WO2016181933A1 - Composition pour système à cycle thermique, et système à cycle thermique - Google Patents

Composition pour système à cycle thermique, et système à cycle thermique Download PDF

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Publication number
WO2016181933A1
WO2016181933A1 PCT/JP2016/063739 JP2016063739W WO2016181933A1 WO 2016181933 A1 WO2016181933 A1 WO 2016181933A1 JP 2016063739 W JP2016063739 W JP 2016063739W WO 2016181933 A1 WO2016181933 A1 WO 2016181933A1
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cycle system
mass
heat cycle
composition
working medium
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PCT/JP2016/063739
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English (en)
Japanese (ja)
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真維 田坂
正人 福島
宏明 光岡
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旭硝子株式会社
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Priority to JP2017517931A priority Critical patent/JPWO2016181933A1/ja
Priority to CN201680027297.8A priority patent/CN107532072A/zh
Publication of WO2016181933A1 publication Critical patent/WO2016181933A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/06—Well-defined hydrocarbons aromatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/48—Esters of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a composition for a heat cycle system and a heat cycle system using the composition.
  • CFC chlorofluorocarbons
  • HCFC hydrochlorofluorocarbons
  • HFC-32 difluoromethane
  • HFC-125 pentafluoroethane
  • R410A a pseudo-azeotropic mixture of HFC-32 and HFC-125 having a mass ratio of 1: 1 is a refrigerant that has been widely used.
  • HFC may cause global warming.
  • R410A has been widely used for ordinary air-conditioning equipment called so-called package air conditioners and room air conditioners because of its high refrigerating capacity.
  • GWP global warming potential
  • the global warming potential (GWP) is as high as 2088, and therefore development of a low GWP working medium is required.
  • R410A is simply replaced and the devices that have been used so far continue to be used.
  • HFO olefins
  • HFC saturated HFC
  • HFC is referred to as HFC, and is used separately from HFO.
  • HFC is specified as a saturated hydrofluorocarbon.
  • heat cycle systems (1) to (3) are known as working media containing HFO.
  • HFO-1243zf 3,3,3-trifluoropropene
  • HFO-1234ze 1,3,3,3-tetrafluoropropene
  • 2-fluoropropene HFO-1261yf
  • 2,3,3 , 3-tetrafluoropropene HFO-1234yf
  • 1,1,2-trifluoropropene HFO-1243yc
  • thermal cycle system using a working medium see, for example, Patent Document 1
  • Patent Document 1 2,3,3,3-pentafluoropropene (HFO-1225ye), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3 Thermal cycle system using a working medium containing 3,3-tetrafluoropropene (HFO-1234ze (Z)), HFO-1234yf, etc.
  • Patent Document 2 (3) Thermal cycle system using a working medium containing 3,3-tetraflu
  • both the thermal cycle systems (1) and (2) have insufficient cycle performance (capability).
  • the thermal cycle system (3) can provide excellent cycle performance, HFO-1123 has combustibility, and thus there is a problem in ensuring safety.
  • a large-scale air conditioning equipment such as a building air conditioner for buildings
  • the refrigerant charging amount is large, even if the working medium in the gas phase formed in the system leaks, mixes with the air, and ignites, It is important to use a working medium that does not spread easily and ensure the safety of the system.
  • HFO-1123 used as such a working medium is a compound containing an unsaturated bond in the molecule and has a very short life in the atmosphere. Therefore, compression and heating in a thermal cycle are repeated. Under such conditions, the stability is inferior to saturated hydrofluorocarbons and hydrochlorofluorocarbons such as conventional HFCs and HCFCs, and lubricity may be reduced in the thermal cycle system.
  • the present invention has been made from the above viewpoint, and in a composition for a thermal cycle system containing trifluoroethylene (HFO-1123), the low global warming potential and excellent cycle performance of HFO-1123 are sufficiently obtained.
  • the purpose of the present invention is to provide a composition for a heat cycle system that is nonflammable, has little influence on the ozone layer even if leaked, is excellent in safety, and can be more stably lubricated.
  • the present invention uses the above composition for a heat cycle system, has little influence on the ozone layer and global warming, has high cycle performance, is excellent in safety, and further has lubricity of the working medium for heat cycle.
  • the purpose is to provide an improved thermal cycle system.
  • the present invention provides a working medium for heat cycle, a composition for heat cycle system, and a heat cycle system having the configurations described in [1] to [14] below.
  • a thermal cycle system composition comprising a thermal cycle working medium and refrigeration oil, wherein the thermal cycle working medium comprises trifluoroethylene, 1,1,1,2-tetrafluoroethane, Containing pentafluoroethane and 2,3,3,3-tetrafluoropropene, and trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane and 2 with respect to the total mass of the working fluid for thermal cycle , 3,3,3-tetrafluoropropene is more than 90% by mass and less than 100% by mass, and trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane and 2 , 3,3,3-tetrafluoropropene, the ratio of trifluoroethylene is 3% by mass to 35% by mass, 1,1,1, -The ratio of tetrafluoroethane is 10 mass% to 53 mass%, the ratio of pentafluoroethanethan
  • a composition for a heat cycle system comprising at least 1% by mass, wherein the refrigerating machine oil comprises at least one selected from an ester refrigerating machine oil, an ether refrigerating machine oil, and an alkylbenzene.
  • the working medium for thermal cycle is trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane and 2,3,3,3-tetrafluoropropene with respect to the total amount.
  • the proportion of ethylene is 6% by mass to 25% by mass
  • the proportion of 1,1,1,2-tetrafluoroethane is 20% by mass to 35% by mass
  • pentafluoroethane is 8% by mass to 30% by mass.
  • composition for a heat cycle system according to [1], wherein the proportion of 2,3,3,3-tetrafluoropropene is 20% by mass or more and 50% by mass or less.
  • Composition for thermal cycle system [4] The composition for a heat cycle system according to any one of [1] to [3], wherein the refrigerating machine oil has a kinematic viscosity at 40 ° C.
  • composition for a heat cycle system according to any one of [1] to [4], wherein the refrigerating machine oil has a kinematic viscosity at 100 ° C. of 1 to 100 mm 2 / s.
  • the thermal cycle system according to any one of [1] to [5], wherein the base oil component of the refrigerating machine oil has a carbon atom to oxygen atom ratio (carbon / oxygen molar ratio) of 2 to 7.5.
  • Composition Composition.
  • thermal cycle system according to any one of [1] to [9], wherein the thermal cycle working medium further includes a hydrofluoroolefin other than trifluoroethylene and 2,3,3,3-tetrafluoropropene.
  • Composition [11] The composition for a heat cycle system according to [10], wherein the hydrofluoroolefin is 1,3,3,3-tetrafluoropropene.
  • the thermal cycle system according to [12] wherein a ratio of trifluoroethylene in the gas phase formed in the thermal cycle system is 50% by mass or less.
  • the thermal cycle system according to [12] or [13], wherein the thermal cycle system is a refrigeration / refrigeration device, an air conditioning device, a power generation system, a heat transport device, or a secondary cooler.
