WO2022191205A1 - 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 - Google Patents

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 Download PDF

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Publication number
WO2022191205A1
WO2022191205A1 PCT/JP2022/010086 JP2022010086W WO2022191205A1 WO 2022191205 A1 WO2022191205 A1 WO 2022191205A1 JP 2022010086 W JP2022010086 W JP 2022010086W WO 2022191205 A1 WO2022191205 A1 WO 2022191205A1
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WIPO (PCT)
Prior art keywords
point
refrigerant
hfo
mass
r1234ze
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PCT/JP2022/010086
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English (en)
French (fr)
Japanese (ja)
Inventor
充司 板野
瞬 大久保
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to EP22767159.1A priority Critical patent/EP4306871B1/en
Priority to CN202280020110.7A priority patent/CN116997632A/zh
Publication of WO2022191205A1 publication Critical patent/WO2022191205A1/ja
Priority to US18/243,359 priority patent/US12540264B2/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
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K2205/40—Replacement mixtures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—Component parts or details not otherwise provided for in this subclass
    • F25B2400/12—Inflammable refrigerants
    • F25B2400/121—Inflammable refrigerants using R1234

Definitions

  • the present disclosure relates to a composition containing a refrigerant, its use, a refrigerator having the same, and a method of operating the refrigerator.
  • Patent Document 1 As a working medium for heat cycle that can be substituted for R410A, a working medium for heat cycle containing trifluoroethylene (HFO-1123) and 1,2-difluoroethylene (HFO-1132) has been proposed (Patent Document 1). .
  • the present disclosure aims to provide a novel low GWP mixed refrigerant.
  • Section 1 A composition comprising a refrigerant, the refrigerant is trans-1,2-difluoroethylene (HFO-1132(E)), 1,3,3,3-tetrafluoropropene (R1234ze) and 2,3,3,3-tetrafluoro-1-propene A composition comprising (R1234yf). Section 2.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segment enclosed by the line segments AB, BF, FE and EA connecting the four points of Line segments AB, BF and EA are straight lines, and a point on line segment FE is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748), Item 1.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segments enclosed by the line segments CD, DF, FE and EC connecting the four points of Line segments DF and EC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment FE The upper point is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748), Item 1.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments AB, BH, HG and GA connecting the four points of Line segments AB, BH, and GA are straight lines,
  • a point on the line segment HG is represented by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242)
  • Item 1 The composition according to item 1.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments AB, BJ, JI and IA connecting the four points of Line segments AB, BJ, and IA are straight lines, and a point on line segment JI is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76), Item 1.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H'(31.3, 1.0, 67.7) and Point G'(44.1, 54.9, 1.0) is within or on the line segment enclosed by the line segments AB, BH', H'G' and G'A connecting the four points of Line segments AB, BH', and G'A are straight lines, and a point on line segment H'G' is (x, -0.08728x2+10.791x-251.26, 0.08728x2 -11.791x+351.26) represented, Item 1.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments CD, DH, HG and GC connecting the four points of Line segments DH and GC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment HG
  • the point above is denoted by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242 ), Item 1.
  • composition according to item 1. Item 8. In the refrigerant, the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments CD, DJ, JI and IC connecting the four points of Line segments DJ and IC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment JI The point above is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76), Item 1.
  • composition according to item 1. Item 9.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7)
  • the line segment DH' is a straight line
  • a point on line segment PD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54)
  • a point on line segment H'P is represented by (x, -0.08728x 2 +10.791x-251.26, 0.08728x 2 -11.791x+351.26), Item 1.
  • composition according to item 1 Item 10.
  • Item 10. The composition according to any one of Items 1 to 9, further comprising refrigerating machine oil.
  • Item 11. The composition according to any one of Items 1 to 10, which is used as a substitute refrigerant for R404A.
  • Item 12. A refrigerator comprising the composition according to any one of Items 1 to 10 as a working fluid.
