WO2015115550A1 - 熱サイクル用作動媒体、熱サイクルシステム用組成物および熱サイクルシステム - Google Patents
熱サイクル用作動媒体、熱サイクルシステム用組成物および熱サイクルシステム Download PDFInfo
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- WO2015115550A1 WO2015115550A1 PCT/JP2015/052533 JP2015052533W WO2015115550A1 WO 2015115550 A1 WO2015115550 A1 WO 2015115550A1 JP 2015052533 W JP2015052533 W JP 2015052533W WO 2015115550 A1 WO2015115550 A1 WO 2015115550A1
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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
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
Definitions
- the present invention relates to a thermal cycle working medium, a thermal cycle system composition including the same, and a thermal cycle system using the composition.
- a working medium for heat cycle such as a refrigerant for a refrigerator, a refrigerant for an air conditioner, a working medium for a power generation system (waste heat recovery power generation, etc.), a working medium for a latent heat transport device (heat pipe, etc.), a secondary cooling medium, etc.
- CFC chlorofluorocarbons
- HCFC hydrochlorofluorocarbons
- HFC-32 difluoromethane
- HFC-125 pentafluoroethane
- HFC-125 hydrofluorocarbons
- R410A a quasi-azeotropic refrigerant mixture having a mass ratio of 1: 1 between HFC-32 and HFC-125 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.
- HFO-1234yf 2,3,3,3-tetrafluoropropene
- GWP global warming potential
- HFO-1234yf has a high coefficient of performance, its refrigerating capacity is lower than that of R410A, so it can be used in equipment that has been used so far, such as so-called packaged air conditioners and room air conditioners. There is a disadvantage that it can not.
- Patent Document 1 discloses a technique related to a working medium using trifluoroethylene (HFO-1123) that has the above-described characteristics and provides excellent cycle performance.
- HFO-1123 trifluoroethylene
- Patent Document 1 an attempt is made to use HFO-1123 in combination with various HFCs as a working medium in order to further improve the nonflammability and cycle performance of the working medium.
- Patent Document 2 describes a composition containing HFO-1234yf obtained when HFO-1234yf is produced by a specific method.
- the composition described in Patent Document 2 includes many compositions, including a composition containing HFO-1234yf and HFO-1123.
- HFO-1123 is only described together with many other compounds as a by-product of HFO-1234yf, and a composition in which both are mixed at a specific ratio is used as a working medium. It does not disclose that the coefficient and refrigerating capacity are excellent.
- Non-patent Document 1 Non-patent Document 1
- Non-Patent Document 1 describes a composition that can be used with durability without special measures while maintaining the cycle performance of HFO-1123 under the temperature and pressure conditions when used as a working medium, and its stable There is no description about a simple manufacturing method.
- HFO-1123 is used as a working medium, a composition that does not self-decompose and a stable manufacturing method are required.
- the present inventors confirmed that the critical temperature of HFO-1123 is 59.2 ° C. From this knowledge, it has been found that HFO-1123 has a low critical temperature and is limited in the range of substitution when used in place of the conventionally used R410A. Furthermore, even when various HFCs described in Patent Document 1 are combined, there may be cases where a sufficient coefficient of performance and refrigeration capacity cannot always be achieved.
- the present invention relates to a working medium for a heat cycle that simultaneously realizes not only a critical temperature but also a sufficient cycle performance to be used as a substitute for R410A, a composition for a heat cycle system including the same, and a heat using the composition The purpose is to provide a cycle system.
- the present invention provides a working medium for a highly durable thermal cycle that can achieve practically sufficient cycle performance while suppressing the influence on global warming, and can be used with durability without any particular measures. It aims at providing the composition for thermal cycle systems containing this, and the thermal cycle system using this composition.
- the present inventors have completed the invention by combining HFO-1234yf, which has a low refrigerating capacity, with HFO-1123, and further combining HFC-32 into a working medium having a specific composition. That is, 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 [8] below.
- the ratio of HFO-1123 to the total amount of HFO-1123, HFO-1234yf, and HFC-32 is 10% by mass or more and less than 70% by mass, and the ratio of HFO-1234yf is 50% by mass or less.
- a ratio of HFC-32 is more than 30% by mass and 75% by mass or less.
- a composition for a heat cycle system comprising the heat cycle working medium according to any one of the above [1] to [4] and a lubricating oil.
- the heat cycle system according to [6] which is a refrigeration / refrigeration device, an air conditioning device, a power generation system, a heat transport device, or a secondary cooler.
- 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, built-in showcases, separate showcases, commercial refrigerators / refrigerators
- the heat cycle system according to [6] which is an ice making machine or a vending machine.
- the working medium for heat cycle of the present invention and the composition for heat cycle system containing the same have a practically sufficient cycle performance when used in the heat cycle while suppressing the influence on global warming, and are also durable. Excellent.
- the thermal cycle system of the present invention has practically sufficient cycle performance and excellent durability while suppressing the influence on global warming by using the composition for thermal cycle system of the present invention.