  • a composition for a thermal cycle system containing trifluoroethylene is nonflammable, ozone while fully utilizing the low global warming potential and excellent cycle performance of HFO-1123. It is possible to provide a composition for a heat cycle system that has less influence on the layer and that can more stably lubricate a working medium for heat cycle containing HFO-1123.
  • the thermal cycle system of the present invention is non-flammable, has little impact on global warming, has high safety by applying a thermal cycle working medium having high cycle performance, and has little impact on the environment.
  • this is a thermal cycle system with improved thermal cycle performance and improved lubrication characteristics of the thermal cycle working medium.
  • FIG. 2 is a cycle diagram in which a change in state of a working medium in the refrigeration cycle system of FIG. 1 is described on a pressure-enthalpy diagram.
  • composition for a heat cycle system includes a working medium for heat cycle containing HFO-1123, HFC-134a, HFC-125, and HFO-1234yf at a predetermined ratio, and refrigeration oil.
  • working medium for heat cycle is also simply referred to as “working medium”.
  • a heat cycle system using a heat exchanger such as a condenser or an evaporator is used without particular limitation.
  • a heat cycle system for example, a refrigeration cycle
  • a gas working medium is compressed by a compressor, cooled by a condenser to produce a high-pressure liquid, the pressure is reduced by an expansion valve, and vaporized at a low temperature by an evaporator. It has a mechanism that takes heat away with heat.
  • HFO-1123 or HFO-1234yf becomes unstable and self-decomposition occurs depending on the temperature and pressure conditions.
  • the function of the working medium may deteriorate.
  • the above mixture is made incombustible by allowing the refrigerating machine oil to coexist in a working medium containing HFO-1123, HFO-1234yf, HFC-134a, and HFC-125 in a predetermined ratio.
  • each component which the composition for thermal cycle systems of this invention contains is demonstrated.
  • the working medium of the present invention includes HFO-1123, HFC-134a, HFC-125, and HFO-1234yf, and the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf with respect to the total amount of the working medium.
  • the ratio is more than 90% by mass and 100% by mass or less, and the ratio of HFO-1123 to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 3% by mass to 35% by mass,
  • the ratio of HFC-134a is preferably 10% by mass to 53% by mass
  • the ratio of HFC-125 is 4% by mass to 50% by mass
  • the ratio of HFO-1234yf is preferably 5% by mass to 50% by mass.
  • the working medium of the present invention includes HFO-1123, HFC-134a, HFC-125, and HFO-1234yf, and the total of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf with respect to the total amount of the working medium.
  • the ratio of the amount is more than 90% by mass and not more than 100% by mass, and the ratio of HFO-1123 to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 6% by mass or more and 25% by mass
  • the ratio of HFC-134a is 20% by mass to 35% by mass
  • the ratio of HFC-125 is 8% by mass to 30% by mass
  • the ratio of HFO-1234yf is 20% by mass to 50% by mass. Even more preferred.
  • the working medium is non-flammable, and is more excellent in safety, has less influence on the ozone layer and global warming, and is even better when used in a heat cycle system.
  • the working medium having a high cycle performance can be obtained.
  • HFO other than HFO-1123 and HFO-1234yf examples include 1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf), 1,1,2-trifluoropropene (HFO-1243yc), Trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)), 3,3,3- Trifluoropropene (HFO-1243zf), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), cis-1,2,3,3,3-pentafluoropropene (HFO) -1225ye (Z)) and the like. HFOs other than HFO-1123 and HFO-1234yf may be used alone or in combination of two or more.
  • the ratio of the total mass of the HFO to the total mass (100% by mass) of the working medium in the system is 10% by mass or less. % By mass is preferable, and 2 to 10% by mass is more preferable.
  • HFCs other than HFC-134a and HFC-125 are components that improve the cycle performance (capability) of the thermal cycle system.
  • HFCs other than HFC-134a and HFC-125 HFCs that have little influence on the ozone layer and little influence on global warming are preferable.
  • HFCs other than HFC-134a and HFC-125 include difluoromethane, difluoroethane, trifluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane, and the like.
  • difluoromethane (HFC-32) and 1,1-difluoroethane (HFC-152a) are particularly preferable because they have little influence on the ozone layer and little influence on global warming.
  • HFCs other than HFC-134a and HFC-125 may be used alone or in combination of two or more.
  • the content of HFC other than HFC-134a and HFC-125 can be controlled according to the required characteristics of the working medium.
  • the working medium includes HFCs other than HFC-134a and HFC-125
  • the ratio of the total mass of the HFC to the total mass (100% by mass) of the working medium in the system is 10% by mass or less. % By mass is preferable, and 2 to 10% by mass is more preferable.
  • hydrocarbon is a component which improves the solubility to the working medium of the mineral oil mentioned later.
  • examples of the hydrocarbon include propane, propylene, cyclopropane, butane, isobutane, pentane, isopentane and the like.
  • a hydrocarbon may be used individually by 1 type and may be used in combination of 2 or more type.
  • the ratio of the total mass of hydrocarbons to the total mass (100% by mass) of the working medium in the system is preferably 10% by mass or less, preferably 1 to 10% by mass, and 2 to 5%. The mass% is more preferable. If the ratio of the total mass of the hydrocarbon is not less than the lower limit value, the solubility of the lubricating oil in the working medium becomes good. If the ratio of the total mass of the hydrocarbon is equal to or less than the upper limit value, it is easy to suppress the combustibility of the working medium.
  • HCFO and CFO are components that suppress the combustibility of the working medium and improve the solubility of the lubricating oil in the working medium.
  • HCFO and CFO having a small influence on the ozone layer and a small influence on global warming are preferable.
  • HCFO examples include hydrochlorofluoropropene and hydrochlorofluoroethylene.
  • hydrochlorofluoropropene examples include hydrochlorofluoropropene and hydrochlorofluoroethylene.
  • HCFO- 1-chloro-2,3,3,3-tetrafluoropropene
  • HCFO-1122 1-chloro-1,2-difluoroethylene
  • HCFO may be used alone or in combination of two or more.
  • CFO examples include chlorofluoropropene and chlorofluoroethylene.
  • 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO) is used from the viewpoint of sufficiently suppressing the flammability of the working medium without greatly reducing the cycle performance (capacity) of the thermal cycle system.
  • CFO-1112 1,2-dichloro-1,2-difluoroethylene
  • the ratio of the total mass of HCFO and CFO to the total mass (100% by mass) of the working medium in the system is 10% by mass or less. 10 mass% is preferable.
  • Chlorine atoms have the effect of suppressing flammability, and the addition of HCFO and CFO can sufficiently suppress the flammability of the working medium without significantly reducing the cycle performance (capability) of the thermal cycle system. .
  • Examples of other compounds include alcohols having 1 to 4 carbon atoms, or compounds used as conventional working media, refrigerants, and heat transfer media. Also, perfluoropropyl methyl ether (C 3 F 7 OCH 3 ), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ), perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ), 1, 1, 2, 2 Fluorine-containing ethers such as tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF 2 HCF 2 OCH 2 CF 3 , manufactured by Asahi Glass Co., Ltd., AE-3000) may be used.
