WO2022075389A1 - 冷媒を含有する組成物 - Google Patents

冷媒を含有する組成物 Download PDF

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Publication number
WO2022075389A1
WO2022075389A1 PCT/JP2021/037080 JP2021037080W WO2022075389A1 WO 2022075389 A1 WO2022075389 A1 WO 2022075389A1 JP 2021037080 W JP2021037080 W JP 2021037080W WO 2022075389 A1 WO2022075389 A1 WO 2022075389A1
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Prior art keywords
refrigerant
hfo
composition
difluoroethylene
log
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2021/037080
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English (en)
French (fr)
Japanese (ja)
Inventor
智行 後藤
崇 吉村
隆 臼井
裕子 伊藤
結香 渡邊
陽平 高倉
拓馬 岩阪
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Daikin Industries Ltd
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Daikin Industries Ltd
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Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Priority to CN202180068975.6A priority Critical patent/CN116568774A/zh
Priority to EP21877688.8A priority patent/EP4227390A4/en
Publication of WO2022075389A1 publication Critical patent/WO2022075389A1/ja
Priority to US18/132,039 priority patent/US20230242801A1/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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • 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—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants
    • F25B2400/121—Inflammable refrigerants using R1234

Definitions

  • the present disclosure relates to a composition containing a refrigerant.
  • Patent Document 1 discloses a working medium for a thermal cycle containing an azeotropic composition composed of trifluoroethylene (HFO-1123) and difluoromethane (HFC-32).
  • Patent Document 2 a refrigerant containing trifluoroethylene (HFO-1123) is used as a working fluid, polyvinyl ether oil is used as a lubricating oil for a compressor, and a fixed scroll and a swivel scroll in which a spiral wrap rises from a mirror plate are bitten.
  • a compressor is disclosed which is provided with a compression chamber formed in both directions and has an injection hole provided in the compression chamber.
  • a compressor, a first heat exchanger, an expansion mechanism, and a second heat exchanger are connected and contain 40 wt% or more of trifluoroethylene (HFO-1123), which is uneven as the pressure increases.
  • HFO-1123 trifluoroethylene
  • the pressure of the refrigerant reaches the threshold value, the neutral point of the three-phase stator winding connected by the Y connection of the electric element of the compressor is cut off, so that the electric element of the compressor and the external power supply are cut off.
  • a refrigerating cycle apparatus including a control mechanism provided in a container of the compressor with an automatic return type pressure fuse that cuts off the energization between the compressor and the compressor.
  • the present disclosure provides inventions of the following aspects.
  • a composition containing a refrigerant which is a composition containing a refrigerant.
  • the refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionate refrigerants are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), and 1,1-difluoroethylene (HFO).
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • y the common logarithm (log) of the thermal diffusivity (mm 2 / s) of the entire refrigerant contained in the composition.
  • the refrigerant is of the formula: y ⁇ -1.5761x + 3.9516 A composition, characterized in that it is in the range indicated by.
  • a composition containing a refrigerant which is a composition containing a refrigerant.
  • the refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionate refrigerants are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), and 1,1-difluoroethylene (HFO).
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • y the common logarithm (log) of the thermal diffusivity (mm 2 / s) of the entire refrigerant contained in the composition.
  • the refrigerant has the formula: y ⁇ -1.4941x + 3.6044 A composition, characterized in that it is in the range indicated by.
  • the non-unequalizing refrigerants are 3,3,3-trifluoropropene (HFO-1243zf), trifluoroiodomethane (CF 3 I), difluoromethane (HFC-32), 2,3,3,3-tetra.
  • Item 4 The composition according to any one of Items 1 to 3 above, which further contains refrigerating machine oil and is used as a refrigerating machine oil-containing working fluid.
  • the refrigerating machine oil contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), polyvinyl ether (PVE), silicon oil, and fluorine-containing oil.
  • PAG polyalkylene glycol
  • POE polyol ester
  • PVE polyvinyl ether
  • silicon oil silicon oil
  • fluorine-containing oil fluorine-containing oil
  • Item 6. The composition according to any one of Items 1 to 5, which is used in an air conditioning system.
  • Item 7 An air conditioning system using the composition according to any one of Items 1 to 6.
  • Item 8 A freezing method comprising a step of operating a freezing cycle using the composition according to any one of Items 1 to 6.
  • Item 9 A method for operating a refrigerating apparatus for operating a refrigerating cycle using the composition according to any one of Items 1 to 6.
  • Item 10 A refrigerating apparatus using the composition according to any one of Items 1 to 6.
  • Item 11 Air-conditioning equipment, refrigerators, freezers, water coolers, ice machines, refrigerating showcases, refrigerating showcases, refrigerating and refrigerating units, refrigerators for refrigerating and refrigerating warehouses, in-vehicle air-conditioning equipment, turbo refrigerators, or screw refrigerators. Refrigerator according to 10.
