satisfy formula (1A), and when Z 1 is more than 23.3 and 24.84 or less, Z 1 and Y 1 preferably satisfies the following formula (1Aa). 3.33333Z 1 ⁇ 77.66667 ⁇ Y 1 ⁇ 0.00288Z 1 3 ⁇ 0.14523Z 1 2 +0.75794Z 1 +31.5 (1Aa)
  • the total content of propane, HFO-1123, and CO2 is more preferably 85% by mass or more, more preferably 90% by mass or more, relative to the total amount of the working medium. More preferably, it is more preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • the content of CO 2 is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, relative to the total content. It is preferably 10.0% by mass or less, and more preferably 10.0% by mass or less.
  • the lower limit of the CO 2 content is not particularly limited, and is, for example, 2.0% by mass. If the content of CO 2 is 20.0% by mass or less with respect to the above total content, the condensation pressure will decrease and 1.7 or less can be achieved.
  • a ninth aspect of the working medium of the present disclosure contains propane, HFO-1123, and CF 3 I, wherein the content of propane relative to the total content of propane, HFO-1123, and CF 3 I is X 2
  • X 2 and Y 2 satisfy the following formula (2A)
  • the total content is relative to the total amount of the working medium is preferably 78.5% by mass or more.
  • the temperature glide becomes small, and a temperature glide of 5 ° C. or less is achieved. can.
  • X 2 and Y 2 when X 2 is 1.0 to 23.3, X 2 and Y 2 satisfy formula (2A), and when X 2 is more than 23.3 and 25.91 or less, X 2 and Y 2 preferably satisfy the following formula (2Aa). 3.83055X 2 ⁇ 89.44721 ⁇ Y 2 ⁇ 1.125X 2 +39 (2Aa)
  • X 2 and Y 2 further satisfy the following formula (2B). Y 2 ⁇ 0.05994X 2 2 + 0.23676X 2 + 11.85165 (2B)
  • the tenth aspect of the working fluid of the present disclosure preferably contains propane, HFO-1132 (E), and the third component, and has a combustion heat quantity of less than 15.250 MJ/kg.
  • the tenth aspect more preferably contains propane, HFO-1132(E), and HFO-1234yf.
  • the combustion heat quantity is more preferably less than 14.0 MJ/kg, even more preferably less than 12.0 MJ/kg.
  • the propane content is preferably 30.0% by mass or less, more preferably 20% by mass or less, relative to the total content of propane and HFO-1132 (E). It is more preferably 0.0% by mass or less, and particularly preferably 8.0% by mass or less. When the propane content is 30.0% by mass or less, the amount of combustion heat can be further reduced. Although the lower limit of the propane content is not particularly limited, it is, for example, 2.0% by mass.
  • the total content of propane, HFO-1132 (E), and the third component is 85% by mass or more with respect to the total amount of the working medium. It is more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • An eleventh aspect of the working medium of the present disclosure contains propane, HFO-1132(E), and the third component, and the content of propane is the total content of propane and HFO-1132(E) It is preferably 10.0% by mass or less with respect to
  • the eleventh aspect more preferably contains propane, HFO-1132(E), and HFO-1234yf.
  • the combustion heat quantity can be further reduced. More preferably, the content of propane is 8.0% by mass or less with respect to the total content of propane and HFO-1132(E). Although the lower limit of the propane content is not particularly limited, it is, for example, 2.0% by mass.
  • the total content of propane, HFO-1132 (E), and the third component is 85% by mass or more with respect to the total amount of the working medium. It is more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • a twelfth aspect of the working medium of the present disclosure contains propane, HFO-1123, HFO-1234yf, and HFC-32, with a total content of propane, HFO-1123, HFO-1234yf, and HFC-32
  • the content of HFC-32 with respect to the amount is A mass%
  • the content of HFO-1234yf with respect to the total content is B mass%
  • the content of propane with respect to the total content is C mass%
  • HFO with respect to the total content - When the content of 1123 is D mass %
  • A, B, C, and D preferably satisfy the following formulas (3A) to (3D).
  • the condensing pressure can be reduced to less than 1.2122 and the compression ratio can be reduced to 0.2122. Less than 9453 can be achieved.
  • the total content is more preferably 85% by mass or more, more preferably 90% by mass or more, relative to the total amount of the working medium. More preferably, it is particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • a thirteenth aspect of the working medium of the present disclosure contains propane, HFO-1123, HFO-1234ze(E), and HFC-32, wherein propane, HFO-1123, HFO-1234ze(E), and The content of HFC-32 with respect to the total content of HFC-32 is E mass%, the content of HFO-1234ze (E) with respect to the total content is F mass%, and the content of propane with respect to the total content is G mass. %, and the content of HFO-1123 with respect to the above total content is H% by mass, E, F, G, and H preferably satisfy the following formulas (4A) to (4D).
  • the total content is more preferably 85% by mass or more, more preferably 90% by mass or more, relative to the total amount of the working medium. More preferably, it is particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • a fourteenth aspect of the working medium of the present disclosure contains propane, HFO-1123, CO 2 and HFC-32, and the total propane, HFO-1123, CO 2 and HFC-32 content
  • the content of HFC-32 is J% by mass
  • the content of CO 2 is K% by mass with respect to the total content
  • the content of propane is L% by mass with respect to the total content
  • the content of HFO-1123 with respect to the total content J, K, L, and M preferably satisfy the following formulas (5A) to (5D), where the amount is M mass %.
  • the condensing pressure can be reduced to less than 1.48789, and the pressure loss can be reduced to 0.48789. Less than 92297 can be achieved.
  • the total content is more preferably 85% by mass or more, more preferably 90% by mass or more, relative to the total amount of the working medium. More preferably, it is particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • the fifteenth aspect of the working medium of the present disclosure preferably contains propane, HFO-1123, CF 3 I, and HFC-32.
  • the combustion calorific value decreases.
  • the total content of propane, HFO-1123, CF 3 I, and HFC-32 is 85% by mass or more with respect to the total amount of the working medium. It is more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the upper limit of the total content is not particularly limited, and the total content may be 100% by mass.
  • a sixteenth aspect of the working medium of the present disclosure contains propane, HFO-1123, and HFO-1234yf, and the content of HFO-1234yf is the total content of propane, HFO-1123, and HFO-1234yf is 25.0 to 70.0% by mass, the content of propane is 9.0% by mass or less with respect to the total content, and the total content is relative to the total amount of the working medium It is preferably at least 78.5% by mass.
  • the content of HFO-1234yf is 25.0 to 43.0% by mass, or 62.0 to 70.0% by mass with respect to the above total content. is preferably
  • the combustion heat quantity is reduced.
  • the lower limit of the propane content is not particularly limited, it is preferably 2.0% by mass from the viewpoint of increasing the latent heat of vaporization.
  • the content of HFO-1123 is appropriately adjusted by the content of propane and the content of HFO-1234yf. From the viewpoint of further lowering the condensation pressure, the content of HFO-1123 is preferably 73% by mass or less with respect to the above total content. Also, from the viewpoint of further reducing CAP, the content of HFO-1123 is preferably 21% by mass or more with respect to the above total content.