  • perfluoropropyl methyl ether C 3 F 7 OCH 3
  • perfluorobutyl methyl ether C 4 F 9 OCH 3
  • perfluorobutyl ethyl ether C 4 F 9 OC 2 H 5
  • the ratio of the total mass of other compounds to the total mass (100 mass%) of the working medium in the system may be in a range that does not significantly reduce the effect of the present invention, and is 10 mass% or less, and 8 mass% or less. Preferably, 6 mass% or less is more preferable.
  • GWP when used in a thermal cycle in combination with HFO-1123, HFC-134a, HFC-125 and HFO-1234yf, GWP has the effect of further increasing the relative coefficient of performance and the relative refrigeration capacity, which will be described later. And a compound that can keep the temperature gradient within an acceptable range is preferable.
  • the working medium contains such a compound in combination with the above-mentioned working medium mixture, a better cycle performance can be obtained while keeping the GWP low, and the influence of the temperature gradient is small.
  • GWP Global warming potential
  • IPCC Intergovernmental Panel on climate Change
  • the global warming potential (100 years) of HFO-1123 contained in the working medium used in the present invention is 0.3. This value is much smaller than GWP of other HFOs, for example, 6 of HFO-1234ze, 4 of HFO-1234yf, and the like.
  • R410A HFC-125 and HFC-32 and HFC-32 used in air conditioning applications such as room air conditioners, store packaged air conditioners, building packaged air conditioners, and facility packaged air conditioners to be replaced by the working medium used in the present invention.
  • the 1: 1 (mass) composition) has a very high GWP of 2088.
  • R404A HFC-125 and 1,1,1-trifluoroethane (HFC-143a) and HFC, which are used for freezing and refrigeration applications such as built-in showcases, stand-alone showcases, and commercial refrigeration / refrigerators.
  • the 11: 13: 1 (mass) composition with -134a) has a GWP that is twice as large as 3922 and R410A.
  • the working medium used in the present invention preferably has a small global warming potential from the viewpoint of the effect on global warming.
  • the GWP of the working medium used in the present invention is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1000 or less.
  • GWP2000 is about 50% of R404A used for freezing and refrigeration applications
  • GWP1000 is about 25% of R404A and about 50% of R410A used for air conditioning applications. It shows that the influence can be reduced.
  • the GWP in the mixture is a weighted average based on the composition mass.
  • the working medium of the present invention contains optional components other than HFO-1123, HFC-134a, and HFC-125
  • the GWP per unit mass of the optional component is further weighted averaged by the composition mass, The GWP of the working medium can be obtained.
  • the composition for a heat cycle system of the present invention comprises a refrigerating machine oil capable of improving the lubrication characteristics of the working medium including HFO-1123, HFC-134a, HFC-125 and HFO-1234yf in addition to the above working medium. .
  • refrigerating machine oil used in the present invention examples include ester refrigerating machine oil, ether refrigerating machine oil, hydrocarbon refrigerating machine oil, and the like.
  • an oxygen-containing synthetic refrigerating machine oil such as an ester refrigerating machine oil, an ether refrigerating machine oil, or a polyglycol based refrigerating machine oil is preferable. More preferred are system refrigerating machine oil and ether type refrigerating machine oil.
  • the kinematic viscosity at 40 ° C. of the refrigeration oil does not decrease the lubricity and the hermeticity of the compressor, and is satisfactory in compatibility with the working medium under low temperature conditions. From the viewpoint of sufficient heat exchange in the evaporator, 1 to 750 mm 2 / s is preferable, and 1 to 400 mm 2 / s is more preferable.
  • the kinematic viscosity at 100 ° C. is preferably 1 to 100 mm 2 / s, more preferably 1 to 50 mm 2 / s from the viewpoint of maintaining power consumption and wear resistance within an appropriate range.
  • carbon atoms and oxygen atoms are typically cited as the atoms constituting the refrigerating machine oil. If the ratio of carbon atoms to oxygen atoms (carbon / oxygen molar ratio) is too small, the hygroscopicity is increased, and if it is too large, the compatibility with the working medium is lowered. From this viewpoint, the molar ratio of the carbon atom and oxygen atom in the base oil component of the refrigerating machine oil is suitably 2 to 7.5.
  • hydrocarbon-based refrigeration oil is required to circulate both the working medium and the refrigeration oil in the heat cycle system. It is most preferable that the refrigerating machine oil dissolves in the working medium. However, if a refrigerating machine oil that can circulate the refrigerating machine oil and the working medium in the heat cycle system is selected, a refrigerating machine oil having a low solubility (for example, in Japanese Patent No. 2803451).
  • the refrigerating machine oils described can be used as one component of the composition for a thermal cycle system of the present invention.
  • the refrigerating machine oil is required to have a low kinematic viscosity.
  • the kinematic viscosity of the hydrocarbon refrigerating machine oil is preferably 1 to 50 mm 2 / s at 40 ° C., particularly preferably 1 to 25 mm 2 / s.
  • These refrigerating machine oils may contain a stabilizer in order to prevent the working medium, base oil components and the like from being deteriorated.
  • Additives include oxidation resistance improvers, heat resistance improvers, metal deactivators, and the stabilizer content may be in a range that does not significantly reduce the effects of the present invention. In an object (100 mass%), it is 5 mass% or less normally, and 3 mass% or less is preferable.
  • ester-based refrigerating machine oil in terms of chemical stability, dibasic acid ester of dibasic acid and monohydric alcohol, polyol ester of polyol and fatty acid, or polyol, polybasic acid and monohydric alcohol ( Or, a complex ester with a fatty acid), a polyol carbonate ester and the like are mentioned as the base oil component.
  • Dibasic acid esters include dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, A dibasic acid having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and a monohydric alcohol having 1 to 15 carbon atoms having a linear or branched alkyl group (methanol) , Ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecan
  • dibasic ester refrigerating machine oil examples include ditridecyl glutarate, di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, di (3-ethylhexyl) sebacate and the like.
  • the polyol ester is an ester synthesized from a polyhydric alcohol and a fatty acid (carboxylic acid), and has a carbon / oxygen molar ratio of 2 to 7.5, preferably 3.2 to 5.8. .
  • polyhydric alcohol constituting the polyol ester examples include diols (ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol.
  • 1,5-pentanediol neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1 , 3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12 -Dodecanediol, etc.), polyols having 3 to 20 hydroxyl groups (trimethylolethane, Tylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- (pentaeryth
  • the number of carbon atoms is not particularly limited, but those having 1 to 24 carbon atoms are usually used.
  • Straight chain fatty acids and branched fatty acids are preferred.
  • Linear fatty acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid , Heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, oleic acid, linoleic acid, linolenic acid, etc., and the hydrocarbon group bonded to the carboxyl group may be all saturated hydrocarbons or unsatur
  • branched fatty acids include 2-methylpropanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid 2,2-dimethylbutanoic acid, 2,3-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2 , 2-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 3,4-dimethylpentanoic acid, 4,4-dimethylpentanoic acid, 2-ethyl Pentanoic acid, 3-ethylpentanoic acid, 2,2,3-trimethylbutanoic acid
  • the polyol constituting the ester may be one kind or a mixture of two or more kinds.