  • Item 13. A method for operating a refrigerator, A method comprising circulating the composition according to any one of Items 1 to 10 as a working fluid in a refrigerator.
  • Item 14. Use of the composition according to any one of items 1 to 10 as a substitute refrigerant for R410A.
  • the refrigerant of the present disclosure has a low GWP.
  • FIG. 1 is a three-component composition diagram in which the sum of HFO-1132(E), R1234ze and R1234y is 100% by mass, and points A to F are indicated.
  • the term "refrigerant” includes at least a compound with a refrigerant number (ASHRAE number) starting with R, which indicates the type of refrigerant, defined by ISO817 (International Organization for Standardization), and furthermore, the refrigerant number is Even if they are not attached yet, those having properties as refrigerants equivalent to those are included.
  • Refrigerants are roughly classified into “fluorocarbon compounds” and “non-fluorocarbon compounds” in terms of compound structure.
  • “Fluorocarbon compounds” include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs).
  • composition containing a refrigerant includes (1) refrigerant itself (including a mixture of refrigerants) and (2) other components, which are mixed with at least refrigerating machine oil. and (3) a working fluid for a refrigerator containing a refrigerator oil.
  • the composition of (2) is referred to as a "refrigerant composition” to distinguish it from the refrigerant itself (including mixtures of refrigerants).
  • the working fluid for a refrigerator (3) is described as a "refrigerating machine oil-containing working fluid” to distinguish it from the "refrigerant composition”.
  • the second refrigerant can be used only by changing a small number of parts (at least one of refrigerating machine oil, gaskets, packing, expansion valves, dryers and other parts) and adjusting the equipment as necessary. means that it can operate under optimum conditions. In other words, this type refers to operating the same equipment by "alternating" the refrigerant.
  • equipment designed to operate with a second refrigerant may be used with a second refrigerant installed for the same use as the existing use of the first refrigerant.
  • alternate This typology refers to providing the same application by "replacement" of the refrigerant.
  • a refrigerator refers to a general device that removes heat from an object or space to make it lower in temperature than the surrounding outside air and maintain this low temperature.
  • a refrigerator is a conversion device that converts energy by obtaining energy from the outside and performing work in order to move heat from a low temperature area to a high temperature area.
  • the refrigerant is "WCF slightly flammable” means that the most flammable composition (Worst case of formulation for flammability; WCF) according to the US ANSI/ASHRAE34-2013 standard has a burning velocity of 10 cm / s or less.
  • the refrigerant is ASHRAE slightly flammable (WCF & WCFF slightly flammable) means that the WCF has a burning rate of 10 cm / s or less, and WCF is used for storage, transportation,
  • the most flammable fraction composition (Worst case of fractionation for flammability; WCFF) specified by performing a leakage test during use has a burning speed of 10 cm/s or less, and meets the American ANSI/ASHRAE34-2013 standard for flammability. It means that the division is judged as "2L class".
  • Refrigerants of the present disclosure include HFO-1132(E), R1234ze and R1234yf.
  • the refrigerant of the present disclosure is a low GWP mixed refrigerant.
  • the refrigerant of the present disclosure preferably satisfies the following requirements. At this time, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 70% or more based on R404A. ⁇ Requirements> In the refrigerant, the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segment enclosed by the line segments AB, BF, FE and EA connecting the four points of Line segments AB, BF and EA are straight lines, and a point on line segment FE is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).
  • the refrigerant of the present disclosure preferably satisfies the following requirements. At this time, the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable), and the refrigerating capacity ratio based on R404A is 70% or more.
  • ASHRAE slightly flammable WCF & WCFF slightly flammable
  • the refrigerating capacity ratio based on R404A is 70% or more.
  • the refrigerant the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segments enclosed by the line segments CD, DF, FE and EC connecting the four points of Line segments DF and EC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment FE The top point is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).