  • the total content of propane, HFO-1123, and HFO-1234yf is 78.5% by mass or more with respect to the total amount of the working medium
  • performance such as combustion heat amount, condensation pressure, and CAP is balanced.
  • the total content is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 99% by mass or more with respect to the total amount of the working medium. It is particularly preferred to have
  • the upper limit of the total content is not particularly limited, and may be 100% by mass.
  • the working medium of the present disclosure may contain any component other than propane, at least one of HFO-1123 and HFO-1132(E), and the third component within the range that does not impair the effects of the present disclosure.
  • Optional components include, for example, HFCs and HFOs other than HFO-1123, HFO-1132(E), and a third component.
  • Optional components may be used singly or in combination of two or more.
  • Optional components include, for example, HFCs such as 1,1-difluoroethane (HFC-152a), trifluoroethane, 1,1,2,2-tetrafluoroethane (HFC-134), pentafluoropropane, hexafluoro Propane, heptafluoropropane, pentafluorobutane, and heptafluorocyclopentane.
  • HFOs include 2-fluoropropene (HFO-1261yf), 1,1,2-trifluoropropene (HFO-1243yc), and 3,3,3-trifluoropropene (HFO-1243zf).
  • Examples of compounds other than HFCs and HFOs include hydrocarbons such as propylene, cyclopropane, butane, isobutane, pentane, and isopentane; 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 other chlorofluoroolefins (CFO) and hydrochlorofluoroolefins (HCFO) such as 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) and 1-chloro-1,2-difluoroethylene (HCFO-1122).
  • the optional component is preferably a component that has less impact on the ozone layer and less impact on global warming.
  • the total content of the optional components is preferably less than 10% by mass, more preferably 8% by mass or less, relative to the total amount of the working medium. , 5% by mass or less.
  • the lower limit of the total content of arbitrary components is not particularly limited, and may be 0% by mass.
  • the method for producing a working medium of the present disclosure comprises propane, at least one of HFO-1123 and HFO-1132(E), HFO-1234yf, HFO-1234ze(E), HFC-32, CO 2 and CF 3 I calculating the combustion heat quantity of the working medium containing at least one selected from the group consisting of; is a manufacturing method for preparing According to the method for producing a working medium of the present disclosure, it is possible to easily produce a working medium containing propane and having excellent performance as a refrigerant.
  • propane, at least one of HFO-1123 and HFO-1132 (E), a third component, and optionally other components are appropriately selected to form a virtual mixture is set, and the heat of combustion for the mixture is calculated by the method described above.
  • the content of the third component is fixed, and the combustion heat of the mixture is calculated while changing the content of propane and HFO-1123 or HFO-1132(E).
  • a working medium can be obtained by determining a desired composition as a working medium from and preparing a mixture of the determined composition.
  • the combustion heat quantity for one example of the working medium of the present disclosure is shown.
  • the composition ratio of each component indicates the content on a mass basis (% by mass).
  • the unit of heat of combustion is (MJ/kg).
  • X indicates that the combustion heat quantity is 19.000 MJ/kg or more, and O indicates that it is less than 19.000 MJ/kg.
  • Examples 1, 2, etc., which are specific examples of the working medium, are expressed as Case 1, Case 2, etc. in the table. It also shows the GWP of the working medium.
  • GWP is used as an index for measuring the impact of working media on global warming.
  • GWP is the 100-year value of the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (2013) unless otherwise specified. Specifically, they are HFC-32(677), CO 2 (1.0), HFO-1234yf ( ⁇ 1.0), HFO-1234ze(E) ( ⁇ 1.0).
  • IPCC Intergovernmental Panel on climate Change
  • GWP in a mixture is a weighted average by composition mass. When considering the GWP in a mixture, those with a GWP of 1 or less are treated as 1 in the calculation.
  • Table 1 shows the composition, heat of combustion and GWP of the two-component working medium of propane and HFO-1123.
  • Tables 2-10 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1123 and HFO-1234yf.
  • FIG. 1 also shows a ternary diagram of the ternary system of propane, HFO-1123 and HFO-1234yf.
  • FIG. 1 shows a straight line connecting (23.3, 76.7, 0.0) and (22.0, 0.0, 78.0) for (propane, HFO-1123, HFO-1234yf). ing.
  • the low propane concentration region including this straight line indicates the region where the combustion calorific value for the three-component system of propane, HFO-1123 and HFO-1234yf is less than 19.000 MJ / kg, and the region where the propane concentration is higher than this straight line , propane, HFO-1123 and HFO-1234yf, the combustion calorific value is 19.000 MJ/kg or more.
  • Tables 11-19 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1123 and HFO-1234ze(E).
  • FIG. 2 shows a ternary diagram of the ternary system of propane, HFO-1123 and HFO-1234ze(E).
  • (propane, HFO-1123, HFO-1234ze (E)) is a straight line connecting (23.3, 76.7, 0.0) and (23.3, 0.0, 76.7) It is shown.
  • the low propane concentration region including this straight line indicates the region where the combustion calorific value for the three-component system of propane, HFO-1123 and HFO-1234ze (E) is less than 19.000 MJ / kg, and the propane concentration is higher than this straight line.
  • Tables 20-23 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1123 and HFC-32.
  • FIG. 3 shows a ternary diagram of the ternary system of propane, HFO-1123 and HFC-32.
  • FIG. 3 shows a straight line connecting (23.3, 76.7, 0.0) and (25.6, 0.0, 74.4) for (propane, HFO-1123, HFC-32). ing.
  • Tables 24-26 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1123 and CO 2 .
  • FIG. 4 Also shown in FIG. 4 is a ternary diagram of the ternary system of propane, HFO-1123 and CO 2 .
  • FIG. 4 shows a straight line for (propane, HFO-1123, CO 2 ) connecting (23.3, 76.7, 0) and (41.0, 0, 59.0).
  • Tables 27-35 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1123 and CF 3 I.
  • FIG. 5 shows a ternary diagram of the ternary system of propane, HFO-1123 and CF 3 I.
  • FIG. 5 shows a straight line connecting (23.3, 76.7, 0.0) and (39.2, 0.0, 60.8) for (propane, HFO-1123, CF 3 I). ing.
  • the low propane concentration region including this straight line indicates the region where the combustion calorific value for the ternary system of propane, HFO-1123 and CF 3 I is less than 19.000 MJ/kg, and the region where the propane concentration is higher than this straight line.
  • Tables 36 to 57 show the composition, heat of combustion and GWP of four-component working media of propane, HFO-1123, HFO-1234yf and HFO-1234ze(E).
  • Tables 58 to 82 show the composition, heat of combustion and GWP for four-component working fluids of propane, HFO-1123, HFO-1234yf and HFC-32.
  • Tables 83-103 show the composition, heat of combustion and GWP for quaternary working fluids of propane, HFO-1123, HFO-1234yf and CO2 .