  • the fatty acid which comprises ester may be 1 type, and 2 or more types of mixtures may be sufficient as it.
  • the polyol ester refrigerating machine oil may have a free hydroxyl group.
  • Specific polyol esters include neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (pentaerythritol), More preferred are esters of hindered alcohols such as tri- (pentaerythritol), even more preferred are esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol, di- (pentaerythritol). Preference is given to esters of pentyl glycol, trimethylolpropane, pentaerythritol, di- (pentaerythritol) and the like with fatty acids having 2 to 20 carbon atoms.
  • the fatty acid may be only a fatty acid having a linear alkyl group or may be selected from fatty acids having a branched structure. Moreover, the mixed ester of a linear and branched fatty acid may be sufficient. Furthermore, the fatty acid which comprises ester may use 2 or more types chosen from the said fatty acid.
  • the molar ratio of the linear fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms is 15:85 to 90:10, preferably 15:85 to 85:15, more preferably 20:80 to 80:20, still more preferably 25:75 to 75:25, and most preferably 30:70. ⁇ 70: 30.
  • the total ratio of the straight chain fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms in the total amount of fatty acids constituting the polyhydric alcohol fatty acid ester is 20 mol% or more.
  • the fatty acid composition should be selected in consideration of sufficient compatibility with the working medium and compatibility with the viscosity required for refrigerating machine oil.
  • the ratio of the fatty acid here is a value based on the total amount of fatty acids constituting the polyhydric alcohol fatty acid ester contained in the refrigerating machine oil.
  • Complex esters are esters of fatty acids and dibasic acids with monohydric alcohols and polyols.
  • fatty acid, dibasic acid, monohydric alcohol, and polyol the same ones as described above can be used.
  • fatty acid As fatty acid, what was shown with the fatty acid of the said polyol ester is mentioned.
  • dibasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.
  • polyol examples include those shown as the polyhydric alcohol of the above polyol ester.
  • Complex esters are esters of these fatty acids, dibasic acids, and polyols, and each may be a single component or an ester composed of a plurality of components.
  • the polyol carbonate ester is an ester of carbonic acid and polyol.
  • Polyols include polyglycols (polyalkylene glycols, ether compounds thereof, modified compounds thereof, etc.) obtained by homopolymerization or copolymerization of diols (same as above), polyols (same as above), polyols and polyglycols. And the like added.
  • polyalkylene glycol examples include those obtained by polymerizing C 2-4 alkylene oxide (ethylene oxide, propylene oxide, etc.) using water or alkali hydroxide as an initiator. Moreover, what etherified the hydroxyl group of polyalkylene glycol may be used.
  • the oxyalkylene units in the polyalkylene glycol may be the same in one molecule, or two or more oxyalkylene units may be included. It is preferable that at least an oxypropylene unit is contained in one molecule.
  • the polyol carbonate refrigerating machine oil may be a ring-opening polymer of cyclic alkylene carbonate.
  • Examples of the base oil component of the ether refrigerating machine oil include polyvinyl ether and polyalkylene glycol.
  • Polyvinyl ethers include those obtained by polymerizing vinyl ether monomers, those obtained by copolymerizing vinyl ether monomers and hydrocarbon monomers having olefinic double bonds, and polyvinyl ether and alkylene glycol or polyalkylene. There are glycols or their copolymers with monoethers.
  • the carbon / oxygen molar ratio of polyvinyl ether is 2 or more and 7.5 or less, preferably 2.5 or more and 5.8 or less. If the carbon / oxygen molar ratio is less than this range, the hygroscopicity is high, and if it exceeds this range, the compatibility is lowered.
  • the weight average molecular weight of polyvinyl ether is preferably 200 or more and 3000 or less, more preferably 500 or more and 1500 or less.
  • Kinematic viscosity at 40 ° C. it is preferably 1 ⁇ 750mm 2 / s kinematic viscosity at 40 °C, 1 ⁇ 400mm 2 / s is more preferable.
  • the kinematic viscosity at 100 ° C. is preferably 1 to 100 mm 2 / s, and more preferably 1 to 50 mm 2 / s.
  • a vinyl ether monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • hydrocarbon monomers having an olefinic double bond include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, ⁇ -methylstyrene, various alkyl-substituted styrenes, etc. Is mentioned.
  • the hydrocarbon monomer which has an olefinic double bond may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the polyvinyl ether copolymer may be either a block or a random copolymer.
  • One type of polyvinyl ether refrigerating machine oil may be used alone, or two or more types may be used in combination.
  • Preferably used polyvinyl ether has a structural unit represented by the following general formula (1).
  • R 1 , R 2 and R 3 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; R 4 is a divalent carbon atom having 1 to 10 carbon atoms
  • R 2 represents a hydrogen group or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms
  • R 5 represents a hydrocarbon group having 1 to 20 carbon atoms
  • m represents an average value of m for the polyvinyl ether.
  • R 1 to R 5 may be the same or different for each structural unit, and when m is 2 or more in one structural unit, a plurality of R 4 O may be the same or different.
  • R 1 , R 2 and R 3 is preferably a hydrogen atom, particularly preferably a hydrogen atom.
  • M in the general formula (1) is 0 or more and 10 or less, particularly 0 or more and 5 or less, and more preferably 0.
  • R 5 in the general formula (1) represents a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, and various hexyl groups.
  • Alkyl groups such as various heptyl groups and various octyl groups, cyclopentyl groups, cyclohexyl groups, various methyl cyclohexyl groups, various ethyl cyclohexyl groups, various dimethyl cyclohexyl groups and other cycloalkyl groups, phenyl groups, various methyl phenyl groups, various ethyl phenyls Groups, aryl groups such as various dimethylphenyl groups, arylalkyl groups such as benzyl groups, various phenylethyl groups, and various methylbenzyl groups. Alkyl groups, particularly alkyl groups having 1 to 5 carbon atoms are preferred.
  • the polyvinyl ether in the present embodiment may be a homopolymer having the same structural unit represented by the general formula (1) or a copolymer composed of two or more structural units.
  • the copolymer may be a block copolymer or a random copolymer.
  • the polyvinyl ether according to the present embodiment may be composed only of the structural unit represented by the general formula (1), but may further include a structural unit represented by the following general formula (2). It may be a polymer. In this case, the copolymer may be a block copolymer or a random copolymer.
  • R 6 to R 9 may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • vinyl ether monomers include those corresponding to the above-mentioned polyvinyl ether, such as vinyl methyl ether; vinyl ethyl ether; vinyl-n-propyl ether; vinyl-isopropyl ether; vinyl-n-butyl ether; Vinyl-sec-butyl ether; vinyl-tert-butyl ether; vinyl-n-pentyl ether; vinyl-n-hexyl ether; vinyl-2-methoxyethyl ether; vinyl-2-ethoxyethyl ether; 1-methylethyl ether; vinyl-2-methoxy-propyl ether; vinyl-3,6-dioxaheptyl ether; vinyl-3,6,9-trioxadecyl ether; vinyl-1,4-dimethyl-3,6 -The Oxaheptyl ether; vinyl-1,4,7-trimethyl-3,6,9-trioxadecyl ether; vinyl-2,6-dioxa
  • the polyvinyl ether having the structural unit represented by the above general formula (1) used as a refrigerating machine oil in the composition for a heat cycle system of the present invention has a method of indicating the terminal in the disclosed example and a known one.