- the working medium for heat cycle of the present invention has the above-described excellent characteristics, and can replace R410A that has been conventionally used.
- the triangular coordinate diagram of the composition (mass%) in the mixture consisting of HFO-1123, HFO-1234yf, and HFC-32 it is a diagram showing the composition range of one embodiment of the working fluid for heat cycle of the present invention. It is a graph which shows the relationship between the composition and temperature gradient in the mixed medium of HFO-1123 and HFO-1234yf. It is the schematic block diagram which showed the refrigerating cycle system which is an example of the thermal cycle system of this invention.
- the triangular coordinate diagram of the composition (mass%) in the mixture consisting of HFO-1123, HFO-1234yf, and HFC-32 it is a diagram showing a preferred composition range of one embodiment of the working fluid for heat cycle of the present invention.
- the working medium of the present invention is a working medium for heat cycle containing HFO-1123, HFO-1234yf, and HFC-32, and the ratio of the total amount of HFO-1123, HFO-1234yf, and HFC-32 to the total amount of the working medium 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, HFO-1234yf and HFC-32 is 10% by mass or more and less than 70% by mass, and the ratio of HFO-1234yf is
- This is a working medium for a heat cycle in which the proportion of HFC-32 is 50% by mass or less and more than 30% by mass and 75% by mass or less.
- a heat cycle using a heat exchanger such as a condenser or an evaporator is used without particular limitation.
- the working medium of the present invention is a well-balanced working medium that takes advantage of the characteristics of individual compounds and complements the disadvantages by combining HFO-1123, HFO-1234yf, and HFC-32 in the above composition range. is there. Specifically, it is a working medium that has a practically sufficient cycle performance that can replace the conventionally used R410A, has a low global warming potential, and does not have self-degradability.
- each side (S1) to (S5) of the pentagon indicating the composition range (S) indicates a boundary line in the following range.
- the abbreviation of each compound indicates the ratio (mass%) of the compound to the total amount of the working medium, that is, the total amount of HFO-1123, HFO-1234yf, and HFC-32.
- composition range (S) composition range
- the performance as a working medium specifically, the global warming potential, cycle performance, temperature gradient, and self-degradability will be described.
- GWP Global warming potential
- IPCC Intergovernmental Panel on climate Change
- the GWP of HFO-1234yf and HFC-32 contained in the working medium of the present invention is 4 and 675, respectively, and the global warming potential (100 years) of HFO-1123 is measured according to the IPCC Fourth Assessment Report The obtained value is 0.3.
- the working medium of the present invention can contain an optional component other than HFO-1123, HFO-1234yf, and HFC-32 in a proportion of 10% by mass or less.
- the optional component preferably does not include a component that excessively increases the GWP of the working medium.
- the GWP in the working medium of the present invention is preferably 500 or less, and more preferably 300 or less.
- Cycle performance examples of the cycle performance in the working medium include a coefficient of performance and a refrigerating capacity.
- the performance coefficients and refrigeration capacities of HFO-1123, HFO-1234yf, and HFC-32 contained in the working medium of the present invention were measured according to Examples described later, and the relative performance with R410A as the reference (1.000) is shown in Table 1. Shown in
- HFC-32 is excellent in coefficient of performance and refrigerating capacity, it has a higher GWP than HFO-1123 and HFO-1234yf. However, the GFC of HFC-32 is much lower than that of R410A.
- the coefficient of performance (hereinafter referred to as “relative performance” as relative performance to R410A).
- the composition having a coefficient of 1.000 or more is a composition in the vicinity including the side of (S5).
- the composition having the smallest relative coefficient of performance is the composition of the lower left corner of the pentagon showing the composition range (S).
- a composition having a refrigeration capacity (hereinafter also referred to as “relative refrigeration capacity”) as a relative performance with respect to R410A of 1.000 or more includes the side of (S2).
- the composition having the smallest relative coefficient of performance is the composition of the corner located on the rightmost side of the pentagon showing the composition range (S). It can be said that the relative refrigeration capacity largely depends on the content of HFO-1234yf.
- Cycle performance is balanced if the relative coefficient of performance and relative refrigeration capacity are values above a certain value, and the product of the relative coefficient of performance and relative refrigeration capacity is a value above a certain value.
- the working medium preferably has a relative coefficient of performance of 0.958 or more and a relative refrigeration performance of 0.820 or more, more preferably a relative coefficient of performance of 0.980 or more and a relative refrigeration performance of 0.950 or more. It is particularly preferable that the relative coefficient of performance is 1.000 or more and the relative refrigeration performance is 1.000 or more. From the viewpoint of relative coefficient of performance, (S2) is preferably 5% by mass ⁇ HFO-1234yf, and more preferably 8% by mass ⁇ HFO-1234yf. Further, regarding the relationship between the relative coefficient of performance and the relative refrigeration performance, when the relative coefficient of performance and the relative refrigeration capacity are both below 1.000, the product is preferably 0.950 or more.