  • Tables 104-120 show the composition, heat of combustion and GWP for quaternary working fluids of propane, HFO-1123, HFO-1234yf and CF 3 I.
  • Tables 121 to 144 show the composition, heat of combustion and GWP for four-component working fluids of propane, HFO-1123, HFO-1234ze (E) and HFC-32.
  • Tables 145-165 show the composition, heat of combustion and GWP for propane, HFO-1123, HFO-1234ze(E) and CO2 quaternary working media.
  • Tables 166-181 show the composition, heat of combustion and GWP for propane, HFO-1123, HFO-1234ze(E) and CF 3 I quaternary working media.
  • Tables 182-191 show the composition, heat of combustion and GWP for quaternary working fluids of propane, HFO-1123, HFC-32 and CO2 .
  • Tables 192-202 show the composition, heat of combustion and GWP for the propane, HFO-1123, HFC-32 and CF 3 I quaternary working fluids.
  • Tables 203-212 show the composition, heat of combustion and GWP for the propane, HFO-1123, CO 2 and CF 3 I quaternary working fluids.
  • Table 213 shows the composition, heat of combustion and GWP for the propane and HFO-1132 (E) binary working fluid.
  • Tables 214-234 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1123 and HFO-1132(E).
  • FIG. 6 shows a ternary diagram of the ternary system of propane, HFO-1123 and HFO-1132(E).
  • propane, HFO-1123, HFO-1132 (E)) is a straight line connecting (23.3, 76.7, 0.0) and (9.1, 0.0, 90.9) It is shown.
  • the low propane concentration region including this straight line indicates the region where the combustion heat value for the three-component system of propane, HFO-1123 and HFO-1132 (E) is less than 19.000 MJ / kg, and the propane concentration is higher than this straight line.
  • Tables 235-257 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1132(E) and HFO-1234yf.
  • FIG. 7 shows a ternary diagram of the ternary system of propane, HFO-1132(E) and HFO-1234yf.
  • (propane, HFO-1132 (E), HFO-1234yf) is a straight line connecting (9.1, 90.9, 0.0) and (22.0, 0.0, 78.0) It is shown.
  • the low propane concentration region including this straight line indicates the region where the combustion calorific value for the three-component system of propane, HFO-1132 (E) and HFO-1234yf is less than 19.000 MJ / kg, and the propane concentration is higher than this straight line.
  • a high region indicates a region where the heat of combustion for the ternary system of propane, HFO-1132(E) and HFO-1234yf is 19.000 MJ/kg or more.
  • Tables 258-263 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1132(E) and HFO-1234ze(E). Also, FIG. 8 shows a ternary diagram of the ternary system of propane, HFO-1132(E) and HFO-1234ze(E). In FIG.
  • a straight line connecting The low propane concentration region including this straight line indicates the region where the combustion calorific value for the ternary system of propane, HFO-1132 (E) and HFO-1234ze (E) is less than 19.000 MJ / kg, and is lower than this straight line.
  • a region with a high propane concentration indicates a region where the combustion calorific value for the ternary system of propane, HFO-1132(E) and HFO-1234ze(E) is 19.000 MJ/kg or more. Further, if the straight line in FIG.
  • Tables 264-265 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1132(E) and HFC-32.
  • FIG. 9 shows a ternary diagram of the ternary system of propane, HFO-1132(E) and HFC-32.
  • (propane, HFO-1132 (E), HFC-32) is a straight line connecting (9.1, 90.9, 0.0) and (25.6, 0.0, 74.4) It is shown.
  • the low propane concentration region including this straight line indicates the region where the combustion heat quantity for the three-component system of propane, HFO-1132 (E) and HFC-32 is less than 19.000 MJ / kg, and the propane concentration is higher than this straight line.
  • Tables 266-267 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1132(E) and CO2 .
  • FIG. 10 Also shown in FIG. 10 is a ternary diagram of the ternary system of propane, HFO-1132(E) and CO 2 .
  • (propane, HFO-1132 (E), CO 2 ) has a straight line connecting (9.1, 90.9, 0.0) and (41.0, 0.0, 59.0) It is shown.
  • the low propane concentration region including this straight line indicates the region where the combustion calorific value for the ternary system of propane, HFO-1132 (E) and CO 2 is less than 19.000 MJ / kg, and the propane concentration is higher than this straight line.
  • Tables 268-274 show the composition, heat of combustion and GWP for ternary working fluids of propane, HFO-1132(E) and CF 3 I.
  • FIG. 11 shows a ternary diagram of the ternary system of propane, HFO-1132(E) and CF 3 I.
  • FIG. 11 shows that (propane, HFO-1132(E), CF 3 I) is a straight line connecting (9.1, 90.9, 0.0) and (39.2, 0.0, 60.8). It is shown.
  • the low propane concentration region including this straight line indicates the region where the combustion calorific value for the ternary system of propane, HFO-1132 (E) and CF 3 I is less than 19.000 MJ/kg, and the propane concentration is higher than this straight line.
  • Tables 275 to 296 show the composition, heat of combustion and GWP of four-component working media of propane, HFO-1132(E), HFO-1234yf and HFO-1234ze(E).
  • Tables 297 to 320 show the composition, heat of combustion and GWP of four-component working fluids of propane, HFO-1132(E), HFO-1234yf and HFC-32.
  • Tables 321-342 show the composition, heat of combustion and GWP for quaternary working media of propane, HFO-1132(E), HFO-1234yf and CO2 .
  • Tables 343-358 show the composition, heat of combustion and GWP for propane, HFO-1132(E), HFO-1234yf and CF 3 I quaternary working fluids.
  • Tables 359 to 382 show the composition, heat of combustion and GWP for four-component working media of propane, HFO-1132 (E), HFO-1234ze (E) and HFC-32.
  • Tables 383-403 show the composition, heat of combustion and GWP for quaternary working media of propane, HFO-1132(E), HFO-1234ze(E) and CO2 .
  • Tables 404-419 show the composition, heat of combustion and GWP for propane, HFO-1132(E), HFO-1234ze(E) and CF 3 I quaternary working fluids.
  • Tables 420-428 show the composition, heat of combustion and GWP for quaternary working fluids of propane, HFO-1132(E), HFC-32 and CO2 .
  • Tables 429-439 show the composition, heat of combustion and GWP for the propane, HFO-1132(E), HFC-32 and CF 3 I quaternary working fluids.
  • Tables 440-449 show the composition, heat of combustion and GWP for the propane, HFO-1132(E), CO 2 and CF 3 I quaternary working fluids.
  • Tables 450 to 458 show the composition, heat of combustion and GWP for four-component working media of propane, HFO-1123, HFO-1132(E) and HFO-1234yf.
  • Tables 459 to 467 show the composition, heat of combustion and GWP for four-component working media of propane, HFO-1123, HFO-1132 (E) and HFO-1234ze (E).
  • Tables 468 to 480 show the composition, heat of combustion and GWP for four-component working fluids of propane, HFO-1123, HFO-1132(E) and HFC-32.