  • the refrigerant of the present disclosure preferably satisfies the following requirements. At this time, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 100% or more based on R134a. ⁇ Requirements> In the refrigerant, the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments AB, BH, HG and GA connecting the four points of Line segments AB, BH, and GA are straight lines,
  • a point on line segment HG is represented by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242).
  • the refrigerant of the present disclosure preferably satisfies the following requirements. At this time, the refrigerant of the present disclosure becomes WCF slightly flammable and has a boiling point of ⁇ 40° C. or less. ⁇ Requirements> In the refrigerant, the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments AB, BJ, JI and IA connecting the four points of Line segments AB, BJ, and IA are straight lines, and a point on line segment JI is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).
  • the refrigerant of the present disclosure preferably satisfies the following requirements.
  • the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a refrigerating capacity ratio of 150% or more based on R134a.
  • ASHRAE slightly flammable WCF & WCFF slightly flammable
  • the refrigerant has a refrigerating capacity ratio of 150% or more based on R134a.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H'(31.3, 1.0, 67.7) and Point G'(44.1, 54.9, 1.0) is within or on the line segment enclosed by the line segments AB, BH', H'G' and G'A connecting the four points of Line segments AB, BH', and G'A are straight lines, and a point on line segment H'G' is (x, -0.08728x2+10.791x-251.26, 0.08728x2 -11.791x+351.26) represented.
  • the refrigerant of the present disclosure preferably satisfies the following requirements.
  • the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a refrigerating capacity ratio of 100% or more based on R134a.
  • ASHRAE slightly flammable WCF & WCFF slightly flammable
  • the refrigerant has a refrigerating capacity ratio of 100% or more based on R134a.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments CD, DH, HG and GC connecting the four points of Line segments DH and GC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment HG The top point is denoted by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242 ).
  • the refrigerant of the present disclosure preferably satisfies the following requirements.
  • the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a boiling point of -40°C or less.
  • ASHRAE slightly flammable WCF & WCFF slightly flammable
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments CD, DJ, JI and IC connecting the four points of Line segments DJ and IC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment JI The top point is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).
  • the refrigerant of the present disclosure preferably satisfies the following requirements.
  • the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a refrigerating capacity ratio of 150% or more based on R134a.
  • ASHRAE slightly flammable WCF & WCFF slightly flammable
  • the refrigerant has a refrigerating capacity ratio of 150% or more based on R134a.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7)
  • the line segment DH' is a straight line
  • a point on line segment PD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54)
  • a point on line segment H'P is represented by (x, -0.08728x 2 +10.791x-251.26, 0.08728x 2 -11.791x+351.26).
  • the refrigerant of the present disclosure may contain additional refrigerants in addition to HFO-1132(E), R1234ze and R1234yf within a range that does not impair the above characteristics and effects.
  • the refrigerant of the present disclosure preferably contains 99.5% by mass or more, and preferably 99.75% by mass or more, of the total of HFO-1132(E), R1234ze and R1234yf relative to the total refrigerant. More preferably, it contains 99.9% by mass or more, even more preferably 99.999% by mass or more, and most preferably 99.9999% by mass or more.
  • the refrigerants of the present disclosure may consist essentially of HFO-1132(E), R1234ze and R1234yf, in which case the refrigerants of the present disclosure comprise HFO-1132(E), R1234ze and R1234y, and It may consist only of unavoidable impurities.
  • Refrigerants of the present disclosure may consist solely of HFO-1132(E), R1234ze and R1234yf.
  • the additional refrigerant is not particularly limited and can be selected from a wide range.
  • the mixed refrigerant may contain one kind alone or two or more kinds as an additional refrigerant.
  • Additional refrigerants include acetylene, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124 , CFC-1113, HFC-152a, HFC-161 and 3,3,3-trifluoropropyne.
  • the total amount of the additional refrigerant is preferably 0.5% by mass or less, more preferably 0.25% by mass or less, further preferably 0.1% by mass or less, and 0.01% by mass with respect to the total refrigerant. Most preferably:
  • Refrigerant compositions of the present disclosure comprise at least the refrigerant of the present disclosure and can be used for the same applications as the refrigerant of the present disclosure.