  • the method can be converted into a desired structure.
  • Examples of the group to be converted include saturated hydrocarbons, ethers, alcohols, ketones, amides, and nitriles.
  • the polyvinyl ether used as the refrigerating machine oil in the composition for a heat cycle system of the present invention preferably has a terminal structure represented by the following formulas (4) to (8).
  • R 11 , R 21 and R 31 may be the same or different from each other and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms;
  • R 41 is a divalent divalent having 1 to 10 carbon atoms;
  • R 51 represents a hydrocarbon group having 1 to 20 carbon atoms, and
  • m represents an average value of m for polyvinyl ether of 0
  • the plurality of R 41 Os may be the same or different.
  • R 61 , R 71 , R 81 and R 91 may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 12 , R 22 and R 32 may be the same as or different from each other, each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 42 is a divalent divalent hydrocarbon having 1 to 10 carbon atoms.
  • R 2 represents a hydrocarbon group or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms
  • R 52 represents a hydrocarbon group having 1 to 20 carbon atoms
  • m represents an average value of m for polyvinyl ether is 0.
  • the plurality of R 42 Os may be the same or different.
  • R 62 , R 72 , R 82 and R 92 may be the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 13 , R 23 and R 33 may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
  • the polyvinyl ether in the present embodiment can be produced by radical polymerization, cationic polymerization, radiation polymerization or the like of the above-described monomer. After completion of the polymerization reaction, a polyvinyl ether compound having the target structural unit represented by the general formula (1) can be obtained by subjecting to an ordinary separation / purification method as necessary.
  • polyalkylene glycol examples include those obtained by polymerizing alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, etc.) using water or alkali hydroxide as an initiator. Moreover, what etherified the hydroxyl group of polyalkylene glycol may be used.
  • the oxyalkylene units in the polyalkylene glycol refrigerating machine oil may be the same in one molecule, or two or more oxyalkylene units may be included. It is preferable that at least an oxypropylene unit is contained in one molecule.
  • R 101 As specific polyalkylene glycol, for example, the following general formula (9) R 101 -[(OR 102 ) k -OR 103 ] l (9) (Wherein R 101 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding parts, R 102 Is an alkylene group having 2 to 4 carbon atoms, R 103 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, l is an integer of 1 to 6, and k is an average value of k ⁇ l Is a number from 6 to 80.).
  • the alkyl group in R 101 and R 103 may be linear, branched or cyclic.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Cyclopentyl group, cyclohexyl group and the like. When the number of carbon atoms of the alkyl group exceeds 10, compatibility with the working medium is lowered, and rough separation may occur.
  • the alkyl group preferably has 1 to 6 carbon atoms.
  • the alkyl group portion of the acyl group in R 101 and R 103 may be linear, branched or cyclic.
  • various groups having 1 to 9 carbon atoms exemplified as specific examples of the alkyl group can be exemplified.
  • compatibility with the working medium may be reduced and phase separation may occur.
  • a preferred acyl group has 2 to 6 carbon atoms.
  • R 101 and R 103 are both alkyl groups or acyl groups, R 101 and R 103 may be the same or different from each other. Further, when l is 2 or more, a plurality of R 103 in one molecule may be the same or different.
  • R 101 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding sites
  • the aliphatic hydrocarbon group may be a chain or a cyclic one. Also good.
  • Examples of the aliphatic hydrocarbon group having two binding sites include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, cyclopentylene group, and cyclohexylene. Group and the like.
  • Examples of the aliphatic hydrocarbon group having 3 to 6 binding sites include trimethylolpropane, glycerin, pentaerythritol, sorbitol; 1,2,3-trihydroxycyclohexane; 1,3,5-trihydroxycyclohexane. Examples thereof include a residue obtained by removing a hydroxyl group from a polyhydric alcohol.
  • the compatibility with the working medium is lowered, and phase separation may occur.
  • a preferred carbon number is 2-6.
  • R 102 in the general formula (9) is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • the oxyalkylene groups in one molecule may be the same or two or more oxyalkylene groups may be contained, but those containing at least an oxypropylene unit in one molecule are preferred, and in particular, oxyalkylene units. Those containing 50 mol% or more of oxypropylene units are preferred.
  • l is an integer of 1 to 6, and is determined according to the number of R 101 binding sites.
  • R 101 is an alkyl group or an acyl group
  • l is 1, and when R 101 is an aliphatic hydrocarbon group having 2, 3, 4, 5, and 6 binding sites, l is 2, 3 respectively. , 4, 5 and 6.
  • k is a number with an average value of k ⁇ l of 6 to 80, and if the average value of k ⁇ l deviates from the above range, the object of the present invention cannot be sufficiently achieved.
  • polyalkylene glycol is such that polypropylene glycol dimethyl ether represented by the following general formula (10) and poly (oxyethyleneoxypropylene) glycol dimethyl ether represented by the following general formula (11) are economical and have the aforementioned effects.
  • a polypropylene glycol monobutyl ether represented by the following general formula (12), a polypropylene glycol monomethyl ether represented by the following general formula (13), and a polyglycol represented by the following general formula (14) (Oxyethyleneoxypropylene) glycol monomethyl ether, poly (oxyethyleneoxypropylene) glycol monobutyl ether represented by the following general formula (15), polypropylene glycol diacetate represented by the following general formula (16), It is preferable in terms of gender, and the like.
  • Kinematic viscosity at 40 ° C. of polyalkylene glycol represented by the above general formula (9) is preferably 1 ⁇ 750mm 2 / s kinematic viscosity at 40 °C, 1 ⁇ 400mm 2 / s is more preferable.
  • the kinematic viscosity at 100 ° C. is preferably 1 to 100 mm 2 / s, and more preferably 1 to 50 mm 2 / s.
  • Alkyl benzene is mentioned as a base oil component of hydrocarbon refrigerating machine oil.
  • alkylbenzene branched alkylbenzene synthesized using propylene polymer and benzene as raw materials using a catalyst such as hydrogen fluoride, and linear alkylbenzene synthesized using normal paraffin and benzene as raw materials using the same catalyst can be used.
  • the number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 4 to 20, from the viewpoint of obtaining a viscosity suitable as a base oil component of a lubricating oil.
  • the number of alkyl groups contained in one molecule of alkylbenzene is preferably 1 to 4, more preferably 1 to 3, in order to keep the viscosity within a set range depending on the number of carbon atoms of the alkyl group.
  • the refrigeration oil is required to circulate in the heat cycle system together with the working medium. It is most preferable that the refrigerating machine oil dissolves with the working medium, but if a refrigerating machine oil that can circulate the refrigerating machine oil and the working medium in the heat cycle system is selected, the refrigerating machine oil with low solubility is used as the refrigerating machine oil composition of the present invention. Can be used.
  • the refrigerating machine oil is required to have a low kinematic viscosity.
  • the kinematic viscosity of alkylbenzene at 40 ° C. is preferably 1 to 50 mm 2 / s, particularly preferably 1 to 25 mm 2 / s.