  • a method of storing a composition containing a refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionate refrigerants are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), and 1,1-difluoroethylene (HFO).
  • HFO-1132 (E) trans-1,2-difluoroethylene
  • HFO-1132 (Z) cis-1,2-difluoroethylene
  • HFO 1,1-difluoroethylene
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • y the common logarithm (log) of the thermal diffusivity (mm 2 / s) of the entire refrigerant contained in the composition.
  • Item 13 A method of storing a composition containing a refrigerant.
  • the refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionate refrigerants are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), and 1,1-difluoroethylene (HFO).
  • HFO-1132 (E) trans-1,2-difluoroethylene
  • HFO-1132 (Z) cis-1,2-difluoroethylene
  • HFO 1,1-difluoroethylene
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • y the common logarithm (log) of the thermal diffusivity (mm 2 / s) of the entire refrigerant contained in the composition.
  • the refrigerant includes a step of mixing a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionate refrigerants are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), and 1,1-difluoroethylene (HFO).
  • HFO-1132 (E) trans-1,2-difluoroethylene
  • HFO-1132 (Z) cis-1,2-difluoroethylene
  • HFO 1,1-difluoroethylene
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • y the common logarithm (log) of the thermal diffusivity (mm 2 / s) of the entire refrigerant contained in the composition.
  • the refrigerant includes a step of mixing a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionate refrigerants are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), and 1,1-difluoroethylene (HFO).
  • HFO-1132 (E) trans-1,2-difluoroethylene
  • HFO-1132 (Z) cis-1,2-difluoroethylene
  • HFO 1,1-difluoroethylene
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • y the common logarithm (log) of the thermal diffusivity (mm 2 / s) of the entire refrigerant contained in the composition.
  • the refrigerant includes a step of mixing a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionate refrigerants are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), and 1,1-difluoroethylene (HFO).
  • HFO-1132 (E) trans-1,2-difluoroethylene
  • HFO-1132 (Z) cis-1,2-difluoroethylene
  • HFO 1,1-difluoroethylene
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • y the common logarithm (log) of the thermal diffusivity (mm 2 / s) of the entire refrigerant contained in the composition.
  • the refrigerant includes a step of mixing a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionate refrigerants are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), and 1,1-difluoroethylene (HFO).
  • HFO-1132 (E) trans-1,2-difluoroethylene
  • HFO-1132 (Z) cis-1,2-difluoroethylene
  • HFO 1,1-difluoroethylene
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • y the common logarithm (log) of the thermal diffusivity (mm 2 / s) of the entire refrigerant contained in the composition.
  • composition containing the refrigerant of the present disclosure suppresses the disproportionation reaction of the refrigerant and is excellent in the stability of the refrigerant.
  • composition containing the refrigerant of the present disclosure is useful for air conditioning systems.
  • the present inventors have made a composition containing a refrigerant disproportionating and a refrigerant not disproportionating when the composition containing the refrigerant is used in an air conditioning system. It has been found that the disproportionation reaction of the refrigerant used is suppressed in the air conditioning system when the entire refrigerant of the object is operated under the condition based on a specific relational expression.
  • refrigerant includes at least a compound having a refrigerant number (ASHRAE number) starting with R indicating the type of refrigerant defined by ISO817 (International Organization for Standardization), and further includes a refrigerant number. Even if it has not been attached yet, those having the same characteristics as a refrigerant are included.
  • ASHRAE number refrigerant number
  • ISO817 International Organization for Standardization
  • Fluorocarbon-based compounds include hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs).
  • HCFCs hydrochlorofluorocarbons
  • HFCs hydrofluorocarbons
  • non-fluorocarbon compound examples include propane (R290), propylene (R1270), butane (R600), isobutane (R600a) and the like.
  • composition containing a refrigerant further contains (1) the refrigerant itself (including a mixture of refrigerants (refrigerant mixture)) and (2) other components, and is mixed with at least a refrigerating machine oil.
  • composition of (2) is referred to as a "refrigerant composition" to distinguish it from the refrigerant itself (including a mixture of refrigerants).
  • working fluid for the refrigerator in (3) is also referred to as "working fluid containing refrigeration oil” to distinguish it from the "refrigerant composition”.
  • the term "alternative” is used in the context of "substituting" a first refrigerant with a second refrigerant to, as the first type, to operate with the first refrigerant.
  • the designed equipment uses a second refrigerant with only minor changes (at least one of refrigerating machine oil, gaskets, packing, expansion valves, dryers and other parts) and equipment adjustments as needed. This means that it can be operated under optimum conditions.
  • this type refers to operating the same equipment by “substituting” the refrigerant.
  • drop-in alternative and “nearly drop-in (nearly drop-in)” are used in ascending order of the degree of change or adjustment required for replacement with the second refrigerant.
  • equipment designed to operate with a second refrigerant can also be used with a second refrigerant for the same use as the existing use of the first refrigerant. Included in the term "alternative”. This type refers to providing the same application as an "alternative" to the refrigerant.