  • the refrigerant composition of the present disclosure can be used to obtain a working fluid for refrigerators by further mixing with at least refrigerator oil.
  • the refrigerant composition of the present disclosure further contains at least one other component in addition to the refrigerant of the present disclosure.
  • the refrigerant composition of the present disclosure may optionally contain at least one of the following other components. As described above, when the refrigerant composition of the present disclosure is used as a working fluid in refrigerators, it is usually mixed with at least refrigerator oil.
  • the refrigerant compositions of the present disclosure are preferably substantially free of refrigerating machine oil.
  • the content of refrigerating machine oil is preferably 1% by mass or less, more preferably 0.1% by mass or less, relative to the entire refrigerant composition.
  • the refrigerant compositions of the present disclosure may contain trace amounts of water.
  • the water content in the refrigerant composition is preferably 0.1% by mass or less with respect to the entire refrigerant. Since the refrigerant composition contains a trace amount of water, the intramolecular double bond of the unsaturated fluorocarbon compound that may be contained in the refrigerant is stabilized, and oxidation of the unsaturated fluorocarbon compound is less likely to occur. , the stability of the refrigerant composition is improved.
  • Tracers are added to the refrigerant compositions of the present disclosure in detectable concentrations so that any dilution, fouling, or other modification of the refrigerant compositions of the present disclosure can be traced.
  • the refrigerant composition of the present disclosure may contain a single tracer, or may contain two or more tracers.
  • the tracer is not particularly limited and can be appropriately selected from commonly used tracers.
  • Tracers include, for example, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, Aldehyde, ketone, nitrous oxide (N 2 O) and the like.
  • Hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons and fluoroethers are particularly preferred as tracers.
  • FC- 14 tetrafluoromethane, CF4
  • HCC-40 chloromethane, CH3Cl
  • HFC-23 trifluoromethane , CHF3
  • HFC-41 fluoromethane, CH3Cl
  • HFC - 125 penentafluoroethane, CF3CHF2
  • HFC-134a (1,1,1,2 - tetrafluoroethane, CF3CH2F
  • HFC-134 1,1,2,2 - tetrafluoroethane, CHF2CHF2
  • HFC-143a 1,1,1 - trifluoroethane, CF3CH3
  • HFC-143 (1,1,2 - trifluoroethane, CHF2CH2F
  • HFC-152a 1,1 - difluoroethane, CHF2CH3
  • HFC-152a (1,1 - difluoroethane, CHF2CH3 ) HFC-152 (1
  • the refrigerant composition of the present disclosure may contain a total of about 10 parts per million (ppm) or more by weight of the tracer relative to the total refrigerant composition.
  • Refrigerant compositions of the present disclosure may also contain less than about 1000 ppm total tracer, based on the total refrigerant composition.
  • Refrigerant compositions of the present disclosure may preferably contain about 30 ppm or more, more preferably about 50 ppm or more of total tracer, based on the total refrigerant composition.
  • Refrigerant compositions of the present disclosure may contain total tracers, preferably less than or equal to about 500 ppm, and less than or equal to about 300 ppm, based on the total refrigerant composition.
  • the refrigerant composition of the present disclosure may contain one type of ultraviolet fluorescent dye alone, or may contain two or more types thereof.
  • the ultraviolet fluorescent dye is not particularly limited, and can be appropriately selected from commonly used ultraviolet fluorescent dyes.
  • ultraviolet fluorescent dyes examples include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof. Either or both of naphthalimide and coumarin are particularly preferred as UV fluorescent dyes.
  • the refrigerant composition of the present disclosure may contain one stabilizer alone, or may contain two or more stabilizers.
  • the stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.
  • stabilizers include nitro compounds, ethers and amines.
  • Nitro compounds include, for example, aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.
  • Ethers include, for example, 1,4-dioxane.
  • amines examples include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.
  • the stabilizer content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the entire refrigerant.