  • These refrigeration oils may be used alone or in combination of two or more.
  • These refrigerating machine oils are preferably mixed with a working medium and used as a composition for a heat cycle system.
  • the blending ratio of the refrigerating machine oil is desirably 5 to 60% by mass and more preferably 10 to 50% by mass with respect to the total amount of the composition for a heat cycle system.
  • composition for thermal cycle systems can contain known optional components as long as the effects of the present invention are not impaired.
  • optional components include known stabilizers and leak detection materials conventionally used in thermal cycle system compositions, and these optional leak detection materials include ultraviolet fluorescent dyes and odorous gases. And odor masking agents.
  • the ultraviolet fluorescent dyes are described in U.S. Pat. No. 4,249,412, JP-T-10-502737, JP-T 2007-511645, JP-T 2008-500437, JP-T 2008-531836.
  • odor masking agent examples include known fragrances used in heat cycle systems, together with working media composed of halogenated hydrocarbons, such as those described in JP-T-2008-500337 and JP-A-2008-531836. Can be mentioned.
  • a solubilizing agent that improves the solubility of the leak detection substance in the working medium may be used.
  • solubilizer examples include those described in JP-T 2007-511645, JP-T 2008-500337, JP-T 2008-531836.
  • the content of the leak detection substance in the composition for a heat cycle system may be in a range that does not significantly reduce the effect of the present invention, and is preferably 2 parts by mass or less, based on 100 parts by mass of the working medium, and 0.5 mass. Part or less is more preferable.
  • the thermal cycle system of the present invention is a system using the composition for a thermal cycle system of the present invention.
  • the heat cycle system of the present invention may be a heat pump system that uses warm heat obtained by a condenser, or may be a refrigeration cycle system that uses cold heat obtained by an evaporator.
  • thermal cycle system of the present invention examples include refrigeration / refrigeration equipment, air conditioning equipment, power generation systems, heat transport devices, and secondary coolers.
  • the thermal cycle system of the present invention can exhibit thermal cycle performance efficiently even in a higher temperature operating environment, it is preferably used as an air conditioner that is often installed outdoors.
  • the thermal cycle system of the present invention is also preferably used as a refrigeration / refrigeration apparatus.
  • air conditioners include room air conditioners, packaged air conditioners (store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, etc.), gas engine heat pumps, train air conditioners, automobile air conditioners, and the like.
  • refrigeration / refrigeration equipment include showcases (built-in showcases, separate showcases, etc.), commercial freezers / refrigerators, vending machines, ice makers, and the like.
  • a power generation system using a Rankine cycle system is preferable.
  • the working medium is heated by geothermal energy, solar heat, waste heat in the middle to high temperature range of about 50 to 200 ° C in the evaporator, and the working medium turned into high-temperature and high-pressure steam is expanded.
  • An example is a system in which power is generated by adiabatic expansion by a machine, and a generator is driven by work generated by the adiabatic expansion.
  • the heat cycle system of the present invention may be a heat transport device.
  • a latent heat transport device is preferable.
  • the latent heat transport device include a heat pipe and a two-phase sealed thermosyphon device that transport latent heat using phenomena such as evaporation, boiling, and condensation of a working medium enclosed in the device.
  • the heat pipe is applied to a relatively small cooling device such as a cooling device for a heat generating part of a semiconductor element or an electronic device. Since the two-phase closed thermosyphon does not require a wig and has a simple structure, it is widely used for a gas-gas heat exchanger, for promoting snow melting on roads, and for preventing freezing.
  • the refrigeration cycle system is a system that uses cold heat obtained by an evaporator.
  • a refrigeration cycle system 10 shown in FIG. 1 cools and liquefies a compressor 11 that compresses the working medium vapor A into a high-temperature and high-pressure working medium vapor B and the working medium vapor B discharged from the compressor 11.
  • the condenser 12 as a low-temperature and high-pressure working medium C
  • the expansion valve 13 that expands the working medium C discharged from the condenser 12 to form a low-temperature and low-pressure working medium D
  • the working medium D discharged from the expansion valve 13 Is composed of an evaporator 14 that heats the working medium vapor A to a high-temperature and low-pressure working medium vapor A, a pump 15 that supplies a load fluid E to the evaporator 14, and a pump 16 that supplies a fluid F to the condenser 12.
  • the working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to obtain a low-temperature and low-pressure working medium D (hereinafter referred to as “CD process”).
  • the working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to obtain high-temperature and low-pressure working medium vapor A. At this time, the load fluid E is cooled to become the load fluid E ′ and discharged from the evaporator 14 (hereinafter referred to as “DA process”).
  • the refrigeration cycle system 10 is a cycle system including adiabatic / isoentropic change, isoenthalpy change, and isopressure change.
  • the state change of the working medium is described on the pressure-enthalpy line (curve) diagram shown in FIG. 2, it can be expressed as a trapezoid having A, B, C, and D as apexes.
  • the AB process is a process in which adiabatic compression is performed by the compressor 11 to convert the high-temperature and low-pressure working medium vapor A into a high-temperature and high-pressure working medium vapor B, which is indicated by an AB line in FIG.
  • the BC process is a process in which the condenser 12 performs isobaric cooling to convert the high-temperature and high-pressure working medium vapor B into a low-temperature and high-pressure working medium C, and is indicated by a BC line in FIG.
  • the pressure at this time is the condensation pressure.
  • Pressure - an intersection T 1 of the high enthalpy side condensing temperature of the intersection of the enthalpy and BC line, the low enthalpy side intersection T 2 is the condensation boiling temperature.
  • the temperature gradient in the case where HFO-1123 is a mixed medium with another working medium and is a non-azeotropic mixed medium is shown as a difference between T 1 and T 2 .
  • the CD process is a process in which the enthalpy expansion is performed by the expansion valve 13 and the low-temperature and high-pressure working medium C is used as the low-temperature and low-pressure working medium D, and is indicated by a CD line in FIG.
  • T 2 -T 3 is (i) ⁇ supercooling degree of the working medium in the cycle of (iv) (hereinafter, optionally in the "SC" It is shown.)
  • the DA process is a process of performing isobaric heating in the evaporator 14 to return the low-temperature and low-pressure working medium D to the high-temperature and low-pressure working medium vapor A, and is indicated by a DA line in FIG.
  • T 6 The pressure at this time is the evaporation pressure.
  • Pressure - intersection T 6 of the high enthalpy side of the intersection of the enthalpy and DA line is evaporating temperature. If Shimese the temperature of the working medium vapor A in T 7, T 7 -T 6 is (i) ⁇ superheat of the working medium in the cycle of (iv) a (hereinafter,. Indicated by "SH", if necessary) .
  • T 4 indicates the temperature of the working medium D.
  • the cycle performance of the working medium is evaluated by, for example, the refrigerating capacity of the working medium (hereinafter, indicated as “Q” as necessary) and the coefficient of performance (hereinafter, indicated as “COP” as necessary).
  • Q and COP of the working medium in each state of A after evaporation, high temperature and low pressure
  • B after compression, high temperature and high pressure
  • C after condensation, low temperature and high pressure
  • D after expansion, low temperature and low pressure.