  • a refrigerator refers to all devices that maintain this low temperature while keeping the temperature lower than the surrounding outside air by removing heat from objects or spaces.
  • a refrigerator is a conversion device that obtains energy from the outside to perform work and convert energy in order to transfer heat from the lower temperature side to the higher temperature side.
  • the terms “contains” and “contains” include the concepts of “contains”, “contains”, “substantially consists”, and “consists of only”.
  • the upper limit value or the lower limit value of the numerical range of one step can be arbitrarily combined with the upper limit value or the lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range described may be replaced with a value shown in Examples or a value that can be uniquely derived from Examples.
  • composition (1) Refrigerant The composition of the present disclosure contains a refrigerant, and the refrigerant includes a refrigerant that disproportionates and a refrigerant that does not disproportionate.
  • the refrigerants to be disproportionate are trans-1,2-difluoroethylene (HFO-1132 (E)), cis-1,2-difluoroethylene (HFO-1132 (Z)), 1,1-. It contains at least one component selected from the group consisting of difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1123), and tetrafluoroethylene (FO-1114).
  • the non-unequalizing refrigerants are preferably 3,3,3-trifluoropropene (HFO-1243zf), trifluoroiodomethane (CF 3 I), difluoromethane (HFC-32), 2, 3,3,3-Tetrafluoropropene (HFO-1234yf), Trans-1,3,3,3-Tetrafluoropropene (HFO-1234ze (E)), Hexafluoropropene (FO-1216), Perfluoromethane ( PFC-14), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1, 1,1-Trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition of the present disclosure, and the thermal diffusion rate (mm 2 / s) of the entire refrigerant contained in the composition. )
  • the common logarithm (log) is y
  • the refrigerant has the formula: y ⁇ -1.5761x + 3.9516. It is the range indicated by.
  • x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition of the present disclosure, and the thermal diffusion rate (mm 2 / s) of the entire refrigerant contained in the composition. )
  • the common logarithm (log) is y
  • the refrigerant has the formula: y ⁇ -1.4941x + 3.6044 It is the range indicated by.
  • the "whole refrigerant” represents the total of "disproportionable refrigerant” and "non-disproportionate refrigerant".
  • the refrigerant used is composed of a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the method for producing the refrigerant to be contained is not particularly limited, and for example, various refrigerants can be produced by a known production method.
  • the refrigerant is HFO-1132 (E / Z), HFO-1132 (E / Z) defluorinated hydrogen 1,1,2-trifluoroethane (HFC-143), (E).
  • HFC-143 HFO-1132 (E / Z) defluorinated hydrogen 1,1,2-trifluoroethane
  • E defluorinated hydrogen 1,1,2-trifluoroethane
  • E defluorinated hydrogen 1,1,2-trifluoroethane
  • HCFC- 1-chloro-1,2-difluoroethane
  • 142a) can be produced by the dehydrochlorination reaction.
  • the total amount of the refrigerant can be specified by a gas chromatograph.
  • the refrigerant contained in the composition is preferably at least one disproportionation selected from the group consisting substantially of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114. It may be a combination composed of a refrigerant that does not disproportionate and a refrigerant that does not disproportionate.
  • the content ratio of the refrigerant is not particularly limited, and is usually preferably 95% by mass or less, more preferably 90% by mass or less, and further, with respect to the entire composition. It is preferably 80% by mass or less, particularly preferably 70% by mass or less, and most preferably 60% by mass or less.
  • the content ratio of the refrigerant is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 20% by mass or more, based on the entire composition. It is 30% by mass or more, and most preferably 40% by mass or more.
  • impurities unavoidable impurities that may be mixed during the production of the refrigerant can be contained.
  • the impurities are, for example, HFO-1132 (E / Z), hydrogen fluoride, fluoroethylene, HFO-1123, 1,1,1-trifluoroethane, propylene, acetylene, HFC-32, trifluoromethane, Fluoromethane, HFO-1123, HFC-152a, HFC-161, HFC-143, 2-chloro-1,1,1-trifluoroethane (HCFC-133b), 1-chloro-1,1,2-trifluoro Etan (HCFC-133), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1-chloro-1,2-difluoroethane (HCFC-142a), 1,2-difluoroethane (HFC) -152), chlorodifluoromethane (HCFC-22), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134),
  • the content thereof is not particularly limited, and may contain, for example, about 0.1 ppm or more and 10,000 ppm or less in terms of weight. Within this range, there is little possibility that the stabilizing action of the refrigerant in the composition will be hindered.
  • the refrigerant contained in the composition is required to have a global warming potential (GWP) of less than 10, low toxicity, and non-combustibility.
  • GWP global warming potential
  • HFO-based refrigerants HFO-1132 (E), HFO-1132 (Z), HFO-1132a, HFO-1123, FO-1114, etc.
  • the GWP is less than 10 and the toxicity is low.