  • the stabilizer content is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the entire refrigerant.
  • the refrigerant composition of the present disclosure may contain a single polymerization inhibitor, or may contain two or more polymerization inhibitors.
  • the polymerization inhibitor is not particularly limited, and can be appropriately selected from commonly used polymerization inhibitors.
  • polymerization inhibitors examples include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.
  • the content of the polymerization inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the entire refrigerant.
  • the content of the polymerization inhibitor is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the entire refrigerant.
  • the refrigerating machine oil-containing working fluid of the present disclosure contains at least the refrigerant or refrigerant composition of the present disclosure and refrigerating machine oil, and is used as a working fluid in a refrigerating machine.
  • the refrigerating machine oil-containing working fluid of the present disclosure is obtained by mixing refrigerating machine oil used in a compressor of a refrigerator with a refrigerant or a refrigerant composition.
  • the working fluid containing refrigerating machine oil generally contains 10% by mass or more of refrigerating machine oil.
  • the working fluid containing refrigerating machine oil generally contains 50% by mass or less of refrigerating machine oil.
  • composition of the present disclosure may contain one type of refrigerating machine oil alone, or may contain two or more types of refrigerating machine oil.
  • the refrigerating machine oil is not particularly limited, and can be appropriately selected from commonly used refrigerating machine oils. In this case, if necessary, it is possible to appropriately select a refrigerating machine oil that is more excellent in terms of the miscibility with the mixture and the effect of improving the stability of the mixture.
  • the base oil of the refrigerator oil for example, at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE) and polyvinyl ether (PVE) is preferable.
  • PAG polyalkylene glycol
  • POE polyol ester
  • PVE polyvinyl ether
  • the refrigerating machine oil may contain additives in addition to the base oil.
  • the additive may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents and antifoaming agents. .
  • a refrigerating machine oil with a kinematic viscosity of 5 cSt or more at 40°C is preferable in terms of lubrication.
  • the refrigerating machine oil having a kinematic viscosity of 400 cSt or less at 40° C. is preferable.
  • the refrigerating machine oil-containing working fluid of the present disclosure may further contain at least one additive, if necessary.
  • additives include the following compatibilizers.
  • the working fluid containing refrigerator oil of the present disclosure may contain one type of compatibilizer alone or may contain two or more types of compatibilizer.
  • the compatibilizer is not particularly limited and can be appropriately selected from commonly used compatibilizers.
  • Compatibilizers include, for example, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.
  • Polyoxyalkylene glycol ether is particularly preferred as the compatibilizer.
  • the refrigerator operation method of the present disclosure is a method of operating the refrigerator using the refrigerant of the present disclosure.
  • the method of operating the refrigerator of the present disclosure includes a step of circulating the refrigerant of the present disclosure in the refrigerator.
  • a mixed refrigerant was prepared by mixing HFO-1132(E), R1234ze and R1234yf in mass % shown in Table 1 based on the sum of these.
  • a GWP of 1 was assumed for HFO-1132(E).
  • the refrigerating capacity of R410A and the above mixed refrigerant was obtained by conducting theoretical calculations of the refrigerating cycle of the mixed refrigerant under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0). .
  • COP (refrigeration capacity or heating capacity) / power consumption
  • the burning rate test was performed using the device shown in Fig. 1 as follows. First, the mixed refrigerant used was made 99.5% pure or better and degassed by repeated freezing, pumping and thawing cycles until no trace of air was visible on the vacuum gauge. Burning rates were measured by the closed method. The initial temperature was ambient temperature. Ignition was achieved by creating an electrical spark between the electrodes in the center of the sample cell. The discharge duration was 1.0-9.9ms and the ignition energy was typically about 0.1-1.0J. Flame propagation was visualized by the Schlieren method. A cylindrical container (inner diameter: 155 mm, length: 198 mm) with two light-transmitting acrylic windows was used as the sample cell, and a xenon lamp was used as the light source. Schlieren images of flames were recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
  • the burning velocity (Su (cm/s)) is expressed by the volume of unburned gas consumed per unit time by a flame front of unit area, and is calculated by the following formula.