  • COP means efficiency in the refrigeration cycle system. The higher the COP value, the smaller the input, for example, the amount of power required to operate the compressor, and the larger the output, for example, Q can be obtained. It represents what you can do.
  • Q means the ability to freeze the load fluid, and the higher Q means that more work can be done in the same system.
  • a large Q indicates that the target performance can be obtained with a small amount of working medium, and the system can be miniaturized.
  • both the Q and COP are high, that is, equivalent to R410A, while keeping the global warming coefficient much lower. It is possible to set a level higher than that.
  • the composition that keeps the temperature gradient of the working medium contained in the composition for the heat cycle system to be a certain value or less, in which case, the composition change when filling from the pressure vessel to the refrigeration air conditioner, A change in the refrigerant composition in the refrigeration air conditioner when the refrigerant leaks from the refrigeration air conditioner can be suppressed to a low level.
  • the composition for a heat cycle system of the present invention since the lubrication characteristics of the working medium containing HFO-1123 and HFO-1234yf can be improved, the heat cycle system using the composition is more effective than the conventional working medium. An efficient circulation state can be maintained, and the system can be operated stably.
  • the thermal cycle system of the present invention is preferably controlled so that the proportion of HFO-1123 in the gas phase formed in the system is 50% by mass or less. If it is a working medium which has the said composition, normally this condition is satisfy
  • a method for controlling the moisture concentration in the thermal cycle system a method using a moisture removing means such as a desiccant (silica gel, activated alumina, zeolite, etc.) can be mentioned.
  • the desiccant is preferably brought into contact with the liquid thermal cycle system composition in terms of dehydration efficiency. For example, it is preferable to place a desiccant at the outlet of the condenser 12 or the inlet of the evaporator 14 to contact the composition for the thermal cycle system.
  • a zeolitic desiccant is preferable from the viewpoint of chemical reactivity between the desiccant and the composition for the heat cycle system and the moisture absorption capacity of the desiccant.
  • the main component is a compound represented by the following formula (C) because it has a high hygroscopic capacity.
  • Zeolite desiccants are preferred.
  • M is a Group 1 element such as Na or K, or a Group 2 element such as Ca
  • n is a valence of M
  • x and y are values determined by a crystal structure. .
  • pore diameter and breaking strength are important.
  • the working medium or the desiccant having a pore size larger than the molecular diameter of the refrigerating machine oil contained in the composition for the heat cycle system is used, the working medium or the refrigerating machine oil is adsorbed in the desiccant, and as a result, the working medium or A chemical reaction occurs between the refrigerating machine oil and the desiccant, and undesired phenomena such as generation of non-condensable gas, a decrease in the strength of the desiccant, and a decrease in adsorption capacity occur.
  • a zeolitic desiccant having a small pore size as the desiccant.
  • a sodium / potassium A type synthetic zeolite having a pore diameter of 3.5 angstroms or less is preferable.
  • sodium / potassium type A synthetic zeolite having a pore size smaller than the molecular diameter of the working medium or refrigerating machine oil only the water in the heat cycle system is selectively absorbed without adsorbing the working medium or refrigerating machine oil. Can be removed by adsorption. In other words, the adsorption of the working medium and the refrigerating machine oil to the desiccant is unlikely to occur, so that the thermal decomposition is difficult to occur. As a result, it is possible to suppress the deterioration of the materials constituting the thermal cycle system and the occurrence of contamination.
  • the size of the zeolitic desiccant is preferably about 0.5 to 5 mm because if it is too small, it will cause clogging of valves and piping details of the heat cycle system, and if it is too large, the drying ability will be reduced.
  • the shape is preferably granular or cylindrical.
  • the zeolitic desiccant can be formed into an arbitrary shape by solidifying powdery zeolite with a binder (such as bentonite).
  • a binder such as bentonite
  • Other desiccants silicon gel, activated alumina, etc.
  • the use ratio of the zeolitic desiccant with respect to the composition for a heat cycle system is not particularly limited.
  • non-condensable gas when non-condensable gas is mixed in the heat cycle system, it adversely affects heat transfer in the condenser and the evaporator and increases in operating pressure. Therefore, it is necessary to suppress mixing as much as possible.
  • oxygen which is one of non-condensable gases, reacts with the working medium and refrigerating machine oil to promote decomposition.
  • the non-condensable gas concentration is preferably 1.5% by volume or less, particularly preferably 0.5% by volume or less in terms of volume ratio to the working medium in the gas phase part of the working medium.
  • the composition for the thermal cycle system of the present invention described above, by using the composition for the thermal cycle system of the present invention, the lubrication characteristics are good, nonflammable and high in safety, and the influence on global warming is suppressed. The practically sufficient cycle performance can be obtained, and there is almost no problem with the temperature gradient.
  • HFO-1123, HFC-134a, HFO-1234yf, and HFC-125 are mixed so that the ratio of each medium is as shown in Table 2, and a four-component working medium for heat cycle is prepared.
  • the combustibility when the medium was mixed with air at a ratio of every 10% by mass between 10 and 90% by mass with respect to the air to reach an equilibrium state was evaluated.
  • Combustibility was evaluated as follows using equipment specified in ASTM E-681. After evacuating the interior of a 12-liter flask set in a thermostat controlled at 25 ° C., each working medium mixed with air at the above-mentioned ratio was sealed up to atmospheric pressure. Thereafter, in the gas phase near the center in the flask, the discharge was ignited at 15 kV and 30 mA for 0.4 seconds, and then the spread of the flame was visually recognized. The case where the upward flame spread angle was 90 degrees or more was judged as combustible, and the case where it was less than 90 degrees was judged as non-combustible.
  • Examples 1 to 152 Comparative Examples (Examples 153 to 190).
  • 50 g of refrigerating machine oil was mixed and dissolved in 50 g of the working medium in the combinations shown in Tables 4 to 20 to produce a composition for a heat cycle system. Therefore, the composition for a heat cycle system in this example is composed of 50% by mass of a working medium and 50% by mass of refrigerating machine oil.
  • the compounds constituting the working medium used here are shown together in Table 3. About the working medium of Table 3, it is a working medium of the range which does not have combustibility, and evaluation of the refrigerating cycle performance about a working medium and evaluation of a global warming potential (GWP) were also shown collectively.
  • GWP global warming potential
  • the refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated as the cycle performance (capacity and efficiency) when the working medium was applied to the refrigeration cycle system 10 of FIG.
  • the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
  • the average condensation temperature of the working medium in the condenser 12 is 40 ° C.
  • the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
  • the operation in the evaporator 14 is performed. It carried out by setting the degree of superheating of the medium to 5 ° C., respectively.
  • the refrigeration capacity Q and the coefficient of performance ⁇ can be obtained from the following expressions (A) and (B) when the enthalpy h of each state (where the subscript h represents the state of the working medium).
  • Q h A -h D (A)
  • the characteristic value of the thermodynamic property necessary for calculating the refrigeration cycle performance was calculated based on the generalized equation of state (Soave-Redrich-Kwong equation) based on the corresponding state principle and the thermodynamic relational equations. When characteristic values were not available, calculations were performed using an estimation method based on the group contribution method.