  • Tables 481-492 show the composition, heat of combustion and GWP for quaternary working fluids of propane, HFO-1123, HFO-1132(E) and CO2 .
  • Tables 493-502 show the composition, heat of combustion and GWP for propane, HFO-1123, HFO-1132(E) and CF 3 I quaternary working fluids.
  • the cycle performance which is the property required when applying the working fluid to the heat cycle system, is the coefficient of performance (also referred to as “COP” in the present disclosure) and per unit volume (compressor suction volume) ability (also referred to as “CAP” in the present disclosure).
  • the capacity is refrigeration capacity.
  • each item is measured by the method described later, for example, using the reference refrigerating cycle with the temperature conditions shown below.
  • the discharge temperature, condensing pressure, evaporating pressure, and compression ratio are based on the HFC-32 values
  • the temperature glide, CAP, COP, and pressure loss are based on the R410A values. Evaluate by converting to a standard difference and relative value.
  • Temperature glide is an index that measures the difference in composition between the liquid phase and the gas phase in the working medium of the mixture. Temperature glide is defined as the property of a heat exchanger, eg, evaporating in an evaporator or condensing in a condenser, to have different starting and finishing temperatures. In azeotropic media, the temperature glide is zero, and in pseudo-azeotropes such as R410A the temperature gradient is very close to zero.
  • the inlet temperature in the evaporator will drop, which will increase the possibility of frost formation, which is a problem.
  • the working medium flowing through the heat exchanger and the heat source fluid such as water or air flow countercurrently, and this is the case in a stable operating state. Due to the small temperature difference of the heat source fluid, it is difficult to obtain an energy efficient thermal cycle system in the case of a non-azeotropic mixed medium with a large temperature glide. For this reason, a working medium with a suitable temperature glide is desired when using a mixture as a working medium.
  • non-azeotropic mixed media have the problem of causing composition changes when they are filled from a pressure vessel into a refrigerating and air-conditioning equipment. Furthermore, when refrigerant leaks from the refrigerating and air-conditioning equipment, it is highly possible that the refrigerant composition in the refrigerating and air-conditioning equipment will change, and it is difficult to restore the refrigerant composition to the initial state.
  • an azeotropic or pseudo-azeotropic mixed medium can avoid the above problems.
  • the compression ratio is represented by condensation pressure Pc (MPa)/evaporation pressure Pe (MPa) in the refrigeration cycle.
  • the compression ratio decreases as the condensing pressure in the refrigeration cycle decreases and as the evaporating pressure increases.
  • the smaller the compression ratio the higher the volumetric efficiency of the compressor, which increases the amount of refrigerant circulated and improves the equipment performance.
  • compression ratios are shown as relative compression ratios with respect to HFC-32.
  • the critical point is the end point of the saturated liquid line and the saturated vapor line on the high pressure and high temperature side.
  • the temperature at this point is the critical temperature.
  • Above the critical point there is neither evaporation nor liquefaction, the liquid and gas phases are indistinguishable, and there is no phase change.
  • a refrigeration cycle system will be described as an example of a heat cycle system.
  • a refrigeration cycle system is a system in which a working medium removes heat energy from a load fluid in an evaporator, thereby cooling the load fluid to a lower temperature.
  • FIG. 12 is a schematic configuration diagram showing an example of the refrigeration cycle system of the present disclosure.
  • the refrigeration cycle system 10 includes a compressor 11 that compresses a working medium vapor A into a high-temperature, high-pressure working medium vapor B, and a low-temperature, high-pressure operation by cooling and liquefying the working medium vapor B discharged from the compressor 11.
  • It is a system roughly configured comprising an evaporator 14 that produces a 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 C discharged from the condenser 12 is expanded by the expansion valve 13 to form a low-temperature, low-pressure working medium D (hereinafter referred to as "CD process”).
  • the working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to produce a high-temperature, low-pressure working medium vapor A. At this time, the load fluid E is cooled to become a load fluid E' and discharged from the evaporator 14 (hereinafter referred to as "DA process").
  • the refrigeration cycle system 10 is a cycle system consisting of adiabatic/isentropic change, isenthalpic change, and isobaric change. If the state change of the working medium is described on the pressure-enthalpy line (curve) diagram shown in FIG. 13, it can be represented as a trapezoid with A, B, C, and D as vertices.
  • the AB process is a process in which the compressor 11 performs adiabatic compression to convert the low-temperature, low-pressure working medium vapor A into the high-temperature, high-pressure working medium vapor B, and is indicated by line AB in FIG.
  • the working medium vapor A is introduced into the compressor 11 in a superheated state, and the resulting working medium vapor B is also in a superheated state.
  • the compressor suction saturated gas density is the density ( ⁇ s) in the state A in FIG.
  • the compressor discharge gas temperature (discharge temperature) is the temperature (Tx) in state B in FIG. 13, which is the highest temperature in the refrigeration cycle.
  • the compressor discharge pressure (discharge pressure) is the pressure (Px) in state B in FIG. 13, which is the maximum pressure in the refrigeration cycle. Since the BC process is isobaric cooling, the discharge pressure shows the same value as the condensation pressure. Therefore, in FIG. 13, the condensing pressure is indicated as Px for convenience.
  • the BC process is a process in which isobaric cooling is performed in the condenser 12 to convert the high-temperature, high-pressure working medium vapor B into the low-temperature, high-pressure working medium C, and is indicated by the BC line in FIG.
  • the pressure at this time is the condensation pressure.
  • the intersection point T1 on the high enthalpy side is the condensation temperature
  • the intersection point T2 on the low enthalpy side is the condensation boiling temperature.
  • the temperature gradient when the working medium is a non-azeotropic mixed medium is shown as the difference between T1 and T2.
  • the CD process is a process in which the expansion valve 13 performs isenthalpic expansion to convert the low-temperature, high-pressure working medium C into a low-temperature, low-pressure working medium D, and is indicated by line CD in FIG. If the temperature of the low-temperature, high-pressure working medium C is denoted by T3, T2-T3 is the degree of supercooling (SC) of the working medium in the cycles (i) to (iv).
  • the DA process is a process in which isobaric heating is performed in the evaporator 14 and the low-temperature, low-pressure working medium D is returned to the high-temperature, low-pressure working medium vapor A, which is indicated by the DA line in FIG.
  • the pressure at this time is the evaporation pressure.
  • T6 on the high enthalpy side is the evaporation temperature.
  • T7-T6 is the superheat (SH) of the working medium in the cycles (i) to (iv).
  • T4 indicates the temperature of the working medium D.
  • the CAP and COP of the working medium are in each state of the working medium A (low temperature and low pressure after evaporation), B (high temperature and high pressure after compression), C (low temperature and high pressure after condensation), and D (low temperature and low pressure after expansion).
  • A low temperature and low pressure after evaporation
  • B high temperature and high pressure after compression
  • C low temperature and high pressure after condensation
  • D low temperature and low pressure after expansion
  • the working medium vapor B′ after the AB step is expressed by the following equation using hA, hB, ⁇ .