  • the problems are solved by mixing with other refrigerants in the refrigerant composition and controlling the operating conditions, mixing, storage and other operating conditions on the equipment side of the air conditioning system. There is an attempt.
  • HFO-1132 (E) and HFO-1132 (Z) as HFO-based refrigerants is expressed by the following equation.
  • CHF CHF ⁇ 2C + 2HF
  • the disproportionation reaction is 1. Temperature , 2. Pressure and refrigerant composition , 3. It is generated when the three elements of ignition energy are aligned.
  • FIG. 1 shows the disproportionation generation range in the air conditioning system of the present disclosure by the composition ratio of the disproportionated refrigerant HFO-1132 (E) and the non-disproportionated refrigerant HFO-1234yf, as an example.
  • disproportionation occurs when there is an ignition source.
  • the "temperature and pressure condition with disproportionation" is on the positive side in the horizontal axis direction of each graph.
  • Ignition energy is not particularly limited.
  • Ignition energy Conditions where 30J is assumed For example, layer short of wiring in the compressor, fusing due to Joule heat, spark, frictional heat of sliding parts, heat generation of motor, adiabatic compression of refrigerant in piping, refrigerant and structure Collision energy etc. can be considered. The magnitude of ignition energy varies, and it is considered that the larger the amount of energy, the more likely it is that disproportionation will occur.
  • the ignition energy used in the combustion evaluation of the refrigerant is set to give 20J or more under the High Pressure Gas Safety Act, and is 30J in the actual measurement.
  • the disproportionation reaction is 1. Temperature, 2. Pressure and refrigerant composition, 3. Since it is generated by aligning the three elements of ignition energy, in a composition containing a specific disproportionating refrigerant and a non-unequalizing refrigerant under an ignition energy of 30J, the said in the gas phase of the composition.
  • x be the common logarithm (log) of the concentration of the refrigerant to be disproportionated (mol / m 3 )
  • y the common logarithm (log) of the thermal diffusion rate (mm 2 / s) of the entire refrigerant contained in the composition.
  • Ignition energy Conditions where 500J is assumed Generally, the ignition energy of the frictional heat of the sliding part reaches 500J.
  • the concentration of the disproportionated refrigerant in the gas phase of the composition (mol / m 3 ) in the composition containing a specific disproportionating refrigerant and a non-disproportionating refrigerant. )
  • Is x, and y is the common logarithm (log) of the thermal diffusion rate (mm 2 / s) of the entire refrigerant contained in the composition.
  • the refrigerant has the formula: y ⁇ -1.4941x + 3.6044 It is possible to suppress the disproportionation reaction by adjusting or controlling the temperature, pressure and / or the refrigerant composition so as to be in the range indicated by.
  • the ignition energy is set to 500 J
  • the ignition energy is set to 30 J under the condition that the disproportionation reaction of the refrigerant contained in the composition can be suppressed (formula: y ⁇ -1.4941x + 3.6044). It can be said that it is a more preferable condition than the condition of the case (formula: y ⁇ -1.5761x + 3.9516).
  • FIG. 2 shows operating conditions of a refrigerant when the composition of the present disclosure contains a disproportionating refrigerant and a non-disproportionating refrigerant, for example, when used in an air conditioning system. It is a graph which generalizes the refrigerant composition, temperature, and pressure conditions which do not cause a disproportionation reaction.
  • composition of the present disclosure for example, in an air conditioning system, as shown in FIG. 2, "disproportionation is suppressed” by plotting "heat diffusion rate of the entire refrigerant” and "concentration of the refrigerant to be disproportionated".
  • the " ⁇ ” in “when it is done” and the “x” in “when disproportionation” straddle the graph and are divided into the lower left ( ⁇ ) of the graph and the upper right (x) of the graph.
  • compositions of the present disclosure are, for example, operated in an air conditioning system under the refrigerant composition, temperature, and pressure conditions at the lower left ( ⁇ ) from the boundary line of the graph (straight line equation) as shown in FIG. That is, since the refrigerant is controlled within the range indicated by y ⁇ -1.5761x + 3.9516, it is possible to operate the air conditioning system in which the disproportionation reaction is suppressed.
  • the common logarithm (log) of the concentration (mol / m3) of the disproportionate refrigerant in the gas phase of the composition of the present disclosure is x
  • the thermal diffusion rate (mm2) of the entire refrigerant contained in the composition is defined as x.
  • the refrigerant has the formula: y ⁇ -1.4941x + 3.6044 It can also be applied when the range is shown by.
  • compositions of the present disclosure are used, for example, in air conditioning systems, where the common log (log) of the concentration of the disproportionating refrigerant (mol / m 3 ) in the gas phase of the composition is "x" (x-axis). ..
  • the range of the x-axis i.e., the range of "log (concentration of disproportionating refrigerant in the gas phase of the composition (mol / m 3 ))" is used, for example, in air conditioning systems. From time to time, the disproportionation reaction is preferably suppressed to -0.59 or more and 4.23 or less, and more preferably 2.2 or more and 3.4 or less.