  • Su Sb* ⁇ u/ ⁇ b Sb; Flame propagation velocity (cm/s) ⁇ u; adiabatic flame temperature (unburned) ⁇ b;Adiabatic flame temperature (burned)
  • Sb was obtained from the Schlieren video image
  • ⁇ u was the measured temperature
  • ⁇ b was calculated from the combustion heat and constant pressure specific heat of the combustion gas.
  • the refrigerant of the present disclosure when the refrigerant of the present disclosure satisfies the following requirements, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 70% or more based on R404A.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segment enclosed by the line segments AB, BF, FE and EA connecting the four points of Line segments AB, BF and EA are straight lines, and a point on line segment FE is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).
  • the refrigerant of the present disclosure satisfies the following requirements, it is found that the refrigerant of the present disclosure becomes WCFF slightly flammable and has a refrigerating capacity ratio of 70% or more based on R404A.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segments enclosed by the line segments CD, DF, FE and EC connecting the four points of Line segments DF and EC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment FE The top point is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).
  • the refrigerant of the present disclosure when the refrigerant of the present disclosure satisfies the following requirements, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 100% or more based on R134a.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments AB, BH, HG and GA connecting the four points of Line segments AB, BH, and GA are straight lines,
  • a point on line segment HG is represented by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242).
  • the refrigerant of the present disclosure when the refrigerant of the present disclosure satisfies the following requirements, the refrigerant of the present disclosure becomes slightly flammable with WCF and has a boiling point of ⁇ 40° C. or lower.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments AB, BJ, JI and IA connecting the four points of Line segments AB, BJ, and IA are straight lines, and a point on line segment JI is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).
  • the refrigerant of the present disclosure when the refrigerant of the present disclosure satisfies the following requirements, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 150% or more based on R134a.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H'(31.3, 1.0, 67.7) and Point G'(44.1, 54.9, 1.0) is within or on the line segment enclosed by the line segments AB, BH', H'G' and G'A connecting the four points of Line segments AB, BH', and G'A are straight lines, and a point on line segment H'G' is (x, -0.08728x2+10.791x-251.26, 0.08728x2 -11.791x+351.26) represented.
  • the refrigerant of the present disclosure satisfies the following requirements, it is found that the refrigerant of the present disclosure becomes WCFF slightly flammable and has a refrigerating capacity ratio of 100% or more based on R134a.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments CD, DH, HG and GC connecting the four points of Line segments DH and GC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment HG The top point is denoted by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242 ).
  • the refrigerant of the present disclosure satisfies the following requirements, it is found that the refrigerant of the present disclosure becomes WCFF slightly flammable and has a boiling point of ⁇ 40° C. or lower.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments CD, DJ, JI and IC connecting the four points of Line segments DJ and IC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment JI The top point is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).
  • the refrigerant of the present disclosure satisfies the following requirements, it is found that the refrigerant of the present disclosure becomes WCFF slightly flammable and has a refrigerating capacity ratio of 150% or more based on R134a.
  • the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
  • the coordinates (x, y, z) are point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7)
  • the line segment DH' is a straight line
  • a point on line segment PD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 +-0.8166x-35.54)
  • a point on line segment H'P is represented by (x, -0.08728 x 2 +10.791x-251.26, 0.08728x 2 -11.791x+351.26).
  • the approximation formula that indicates the coordinates of the points on each line segment was obtained by obtaining the approximation formula for the curve that connects the three points using the least-squares method.

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PCT/JP2022/010086 2021-03-09 2022-03-08 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 Ceased WO2022191205A1 (ja)

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CN202280020110.7A CN116997632A (zh) 2021-03-09 2022-03-08 含有制冷剂的组合物、其用途以及具有该组合物的冷冻机和该冷冻机的运转方法
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