  • hB' hA+(hB-hA)/ ⁇
  • thermodynamic properties required to calculate the cycle performance of the working medium are found in the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (REFPROP 10.0) and the principle of corresponding states. based on the generalized equation of state (Soave - Redlich-Kwong equation) and thermodynamic equations.
  • CAP (hA ⁇ hD) ⁇ s (11)
  • Q qmr(hA ⁇ hD) (13)
  • P qmr(hB ⁇ hA) (14)
  • COP and P are given by the following equations.
  • P qmr(hB'-hA) (16)
  • the change in state of the working medium can be represented as shown in FIG. 14 by describing it on the temperature-entropy diagram.
  • Pressure loss increases the condensation pressure in the refrigeration cycle and decreases the evaporation pressure, which is a factor that lowers the performance.
  • the pressure loss is caused by the friction in the flow in the condenser, evaporator, and connecting pipes in the refrigeration cycle, and the coefficient of friction f (-), length L (m), diameter d (m), evaporator capacity Using ⁇ 0 (kW), latent heat of vaporization W r (kJ/kg), and specific volume ⁇ s (m 3 /kg), it is expressed by the following equation.
  • the values in parentheses in the first half of the formula are determined by the specifications of the dimensions and performance of the parts that make up the refrigeration cycle.
  • the values in the latter half of the parentheses are determined by the thermal properties of the refrigerant, the values in the latter half of the parentheses should be taken into consideration when the device specifications and device performance are the same. Therefore, the pressure loss decreases as the specific volume of the refrigerant decreases and the latent heat of vaporization increases, and increases as the specific volume of the refrigerant increases and the latent heat of vaporization decreases. The smaller the pressure loss, the smaller the work loss, so the equipment performance is improved. In the present disclosure, pressure loss is shown in parentheses in the latter half of the formula, and is shown as relative pressure loss with respect to R410A.
  • the working medium of the present disclosure is a refrigerant for refrigerators, a refrigerant for air conditioners, a working medium for power generation systems (waste heat recovery power generation, etc.), a working medium for latent heat transport devices (heat pipes, etc.), a heat cycle such as a secondary cooling medium It can be suitably used as a working medium for systems.
  • composition for heat cycle system When applied to a heat cycle system, the working medium of the present disclosure can be used as a composition for a heat cycle system, usually by being mixed with a lubricating oil.
  • a composition for a thermal cycle system of the present disclosure includes a working medium of the present disclosure and lubricating oil.
  • the composition for a thermal cycle system of the present disclosure may further contain known additives such as stabilizers and leak detection substances in addition to the working medium and lubricating oil of the present disclosure.
  • the type of lubricating oil is not particularly limited, but it is preferable to select a lubricating oil that does not greatly change the solubility of propane, HFO-1123, and the third component contained in the working medium. Specifically, when the working medium contacts the lubricating oil and some of the components contained in the working medium dissolve in the lubricating oil, each component (propane, HFO- 1123, third component, etc.) is preferably within ⁇ 5% by mass of the content of each component in the working medium.
  • Lubricating oils include known lubricating oils used in thermal cycle systems.
  • the lubricating oil is contained in the heat cycle system composition together with the working medium, circulates in the heat cycle system, and particularly functions as a lubricating oil in the compressor in the heat cycle system.
  • the lubricating oil has sufficient compatibility with the working medium under low-temperature conditions while ensuring lubricity and airtightness of the compressor.
  • the kinematic viscosity of the lubricating oil at 40° C. is preferably 1 to 750 mm 2 /sec, more preferably 1 to 400 mm 2 /sec.
  • the kinematic viscosity at 100° C. is preferably 1 to 100 mm 2 /sec, more preferably 1 to 50 mm 2 /sec.
  • lubricating oils examples include ester-based lubricating oils, ether-based lubricating oils, fluorine-based lubricating oils, hydrocarbon-based synthetic oils, and mineral oils.
  • Ester-based lubricating oil is an oily ester compound with an ester bond in the molecule.
  • Ester-based lubricating oils include, for example, dibasic acid esters, polyol esters, complex esters, and polyol carbonates.
  • the dibasic acid ester includes, for example, a dibasic acid having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and a linear or branched alkyl group.
  • monohydric alcohol having 1 to 15 carbon atoms methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, 2-ethylhexanol , isodecyl alcohol, 3-ethyl-3-hexanol, etc.) are preferred.
  • ditridecyl glutarate di(2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, and di(3-ethyl-3-hexyl) sebacate.
  • a polyol ester is an ester synthesized from a polyol and a fatty acid (monohydric aliphatic carboxylic acid).
  • Polyol esters include diols (ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5-pentadiol, neopentyl glycol, 1,7-heptanediol, , 1,12-dodecanediol, etc.) or a polyol having 3 to 20 hydroxyl groups (trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, glycerin, sorbitol, sorbitan, sorbitol glycerin condensate, etc.) and a carbon number 6 to 20 fatty acids (straight or branched fatty acids such as hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, pelargonic acid, decan
  • Polyol esters are esters of hindered alcohols (e.g., neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, etc.), specifically trimethylolpropane tripelargonate, pentaerythritol 2 - Ethylhexanoate or pentaerythritol tetrapelargonate is more preferred.
  • hindered alcohols e.g., neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, etc.
  • trimethylolpropane tripelargonate pentaerythritol 2 - Ethylhexanoate or pentaerythritol tetrapelargonate is more preferred.
  • a complex ester is a combination (complex) of several esters.
  • Complex esters are mixtures of esters synthesized from at least one of fatty acids and dibasic acids and at least one of monohydric alcohols and polyols. Examples of fatty acids, dibasic acids, monohydric alcohols and polyols include the same as those exemplified for the above dibasic acid esters and polyol esters.
  • a polyol carbonate is an ester of carbonic acid and a polyol, or a ring-opening polymer of a cyclic alkylene carbonate.
  • Examples of the polyol include the same ones as those mentioned in the above polyol ester.
  • Ether-based lubricating oil is an oily ether compound with an ether bond in the molecule.
  • Ether-based lubricating oils include, for example, polyalkylene glycols and polyvinyl ethers.
  • polyalkylene glycols examples include polyalkylene polyols and compounds obtained by alkyl-etherifying some or all of the hydroxyl groups of polyalkylene polyols.
  • Polyalkylene glycol can be obtained, for example, by polymerizing an alkylene oxide having 2 to 4 carbon atoms (eg, ethylene oxide, propylene oxide, etc.) using water, an alkanemonool, a diol, or a polyol as an initiator.
  • the number of oxyalkylene units in one polyalkylene glycol molecule may be one, or two or more.
  • the polyalkylene glycol is preferably a compound containing at least oxypropylene units in one molecule, more preferably polypropylene glycol or polypropylene glycol dialkyl ether.
  • a polyvinyl ether is a polymer having at least a structural unit derived from a vinyl ether monomer.
  • polyvinyl ether examples include polymers of vinyl ether monomers, copolymers of vinyl ether monomers and hydrocarbon monomers having unsaturated double bonds, and copolymers of vinyl ether monomers and vinyl ether monomers having a polyalkylene oxide chain. are mentioned. Ethylene oxide or propylene oxide is preferred as the alkylene oxide contained in the polyalkylene oxide chain.