  • Total number of disproportionated refrigerants is the total number of disproportionated refrigerants in the refrigerant composition, and when one type of disproportionated refrigerant is used alone, it refers to that one type and is disproportionated. When two or more types of refrigerants are used in combination, it refers to the total of the two or more types used in combination.
  • the “concentration of the disproportionating refrigerant in the gas phase of the composition (mol / m 3 )" which is included in the common logarithm (log) of the value of "x" (x-axis), depends on the temperature, pressure, and refrigerant composition. do.
  • the range of the y-axis that is, the range of "log (thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s))" follows the range of the x-axis based on the formula. ..
  • thermo diffusivity of the entire refrigerant (mm 2 / s)
  • log log
  • the above "thermal conductivity [mW / (m K)]" is the composition of the refrigerant. Depends on temperature, and pressure.
  • the “density [kg / (m 3 )]” depends on the refrigerant composition, temperature, and pressure.
  • Specific heat means constant pressure molar specific heat.
  • the thermal conductivity [m W / (m K)] ”,“ density [kg / (m 3 )] ”, and“ specific heat [kJ / kg K] may be actually measured, or the National Institute of Science and Technology (National Institute of Science and Technology) NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop) may be used to perform theoretical calculations.
  • the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition of the present disclosure is defined as x, and the thermal diffusion rate of the entire refrigerant contained in the composition (
  • x the common logarithm (log) of mm 2 / s)
  • y for example, under an ignition energy of 500 J
  • the refrigerant has the formula: y ⁇ -1.4941x + 3.6044 It can also be applied when the range is shown by.
  • the range of x is preferably -0.59 or more and 4.23 or less in that the disproportionation reaction is well suppressed when the composition of the present disclosure is used, for example, in an air conditioning system.
  • the range of y follows the range of x, based on the equation.
  • the conditions under which the disproportionation reaction occurs at the ignition energy of 500J include the conditions under which the disproportionation reaction is suppressed at the ignition energy of 30J.
  • the condition at which the disproportionation reaction occurs at the ignition energy of 500 J is a condition within an allowable range in which the disproportionation reaction is suppressed.
  • the condition in which the disproportionation reaction is suppressed at the ignition energy of 500J is higher than the condition in which the disproportionation reaction is suppressed at the ignition energy of 30J, even in a more severe situation such as a device failure or an emergency. In terms of suppressing disproportionation, it is safer and more preferable.
  • the “whole refrigerant” is the total of the disproportionated refrigerant and the non-disproportionated refrigerant in the refrigerant composition.
  • the disproportionating refrigerant contains at least one component selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114, and can be used alone. It is good, or it may be used in combination of two or more types.
  • Refrigerants that do not disproportionate are preferably HFO-1243zf, CF 3 I, HFC-32, HFO-1234yf, HFO-1234ze (E), FO-1216, PFC-14, HFC-125, HFC-134, HFC. -134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye (Z), HFO-1225ye (E), CF 3 SCF 3 , propane, cyclopropane, propylene, isobutane, isobutane, dioxide It contains at least one component selected from the group consisting of carbon and ammonia, and may be used alone or in combination of two or more.
  • composition of the present disclosure when used in an air conditioning system, has the above-mentioned configuration, so that it is possible to provide an air conditioning system containing a refrigerant in which the disproportionation reaction of the refrigerant is suppressed.
  • Specific examples of use of the composition (1) Specific examples 1 As the refrigerant composition, 60% by mass of HFO-1132 (E / Z) is contained as a disproportionating refrigerant and 40% by mass of HFO-1234yf is contained as a non-disproportionating refrigerant in the entire refrigerant contained in the composition.
  • the temperature condition is 150 ° C.
  • the pressure condition is 3.00 MPa.
  • log heat diffusion rate of the entire refrigerant contained in the composition (mm 2 / s)
  • the air conditioning system has the refrigerant composition, temperature, and pressure conditions. It is possible to operate the air conditioning system by using the composition that "suppresses the disproportionation reaction" when operating in.
  • “Lower left of the graph” is "the position on the negative side in the y-axis direction with respect to the graph (straight line equation)".
  • log heat diffusion rate of the entire refrigerant contained in the composition (mm 2 / s)
  • the calculated value is "higher” than the above-mentioned "y” value "-0.55242”.
  • the temperature condition is 150 ° C.
  • the pressure condition is 2.00 MPa.
  • Equation (2-1): Calculation of "-1.5761x + 3.9516” on the right side of “y -1.5761x + 3.9516”” Disproportionating refrigerant in the gas phase of the composition” included in the common logarithm (log) of the x-axis Concentration (mol / m 3 ) ”is calculated.
  • log heat diffusion rate of the entire refrigerant contained in the composition (mm 2 / s)
  • the air conditioning system has the refrigerant composition, temperature, and pressure conditions. It is possible to operate the air conditioning system by using the composition that "suppresses the disproportionation reaction" when operating in.