  • the coefficient of performance represents the refrigeration efficiency in the refrigeration cycle system 10, and the higher the coefficient of performance, the smaller the input (the amount of power required to operate the compressor) and the larger the output (refrigeration capacity). It represents what can be obtained.
  • the refrigeration capacity represents the ability to cool the load fluid, and the higher the refrigeration capacity, the more work can be done in the same system. In other words, the larger the refrigeration capacity, the more the target performance can be obtained with a small amount of working medium, and the system can be miniaturized.
  • Table 3 also shows the values of the global warming potential of the working medium used.
  • HFC-134a GWP (100) is 1430 according to the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (2007) and HFC-125 GWP (100) is 3500 .
  • the HWP-1234yf has a GWP (100 years) of 4.
  • the GWP (100 years) of HFO-1123 is 0.3 as a value measured according to the IPCC Fourth Assessment Report.
  • GWP in a mixture is shown as a weighted average by a composition mass.
  • Refrigerating machine oil 1 Refrigerating machine oil mainly composed of polyol ester (trade name: Ze-GLES RB-68, JX Nippon Oil & Energy Corporation product: kinematic viscosity at 40 ° C. 68 mm 2 / s)
  • Refrigerating machine oil 2 Refrigerating machine oil mainly composed of polyvinyl ether (trade name: Daphne Hermetic Oil FVC68D, Idemitsu Kosan Co., Ltd. product: kinematic viscosity at 40 ° C.
  • Refrigerating machine oil 3 Refrigerating machine oil mainly composed of polyalkylene glycol (trade name: ND-8, DENSO Corporation product: kinematic viscosity at 40 ° C. is 41 mm 2 / s)
  • Refrigerating machine oil 4 Refrigerating machine oil mainly composed of alkylbenzene (trade name: Atmos N22, JX Nippon Mining & Energy Corporation product; kinematic viscosity at 40 ° C. is 21.5 mm 2 / s)
  • Refrigerating machine oil 5 naphthenic high-grade refrigerating machine oil (trade name: Suniso 4GS, Idemitsu Kosan Co., Ltd. product: kinematic viscosity at 40 ° C. is 56 mm 2 / s).
  • the composition for a heat cycle system obtained in each example was put into the heat cycle system 10 shown in FIG. 1, and the heat cycle system was continuously operated.
  • a part of the flow path from the evaporator 14 to the compressor 11 in the heat cycle system was made into glass piping.
  • the inside of the glass pipe was observed to evaluate the circulation state of the composition for the heat cycle system in the heat cycle system.
  • the circulation state was visually evaluated according to the following criteria. ⁇ : Refrigerating machine oil circulation was confirmed. ⁇ : Refrigerating machine oil is circulated, but the circulation rate is insufficient. X: Refrigerating machine oil circulation cannot be confirmed.
  • the stability test conforms to “Chemical stability test method of refrigerant and refrigerating machine oil (autoclave)” described in JIS K 2211 for the composition for thermal cycle system of Examples 1-152 in good circulation condition. And carried out.
  • the composition for a heat cycle system obtained in Examples 1-152 was placed in a 200 ml stainless steel pressure vessel containing a 150 ml glass tube inside, and further, as a catalyst, iron, copper and An aluminum specimen was placed and sealed.
  • the sealed pressure vessel was then stored in a thermostatic chamber (Perfect Oven PHH-202, manufactured by ESPEC Corporation) at 175 ° C. for 14 days.
  • the acid content of the working medium was measured, the hue of the refrigerating machine oil was observed, and the catalyst The appearance change was observed.
  • the following metal pieces were used as the catalyst.
  • a) Iron Cold-rolled steel sheet for general use (as defined in JIS G3141, symbol type SPCC-SB), 30 mm ⁇ 25 mm ⁇ thickness 3.2 mm
  • b) Copper Tough pitch copper (as defined in JIS H3100, alloy number C1100, symbol C1100P) test piece, 30 mm ⁇ 25 mm ⁇ thickness 2 mm
  • c) Aluminum Test piece of pure aluminum as defined in JIS H4000, alloy number 1050, symbol A1050P), 30 mm ⁇ 25 mm ⁇ thickness 2 mm
  • the acid content of the working medium after the test was measured according to JIS K1560 (1,1,1,2-tetrafluoroethane (HFC-134a)).
  • the pressure vessel after the test was allowed to stand until it reached room temperature. 100 ml of pure water was put in each of four absorption bottles, and a series of pipes connected in series was prepared. Connect a pressure vessel at room temperature to which an absorption bottle containing pure water is connected, and gradually open the valve of the pressure vessel to introduce refrigerant gas into the water in the absorption bottle. Minutes were extracted.
  • the water in the absorption bottle after extraction was added with 1 drop of an indicator (BTB: bromothymol blue) for the 1st and 2nd bottles, and titrated with 1/100 N-NaOH alkaline standard solution.
  • BTB bromothymol blue
  • the third and fourth water in the absorption bottle were combined and titrated in the same manner to obtain a measurement blank. From these measurement values and measurement blank values, the acid content in the refrigerant after the test was determined as the HCl concentration.
  • the composition for a heat cycle system of the present invention and the heat cycle system using the composition are refrigeration / refrigeration equipment (built-in showcase, separate-type showcase, commercial refrigeration / refrigerator, vending machine, ice maker, etc.) , Air conditioners (room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.), power generation systems (waste heat recovery power generation, etc.), heat transport It can be used for equipment (heat pipe, etc.).
  • refrigeration / refrigeration equipment built-in showcase, separate-type showcase, commercial refrigeration / refrigerator, vending machine, ice maker, etc.
  • Air conditioners room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.
  • power generation systems waste heat recovery power generation, etc.
  • heat transport It can be used for equipment (heat pipe, etc.).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

Cette invention concerne une composition pour système à cycle thermique contenant un composé qui contient une liaison insaturée, ladite composition étant non combustible, et ayant, même en cas de fuite, un impact minimal sur la couche d'ozone et sur le réchauffement de la planète, ainsi qu'une excellente performance de cycle, et une excellente sécurité, en plus de permettre une lubrification plus stable. Un système à cycle thermique utilisant ladite composition est en outre décrit. La composition pour système à cycle thermique selon l'invention contient : un milieu opérationnel en cycle thermique contenant du trifluoroéthylène, du 1,1,1,2-tétrafluoroéthane, du pentafluoroéthane et du 2,3,3,3-tétrafluoropropène; et une huile de réfrigération. La composition pour système à cycle thermique contient, dans des proportions prédéterminées, les quatre composants qui constituent le milieu opérationnel. Le système à cycle thermique ci-décrit utilise ladite composition pour système à cycle thermique.
PCT/JP2016/063739 2015-05-12 2016-05-09 Composition pour système à cycle thermique, et système à cycle thermique WO2016181933A1 (fr)

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WO2019033189A1 (fr) * 2017-08-16 2019-02-21 Ideal Eficiência Energética Ltda. Composition de fluide frigorigène, utilisation de cette composition, appareil de réfrigération, produit conditionné et procédé de conditionnement

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