  • the polymer may be either a block copolymer or a random copolymer.
  • the vinyl ether monomer is an alkyl vinyl ether.
  • the alkyl group contained in the alkyl vinyl ether is preferably an alkyl group having 6 or less carbon atoms.
  • the vinyl ether monomers may be used singly or in combination of two or more.
  • Hydrocarbon monomers having unsaturated double bonds include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, ⁇ -methylstyrene, and various alkyl-substituted styrenes. is mentioned.
  • the hydrocarbon monomers having unsaturated double bonds may be used singly or in combination of two or more.
  • a fluorine-based lubricating oil is an oily compound that has a fluorine atom in its molecule.
  • fluorine-based lubricating oils mineral oils or hydrocarbon-based synthetic oils (e.g., poly- ⁇ -olefins, alkylbenzenes, alkylnaphthalenes, etc.) described below in which hydrogen atoms are substituted with fluorine atoms, perfluoropolyether oils, and fluorinated A silicone oil is mentioned.
  • mineral oils or hydrocarbon-based synthetic oils e.g., poly- ⁇ -olefins, alkylbenzenes, alkylnaphthalenes, etc.
  • Mineral oil is a lubricating oil fraction obtained by atmospheric distillation or vacuum distillation of crude oil, and is subjected to refining treatment (e.g., solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation Refining, white clay treatment, etc.) are combined as appropriate.
  • Mineral oils include, for example, paraffinic mineral oils and naphthenic mineral oils.
  • a hydrocarbon-based synthetic oil is an oily synthetic compound whose molecules are composed only of carbon and hydrogen atoms.
  • Hydrocarbon synthetic oils include, for example, poly ⁇ -olefins, alkylbenzenes, and alkylnaphthalenes.
  • Lubricating oils may be used singly or in combination of two or more.
  • the lubricating oil is preferably one or both of a polyol ester and a polyalkylene glycol from the viewpoint of compatibility with the working medium, and more preferably a polyalkylene glycol from the viewpoint that a significant antioxidant effect can be obtained by the stabilizer.
  • the content of the lubricating oil in the composition for a heat cycle system may be within a range that does not significantly reduce the effects of the present disclosure, and is preferably 10 to 100 parts by mass, preferably 20 to 50 parts by mass, relative to 100 parts by mass of the working medium. part is more preferred.
  • Stabilizers are ingredients that improve the stability of the working medium against heat and oxidation. Stabilizers include, for example, oxidation resistance improvers, heat resistance improvers, and metal deactivators.
  • the oxidation resistance improver is a stabilizer that stabilizes the working medium by suppressing decomposition of the working medium mainly by oxygen under conditions where the working medium is repeatedly compressed and heated in a thermal cycle system.
  • a heat resistance improver is a stabilizer that stabilizes the working medium by suppressing decomposition of the working medium mainly due to heat under conditions where the working medium is repeatedly compressed and heated in a thermal cycle system.
  • oxidation resistance improvers and heat resistance improvers examples include N,N'-diphenylphenylenediamine, p-octyldiphenylamine, p,p'-dioctyldiphenylamine, N-phenyl-1-naphthylamine, and N-phenyl-2.
  • oxidation resistance improver and the heat resistance improver may be used alone, or two or more thereof may be used in combination.
  • the metal deactivator is used for the purpose of preventing the metal materials in the thermal cycle system from adversely affecting the working medium and lubricating oil, or for the purpose of protecting the metal materials from the working medium and lubricating oil.
  • Specific examples include agents that form a film on the surface of the metal material.
  • metal deactivators examples include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimercaptothiadiazole, salicyridin-propylenediamine, pyrazole, benzotriazole, tolyltriazole, 2-methylbenzimidazole, 3,5 organic acids or their esters; primary, secondary or tertiary aliphatic amines; amine salts of organic or inorganic acids; heterocyclic nitrogen-containing compounds, alkyl acids. Amine salts of phosphates or derivatives thereof may be mentioned.
  • the content of the stabilizer with respect to the total amount (100% by mass) of the working medium is not particularly limited as long as it does not significantly reduce the effects of the present disclosure, but is preferably 5% by mass or less. % by mass or less is more preferable.
  • a leak detection substance is a substance added for the purpose of facilitating detection by odor, color, etc. when a working medium or the like leaks from a thermal cycle system.
  • Leak detection materials include, for example, ultraviolet fluorescent dyes, odorous gases, and odor masking agents.
  • ultraviolet fluorescent dyes include, for example, US Pat. known ultraviolet fluorescent dyes such as those described above.
  • Odor masking agents refer to substances added for the purpose of improving the fragrance.
  • Examples of the odor masking agent include known perfumes such as those described in JP-A-2008-500437 and JP-A-2008-531836.
  • solubilizer that improves the solubility of the leak detection substance in the working medium may be used.
  • solubilizers include those described in JP-T-2007-511645, JP-T-2008-500437, and JP-T-2008-531836.
  • the content of the leak detection substance relative to the total amount (100% by mass) of the working medium in the composition for a heat cycle system is not particularly limited as long as it does not significantly reduce the effects of the present disclosure, but is preferably 2% by mass or less, 0.5% by mass or less is more preferable.
  • the heat cycle system of the present disclosure is a heat cycle system using the working fluid of the present disclosure or the composition for heat cycle system of the present disclosure.
  • the heat cycle system of the present disclosure may be a heat pump system that uses hot heat obtained from a condenser, or a refrigeration cycle system that uses cold heat obtained from an evaporator.
  • the heat cycle system of the present disclosure include freezing/refrigerating equipment, air conditioning equipment, power generation systems, heat transport devices, and secondary coolers. Above all, the heat cycle system of the present disclosure can stably and safely exhibit heat cycle performance even in a higher temperature operating environment, so it is preferably used as an air conditioner that is often installed outdoors. Also, the heat cycle system of the present disclosure is preferably used as a freezer/refrigerator.
  • air conditioning equipment include room air conditioners, package air conditioners (package air conditioners for stores, package air conditioners for buildings, package air conditioners for facilities, etc.), gas engine heat pumps, air conditioners for trains, and air conditioners for automobiles.
  • freezing/refrigerating equipment include showcases (built-in showcases, separate showcases, etc.), commercial freezers/refrigerators, vending machines, and ice machines.
  • a power generation system based on the Rankine cycle system is preferable.
  • the working medium is heated by geothermal energy, solar heat, waste heat in a medium to high temperature range of 50 ° C to 200 ° C in an evaporator, etc., and the working medium becomes steam in a high temperature and high pressure state. is adiabatically expanded by an expander, and the work generated by the adiabatic expansion drives a generator to generate power.
  • a latent heat transport device is preferable as a heat transport device.
  • latent heat transport devices include heat pipes and two-phase closed thermosiphon devices that transport latent heat using phenomena such as evaporation, boiling, and condensation of a working medium enclosed in the device.