  • “Lower left of the graph” is "the position on the negative side in the y-axis direction with respect to the graph (straight line equation)".
  • log heat diffusion rate of the entire refrigerant contained in the composition (mm 2 / s)
  • the calculated value is "higher” than the above-mentioned "y” value "-0.23909”.
  • Equation (2-2): Calculation of the left side "y” of "y -1.5761x + 3.9516" The thermal diffusivity of the entire refrigerant contained in the composition (mm 2 /) included in the common logarithm (log) of the y-axis. s) ”is calculated.
  • the refrigerant composition for example, 60% by mass of HFO-1132 (E / Z) is contained as a refrigerant to be disproportionated in the entire refrigerant contained in the air conditioning system, and the refrigerant is disproportionated.
  • the temperature condition is 130 ° C and the pressure condition is 2.00 MPa
  • the composition contains 40% by mass of HFO-1234yf, and the refrigerant contains "the disproportionation reaction is suppressed (does not occur)". It becomes a thing.
  • the refrigerant composition contains 50% by mass of HFO-1132 (E / Z) as a disproportionating refrigerant and 50% by mass of HFO-1234yf as a non-disproportionating refrigerant in the entire refrigerant contained in the composition.
  • the temperature condition is 150 ° C.
  • the pressure condition is 5.00MPa.
  • log heat diffusion rate of the entire refrigerant contained in the composition (mm 2 / s)
  • the air conditioning system has the refrigerant composition, temperature, and pressure conditions. It is possible to operate the air conditioning system by using the composition that "suppresses the disproportionation reaction" when operating in.
  • “Lower left of the graph” is "the position on the negative side in the y-axis direction with respect to the graph (straight line equation)".
  • log heat diffusion rate of the entire refrigerant contained in the composition (mm 2 / s)
  • the calculated value is "higher” than the above-mentioned "y” value "-0.89995".
  • the refrigerant composition for example, 50% by mass of HFO-1132 (E / Z) is contained as a refrigerant to be disproportionated in the entire refrigerant contained in the air conditioning system, and the refrigerant is disproportionated.
  • HFO-1234yf is contained in an amount of 50% by mass, the temperature condition is 150 ° C., and the pressure condition is 5.00 MPa, the composition contains a refrigerant that “disproportionates”.
  • the refrigerant composition contains 50% by mass of HFO-1132 (E / Z) as a disproportionating refrigerant and 50% by mass of HFO-1234yf as a non-disproportionating refrigerant in the entire refrigerant contained in the composition.
  • the temperature condition is 150 ° C.
  • the pressure condition is 4.00 MPa.
  • log heat diffusion rate of the entire refrigerant contained in the composition (mm 2 / s)
  • the air conditioning system has the refrigerant composition, temperature, and pressure conditions.
  • the air conditioning system can be operated with a composition that "suppresses the disproportionation reaction”.
  • “Lower left of the graph” is "the position on the negative side in the y-axis direction with respect to the graph (straight line equation)”.
  • log heat diffusion rate of the entire refrigerant contained in the composition (mm 2 / s)
  • the calculated value is "higher” than the above-mentioned "y” value "-0.70578”.
  • the refrigerant composition for example, 50% by mass of HFO-1132 (E / Z) is contained as a refrigerant to be disproportionated in the entire refrigerant contained in the air conditioning system, and the refrigerant is disproportionated.
  • the temperature condition is 150 ° C and the pressure condition is 4.00 MPa
  • the composition contains 50% by mass of HFO-1234yf, and the refrigerant contains "the disproportionation reaction is suppressed (does not occur)". It becomes the driving of things.
  • composition of the present disclosure is used, for example, in an air conditioning system, as described in the above specific examples 1 to 4, for example, under an ignition energy of 30 J.
  • y log (Thermal diffusivity of the entire refrigerant contained in the composition (mm 2 / s))
  • the air conditioning system in which the disproportionation reaction is suppressed can be operated.
  • the above description is described, for example, under an ignition energy of 500J.
  • the refrigerant is the formula: y ⁇ -1.4941x + 3.6044 It can also be applied to the range indicated by, and it is possible to operate the air conditioning system in which the disproportionation reaction is suppressed when operating under the conditions controlled in this range.
  • the range of x is preferably -0.59 or higher, 4.23 or lower, and further, in that the disproportionation reaction is well suppressed when the compositions of the present disclosure are used, for example, in an air conditioning system. It is preferably 2.2 or more and 3.4 or less.
  • the range of y follows the range of x based on the equation.
  • the conditions under which the disproportionation reaction occurs at the ignition energy of 500J include the conditions under which the disproportionation reaction is suppressed at the ignition energy of 30J.