  • a heat pipe is applied to a relatively small cooling device such as a cooling device for a semiconductor device or a heat-generating part of an electronic device.
  • the two-phase closed thermosiphon device does not require a wig and has a simple structure, so it is widely used for gas-to-gas heat exchangers, promoting snow melting on roads, and preventing freezing.
  • a method of preserving the composition of the present disclosure includes propane, at least one of HFO-1123 and HFO-1132(E), HFO-1234yf, HFO-1234ze(E), HFC-32, CO 2 , CF 3 I, at least selected from the group consisting of HCFO-1224yd(Z), HCFO-1224yd(E), HFO-1233zd(E), HFO-1336mzz(E), HFO-1225ye(Z), and HFO-1225ye(E)
  • compositions are the same as the preferred aspects of the working medium described above.
  • the method of filling the container with the composition is not particularly limited, and generally known methods can be used.
  • the mixed composition may be introduced into a container.
  • each component contained in the composition may be individually introduced into a container and mixed in the container.
  • only some of the components contained in the composition may be mixed, the mixed components and the remaining components may be separately introduced into a container, and the components may be mixed in the container.
  • Methods of making the composition liquid include a method of cooling the composition and a method of pressurizing the composition.
  • "filling a liquid composition into a container” means not only the mode of introducing the liquid composition into the container, but also each component contained in the composition (however, even if some components are mixed in advance) (good) is separately introduced into a container to obtain a liquid composition in the container.
  • the container for storing the composition is not particularly limited as long as it can store the composition in a gas-liquid state under internal pressure.
  • containers include pressure-resistant containers such as storage tanks that are fixed storage containers, filled cylinders used for transportation, and secondary filled cylinders (service cans).
  • the container may be a simple container for temporary storage.
  • the material of the container is not particularly limited, and examples include glass, carbon steel, manganese steel, chrome molybdenum steel, stainless steel, and aluminum alloy. Also, the inner wall of the container may be lined with resin or the like.
  • the concentration of oxygen in the gas phase at 25° C. is kept below 3000 ppm by volume. If the oxygen concentration in the gas phase is 3000 ppm by volume or less, the polymerization reaction of the composition can be suppressed.
  • the storage method of the present disclosure can suppress polymerization reactions and the like even when the oxygen concentration is as high as 3000 ppm by volume. The reason for this is presumed as follows. Polymerization of HFO-1123 with oxygen proceeds through by-products such as peroxides generated by the reaction of oxygen with unsaturated bonds, and radical active species act as starting points for polymerization, and HFO-1123 undergoes a chain reaction. It is thought that it progresses by doing.
  • the polymerization chain reaction is terminated. Since the composition in the storage method of the present disclosure contains propane together with HFO-1123, it is thought that even if the oxygen concentration is as high as 3000 ppm by volume, the polymerization reaction and the like can be suppressed.
  • the concentration of oxygen in the gas phase at 25 ° C. is preferably 1 to 3000 volume ppm, more preferably 3 to 1000 volume ppm, even more preferably 3 to 300 volume ppm, 3 to 50 volume ppm ppm is particularly preferred.
  • Productivity improves that the concentration of oxygen is 1 volume ppm or more.
  • the concentration of oxygen in the gas phase can be measured by gas chromatography.
  • the method for storing the composition of the present disclosure it is preferable to fill the container with the liquid composition after degassing the inside of the container.
  • the method for degassing the inside of the container is not particularly limited, and a commonly known method can be used.
  • Oxygen in the container is removed by degassing the container.
  • a container having a reduced concentration of oxygen is filled with a composition in liquid form, the space within the container is quickly saturated with vapor from the liquid. Then, the concentration of oxygen in the gas phase filled with saturated steam is 3000 ppm by volume or less.
  • non-condensable gases such as nitrogen are also removed together with oxygen. ppm) or less.
  • the pressure and temperature during storage must be maintained below the prescribed level according to the design pressure and temperature of the container.
  • the temperature during storage is preferably 60° C. or lower, more preferably 50° C. or lower, more preferably 40° C. or lower, and even more preferably 30° C. or lower, from the viewpoint of safety.
  • the lower limit of the temperature during storage is not particularly limited, but when the temperature is below the boiling point of the composition, the inside of the container becomes negative pressure, and air, moisture, etc. may be mixed, so the temperature during storage is - 30° C. or higher is preferred, ⁇ 15° C. or higher is more preferred, and 0° C. or higher is even more preferred.
  • composition can be stored, for example, in a well-ventilated environment without direct sunlight. You may preserve
  • the quality can be maintained so that the composition satisfies one or more of the following (1) to (4) during or after storage. Two or more of the following (1) to (4) are preferably satisfied, three or more are more preferable, and all of them are most preferable.
  • Moisture content is 500 ppm or less.
  • Evaporation residue is 100 ppm or less.
  • Acid content is 1 ppm or less. (4) Colorless and transparent in hue.
  • the polymerization reaction and the like of the composition filled in the container in a gas-liquid state is suppressed, so the purity and refrigerant performance of the composition can be maintained.
  • the composition since no solid polymerized product is generated in the container, there is no risk of blockage of valves or contamination of the refrigerant system.
  • the composition can be stored at low cost.
  • the composition can be stably stored for a long period of time.
  • the composition may be stored in the container for 1 week or more, 1 month or more, 3 months or more, 6 months or more, or 1 year or more.
  • One aspect of the storage container of the composition of the present disclosure is propane, at least one of HFO-1123 and HFO-1132(E), and HFO-1234yf and HFO-1234ze in a state where a gas phase and a liquid phase coexist.
  • kg, and the concentration of oxygen in the gas phase at a temperature of 25° C. is 3000 ppm by volume or less.
  • the concentration of oxygen in the gas phase at 25 ° C. is preferably 1 to 3000 volume ppm, more preferably 3 to 1000 volume ppm, even more preferably 3 to 300 volume ppm, 3 to 50 volume ppm ppm is particularly preferred.
  • Productivity improves that the concentration of oxygen is 1 volume ppm or more.
  • Preferred aspects of the components contained in the composition are the same as preferred aspects of the components contained in the working medium.
  • Preferred aspects of the storage container are the same as the preferred aspects of the container used in the storage method described above.
  • Another aspect of the storage container of the composition of the present disclosure is propane, at least one of HFO-1123 and HFO-1132(E), HFO-1234yf, HFO-1234ze(E), HFC-32, from CO 2 , CF 3 I, HCFO-1224yd(Z), HCFO-1224yd(E), HFO-1233zd(E), HFO-1336mzz(E), HFO-1225ye(Z), and HFO-1225ye(E)
  • the water content is preferably 100 mass ppm or less, more preferably 50 ppm or less, relative to the total amount of the composition.
  • the lower limit of water content is not particularly limited.
  • the water content is measured by Karl Fischer coulometric titration by sending the sample to the Karl Fischer reagent.
  • Preferred embodiments of the components other than water contained in the composition are the same as the preferred embodiments of the components contained in the working medium.
  • Preferred aspects of the storage container are the same as the preferred aspects of the container used in the storage method described above.
  • the water content during storage is 500 ppm or less, quality deterioration due to storage of the composition is suppressed.
  • (Appendix 5) The working medium according to appendix 1, wherein the propane content is 1.0% by mass or more relative to the total amount of the working medium.
  • (Appendix 6) containing the difluoromethane, The working medium according to appendix 1, wherein the content of the difluoromethane is 22.0% by mass or less with respect to the total amount of the working medium.
  • (Appendix 7) containing said CO2 , The working medium according to appendix 1, wherein the CO 2 content is 15.0% by mass or less with respect to the total amount of the working medium.
  • the mass ratio of the propane content to the 1,1,2-trifluoroethylene content is 5:95 to 29:71
  • the content of the 2,3,3,3-tetrafluoro-1-propene is the propane, the 1,1,2-trifluoroethylene, and the 2,3,3,3-tetrafluoro-1-propene 10.5 to 25.0% by mass with respect to the total content of
  • the total content of propane, 1,1,2-trifluoroethylene, and 2,3,3,3-tetrafluoro-1-propene is 80% by mass or more relative to the total amount of the working medium.
  • (Appendix 9) containing the propane, the 1,1,2-trifluoroethylene, and the difluoromethane;
  • the mass ratio of the propane content to the 1,1,2-trifluoroethylene content is 18:82 to 22:78,
  • the content of the difluoromethane is 5.5 to 19.5% by mass with respect to the total content of the propane, the 1,1,2-trifluoroethylene, and the difluoromethane. working medium.
  • the mass ratio of the propane content to the 1,1,2-trifluoroethylene content is 18.9:81.1 to 23:77,
  • the content of the difluoromethane is 12.5 to 21.5% by mass with respect to the total content of the propane, the 1,1,2-trifluoroethylene, and the difluoromethane. working medium.
  • (Appendix 12) containing the propane, the 1,1,2-trifluoroethylene, and the (E)-1,3,3,3-tetrafluoropropene The propane content is 25.0% by mass or less with respect to the total content of the propane and the 1,1,2-trifluoroethylene, The content of the (E)-1,3,3,3-tetrafluoropropene is the propane, the 1,1,2-trifluoroethylene, and the (E)-1,3,3,3-tetrafluoropropene. 11.0 to 25.0% by mass with respect to the total content of fluoropropene, The working medium according to appendix 1, wherein the total content is 78.5% by mass or more with respect to the total amount of the working medium.
  • (Appendix 13) containing the propane, the 1,1,2-trifluoroethylene, and the (E)-1,3,3,3-tetrafluoropropene The propane content is 10.0% by mass or less with respect to the total content of the propane and the 1,1,2-trifluoroethylene,
  • the content of the (E)-1,3,3,3-tetrafluoropropene is the propane, the 1,1,2-trifluoroethylene, and the (E)-1,3,3,3-tetrafluoropropene.
  • (Appendix 14) containing the propane, the 1,1,2-trifluoroethylene, and the (E)-1,3,3,3-tetrafluoropropene The propane content is 20.0% by mass or less with respect to the total content of the propane and the 1,1,2-trifluoroethylene, The content of the (E)-1,3,3,3-tetrafluoropropene is the propane, the 1,1,2-trifluoroethylene, and the (E)-1,3,3,3-tetrafluoropropene.
  • the propane content with respect to the total content of the propane, the 1,1,2-trifluoroethylene, and the CF 3 I is X 2 % by mass, and the CF 3 I content with respect to the total content is Y 2
  • the X 2 and the Y 2 satisfy the following formula (2A)
  • the content of the difluoromethane with respect to the total content of the propane, the 1,1,2-trifluoroethylene, the 2,3,3,3-tetrafluoro-1-propene, and the difluoromethane is A% by mass
  • the content of 2,3,3,3-tetrafluoro-1-propene with respect to the total content is B% by mass
  • the content of propane with respect to the total content is C% by mass
  • the content of 1 with respect to the total content where the content of 1,2-trifluoroethylene is D mass%
  • the A, the B, the C, and the D satisfy the following formulas (3A) to (3D).
  • (3D) (Appendix 22) containing the propane, the 1,1,2-trifluoroethylene, the (E)-1,3,3,3-tetrafluoropropene, and the difluoromethane;
  • the content of the difluoromethane with respect to the total content of the propane, the 1,1,2-trifluoroethylene, the (E)-1,3,3,3-tetrafluoropropene, and the difluoromethane is E% by mass.
  • the content of (E)-1,3,3,3-tetrafluoropropene with respect to the total content is F mass%
  • the content of propane with respect to the total content is G mass%
  • the total content is
  • the content of the 1,1,2-trifluoroethylene is H mass%
  • the E, the F, the G, and the H satisfy the following formulas (4A) to (4D).
  • (4D) (Appendix 23) containing the propane, the 1,1,2-trifluoroethylene, the CO2 , and the difluoromethane;
  • the content of the difluoromethane with respect to the total content of the propane, the 1,1,2-trifluoroethylene, the CO 2 and the difluoromethane is J% by mass, and the content of the CO 2 with respect to the total content is K% by mass, L% by mass for the content of propane relative to the total content, and M% by mass for the content of 1,1,2-trifluoroethylene relative to the total content.
  • Appendix 26 A composition for a thermal cycle system, comprising the working medium according to any one of appendices 1 to 25, and lubricating oil.
  • Appendix 27 A heat cycle system using the working medium according to any one of appendices 1 to 25.
  • Discharge Temperature (Difference) of the working medium (Relative) Condensing Pressure, (Relative) Evaporating Pressure, CAP (Relative) Capacity and COP (performance A coefficient (Relative Coefficient of Performance) was obtained by the method described above. Also, the temperature glide (Difference) was obtained by the following method. The results obtained are shown in Tables 503-713. "-" in the table indicates that the evaluation was not performed. In the table, the unit of discharge temperature (Difference) and temperature glide (Difference) is "°C".
  • temperature glide was calculated as the difference between the temperature at which evaporation begins and the temperature at which evaporation completes in the evaporator. This disclosure shows the difference from R410A.
  • CAP which is the refrigerating capacity per unit volume of the evaporator
  • CAP which is the refrigerating capacity per unit volume
  • the present disclosure provides relative coefficients of performance for R410A.
  • -COP- COP is a value obtained by dividing the output Q (kW) by the power P (kW) consumed to obtain the output Q (kW), and corresponds to energy consumption efficiency. The higher the COP value, the greater output can be obtained with less input.
  • the present disclosure provides relative coefficients of performance for R410A.

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WO2026079472A1 (ja) * 2024-10-09 2026-04-16 ダイキン工業株式会社 冷媒を含む組成物、その使用、並びにそれを有する冷凍機及びその冷凍機の運転方法

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WO2026079472A1 (ja) * 2024-10-09 2026-04-16 ダイキン工業株式会社 冷媒を含む組成物、その使用、並びにそれを有する冷凍機及びその冷凍機の運転方法

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