  • the condition at which the disproportionation reaction occurs at the ignition energy of 500 J is a condition within an allowable range in which the disproportionation reaction is suppressed. It can be said that the condition in which the disproportionation reaction is suppressed at the ignition energy of 500 J is more preferable than the condition in which the disproportionation reaction is suppressed at the ignition energy of 30 J, and the condition in which the disproportionation reaction is suppressed.
  • Refrigerating machine oil The composition of the present disclosure preferably further contains refrigerating machine oil and is used as a working fluid (working fluid for a refrigerating machine) in a refrigerating machine or a working fluid containing refrigerating machine oil.
  • composition of the present disclosure is obtained as a refrigerating machine oil-containing working fluid by mixing the refrigerating machine oil used in the compressor of the refrigerating machine and the refrigerant with each other.
  • the composition of the present disclosure changes its composition in the refrigerating cycle due to the inclusion of refrigerating machine oil.
  • the refrigerating machine oil content of the composition of the present disclosure is relatively high in the compressor, and it is relatively discharged from the compressor in the form of mist, circulates in the refrigerating cycle, and returns to the compressor. few.
  • the refrigerating machine oil content of the composition of the present disclosure is 30% by mass to 70% by mass in the compressor, and is preferably 0 to 20 in the period from being discharged from the compressor to returning to the compressor again. It is mass%, more preferably 1 mass ppm to 10 mass%.
  • Refrigerating machine oil is mainly a base oil and a lubricating oil.
  • the refrigerating machine oil preferably contains at least one polymer selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE), silicon oil, and fluorine-containing oil.
  • PAG polyalkylene glycol
  • POE polyol ester
  • PVE polyvinyl ether
  • silicon oil silicon oil
  • fluorine-containing oil fluorine-containing oil
  • PAG polyalkylene glycol
  • POE polyol ester
  • the refrigerating machine oil preferably contains at least one additive in addition to the base oil.
  • Additives are preferably compatibilizers, UV fluorescent dyes, stabilizers, polymerization inhibitors, antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper inactivating agents, rust inhibitors, oily It is at least one component selected from the group consisting of agents and antifoaming agents.
  • the refrigerating machine oil preferably has a kinematic viscosity of 5cSt to 400cSt at 40 ° C. from the viewpoint of lubrication.
  • the refrigerating machine oil preferably contains an additive in addition to the base oil.
  • the additive is preferably selected from the group consisting of compatibilizers, antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oily agents and defoamers. At least one species.
  • the compatibilizer is not particularly limited and can be appropriately selected from commonly used compatibilizers.
  • the compatibilizer is preferably, for example, polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoroether, 1,1,1-trifluoroalkane and the like. Among these, polyoxyalkylene glycol ether is more preferable.
  • the refrigerating machine oil may preferably contain one type of compatibilizer alone or may contain two or more types of compatibilizer.
  • the refrigerating machine oil-containing working fluid preferably contains a small amount of water to stabilize the intramolecular double bond of the unsaturated fluorocarbon compound that may be contained in the refrigerant. Further, since the refrigerating machine oil-containing working fluid contains a small amount of water, oxidation of unsaturated fluorocarbon-based compounds is less likely to occur, so that the stability of the refrigerant is improved.
  • the tracer is added to the refrigerant at a detectable concentration so that if the refrigerating machine oil-containing working fluid is diluted, contaminated, or otherwise modified, the changes can be tracked.
  • the tracer may be contained alone or in combination of two or more.
  • the ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.
  • the ultraviolet fluorescent dye preferably includes, for example, naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene and fluorescein, and derivatives thereof. Among these are naphthalimide and coumarin.
  • the ultraviolet fluorescent dye may be contained alone or in combination of two or more.
  • the stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.
  • the stabilizer is preferably, for example, a nitro compound, ethers, amines, butyl hydroxyxylene, benzotriazole and the like.
  • the nitro compound is preferably, for example, an aliphatic nitro compound such as nitromethane or nitroethane, or an aromatic nitro compound such as nitrobenzene or nitrostyrene.
  • the ethers are preferably, for example, 1,4-dioxane and the like.
  • the amines are preferably, for example, 2,2,3,3,3-pentafluoropropylamine, diphenylamine and the like.
  • the stabilizer may be contained alone or in combination of two or more.
  • the polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.
  • the polymerization inhibitor is preferably, for example, 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, benzotriazole and the like. ..
  • the polymerization inhibitor may be contained alone or in combination of two or more.
  • composition of the present disclosure is preferably used for operating an air conditioning system.
  • composition of the present disclosure is preferably used in a freezing method including a step of operating a freezing cycle.
  • the composition of the present disclosure is preferably used in a method of operating a refrigerating apparatus for operating a refrigerating cycle.
  • the refrigerating device is preferably an air conditioner, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated showcase, a refrigerated showcase, a refrigerating / refrigerating unit, a refrigerating / refrigerating warehouse refrigerator, an in-vehicle air conditioner, a turbo refrigerator, or a refrigerator. It is a screw refrigerator.
  • the method for storing the composition contains the refrigerant.
  • the refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionating refrigerant contains at least one component selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114. Let x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • the refrigerant includes a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionating refrigerant contains at least one component selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114.
  • Let x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • the non-unequalizing refrigerant is preferably HFO-1243zf, CF 3 I, HFC-32, HFO-1234yf, HFO-1234ze ( E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye (E / Z), CF 3 It contains at least one component selected from the group consisting of SCF 3 , propane, cyclopropane, propylene, isobutane, isobutane, carbon dioxide, and ammonia.
  • the method for storing the composition containing the refrigerant of the present disclosure preferably further comprises a step of containing refrigerating machine oil.
  • the components described in the item of the composition can be used.
  • the method of mixing the refrigerant includes a step of mixing a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionating refrigerant contains at least one component selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114.
  • Let x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • the refrigerant includes a step of mixing a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionating refrigerant contains at least one component selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114.
  • Let x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • the non-unequalizing refrigerant is HFO-1243zf, CF 3 I, HFC-32, HFO-1234yf, HFO-1234ze (E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye (E / Z), CF 3 SCF 3 , It contains at least one component selected from the group consisting of propane, cyclopropane, propylene, isobutane, isobutane, carbon dioxide, and ammonia.
  • the method of mixing the composition containing the refrigerant of the present disclosure preferably further includes a step of containing refrigerating machine oil.
  • the components described in the item of the above composition can be used.
  • the refrigerant includes a step of mixing a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionating refrigerant contains at least one component selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114.
  • Let x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • the refrigerant includes a step of mixing a disproportionating refrigerant and a non-disproportionating refrigerant.
  • the disproportionating refrigerant contains at least one component selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114.
  • Let x be the common logarithm (log) of the concentration (mol / m 3 ) of the disproportionated refrigerant in the gas phase of the composition.
  • Disproportionation means that two or more chemical species of the same type (each component of an ethylene-based fluorinated hydrocarbon having a double bond such as HFO-1132 (E)) react with each other, and two or more types are different. A chemical reaction that gives a kind of product.
  • the method for suppressing the disproportionation reaction of the present disclosure is at least one selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114 by having the above-mentioned configuration. It has the property of suppressing the disproportionation reaction of the refrigerant.
  • the method of suppressing the disproportionation reaction of the present disclosure includes at least one refrigerant (or a refrigerant thereof selected from the group consisting of HFO-1132 (E / Z), HFO-1132a, HFO-1123, and FO-1114.
  • the composition) and the non-unequalizing refrigerant are the refrigerant contained in the composition, where x is the common log (log) of the concentration (mol / m 3 ) of the disproportionating refrigerant in the gas phase of the composition.
  • x is the common log (log) of the concentration (mol / m 3 ) of the disproportionating refrigerant in the gas phase of the composition.
  • the common log (log) of the total heat diffusion rate (mm 2 / s) is y, the above-mentioned refrigerant is used.
  • the non-unequalizing refrigerant is HFO-1243zf, CF 3 I, HFC-32, HFO-1234yf, HFO-1234ze (E), FO-1216, PFC-14, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFO-1225ye (E / Z), CF 3 SCF 3 , It contains at least one component selected from the group consisting of propane, cyclopropane, propylene, isobutane, isobutane, carbon dioxide, and ammonia.
  • the method for suppressing the disproportionation reaction of the refrigerant of the present disclosure preferably further includes a step of containing refrigerating machine oil.
  • the components described in the item of the above composition can be used.
  • the refrigerant composition of the refrigerant is a mixed refrigerant containing a disproportionating refrigerant and a non-disproportionating refrigerant, and the conditions of the temperature and pressure of the refrigerant are adjusted.
  • Ignition energy 30J (Tables 1 to 5)
  • Ignition energy 500J (Table 6)
  • the ignition energy was optimized by adjusting the voltage, current, and time so that disproportionation was most likely to occur under the same amount of heat.
  • the condition in which the disproportionation reaction is suppressed at the ignition energy of 500 J is represented by " ⁇ " evaluation, and the more preferable condition in which the disproportionation reaction is suppressed is represented.
  • the “ ⁇ ” evaluation under the condition that the disproportionation reaction occurs at the ignition energy of 500 J falls within the “ ⁇ ” evaluation under the condition that the disproportionation reaction is suppressed at the ignition energy of 30 J.
  • the “ ⁇ ” evaluation of the condition under which the disproportionation reaction occurs at the ignition energy of 500 J is referred to as “reference example” because it is a condition within the allowable range in which the disproportionation reaction is suppressed in the present disclosure.
  • the y-axis the thermal diffusion rate of the entire refrigerant and the x-axis: the concentration of the disproportionated refrigerant in the gas phase of the composition, the conditions under which the disproportionation reaction is suppressed (result of ⁇ ) and the disproportionation.
  • the boundary between the two can be expressed by an approximate expression as follows.

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