- the working medium of the present invention can contain an optional component other than HFO-1123, HFO-1234yf, and HFC-32 in a proportion of 10% by mass or less.
- the optional component preferably does not include a component that excessively decreases the relative coefficient of performance and relative refrigeration performance of the working medium.
- a mixture When a mixture is used as the working medium, it is preferably an azeotropic or pseudo-azeotropic mixture such as R410A.
- Non-azeotropic compositions have the problem of causing composition changes when filled from a pressure vessel to a refrigeration air conditioner. Furthermore, when refrigerant leakage from the refrigeration air conditioner occurs, the refrigerant composition in the refrigeration air conditioner is very likely to change, and it is difficult to restore the refrigerant composition to the initial state. On the other hand, the above problem can be avoided if the mixture is azeotropic or pseudo-azeotropic.
- temperature gradient is generally used as an index for measuring the above properties of the working medium of the mixture.
- a temperature gradient is defined as the nature of heat exchangers, such as evaporation in an evaporator or condensation in a condenser, with different start and end temperatures.
- the temperature gradient is 0, and in the pseudo-azeotropic refrigerant mixture such as R410A, the temperature gradient is extremely close to zero.
- the inlet temperature in the evaporator decreases, which increases the possibility of frost formation, which is a problem.
- a heat cycle system in order to improve heat exchange efficiency, it is common to make the working medium flowing through the heat exchanger and a heat source fluid such as water or air counter flow, and in a stable operation state, Since the temperature difference of the heat source fluid is small, it is difficult to obtain an energy efficient heat cycle system in the case of a non-azeotropic mixed medium having a large temperature gradient. For this reason, a non-azeotropic mixing medium having an appropriate temperature gradient is desired.
- FIG. 2 shows the relationship between the composition and the temperature gradient in the mixed medium of HFO-1123 and HFO-1234yf, which was measured by the method shown in the examples described later. Further, the present inventor has confirmed that HFO-1123 and HFC-32 are near-azeotropic azeotropic mixtures in a composition range of 99: 1 to 1:99 by mass ratio.
- FIG. 1 shows the composition range of HFO-1123, HFO-1234yf, and HFC-32 in the working medium of the present invention based on the relationship between HFO-1123 and HFO-1234yf and the relationship between HFO-1123 and HFC-32.
- S the following can be confirmed.
- composition range (S) of FIG. 1 the closer to the side of (S2), that is, the smaller the content of HFO-1234yf, the closer the temperature gradient becomes to 0, and the lower end of (S2), ie, the composition range (S The composition of the lower left corner of the pentagon indicating) has the smallest temperature gradient. Conversely, the greater the HFO-1234yf content, that is, the closer to the side of (S4), the greater the temperature gradient. Further, the composition of the lower right corner of the pentagon showing the composition range (S) has the largest temperature gradient at the lower end of (S4).
- Table 2 shows the composition, temperature gradient, and GWP of the working medium in which the content of HFO-1234yf is 50% by mass among the working media produced in the examples and comparative examples. Further, for comparison, the temperature gradient and GWP of a working medium having a 1: 1 (mass ratio) composition of HFO-1123 and HFO-1234yf, and R410A are shown.
- the composition range (S) having a composition with a low GWP and a low temperature gradient in the triangular coordinate diagram of FIG. 1 is selected.
- the temperature gradient in the working medium composed of HFO-1123, HFO-1234yf, and HFC-32 is more preferably less than 5.8 ° C.
- the working medium of the present invention can contain an optional component other than HFO-1123, HFO-1234yf, and HFC-32 in a proportion of 10% by mass or less.
- the optional component preferably does not include a component that excessively raises the temperature gradient of the working medium.
- the temperature gradient in the working medium of the present invention is preferably 6 ° C. or less, and more preferably 5 ° C. or less.
- FIG. 3 is a schematic configuration diagram showing a refrigeration cycle system which is an example of the thermal cycle system of the present invention.
- the refrigeration cycle system 10 includes a compressor 11 that compresses a working medium (steam), a condenser 12 that cools the steam of the working medium discharged from the compressor 11 to form a liquid, and a working medium discharged from the condenser 12.
- An expansion valve 13 that expands (liquid) and an evaporator 14 that heats the liquid working medium discharged from the expansion valve 13 to vapor are provided.
- the temperature of the working medium rises from the inlet of the evaporator 14 to the outlet during evaporation, and conversely, the temperature of the working medium decreases from the inlet of the condenser 12 to the outlet during condensation.
- the evaporator 14 and the condenser 12 are configured by exchanging heat with a heat source fluid such as water or air that flows facing the working medium.
- the heat source fluid is indicated by “E ⁇ E ′” in the evaporator 14 and “F ⁇ F ′” in the condenser 12 in the refrigeration cycle system 10.
- the temperature difference between the outlet temperature and the inlet temperature of the evaporator 14 is almost constant, but a non-azeotropic mixture medium is used. If this happens, the temperature difference will not be constant. For example, when vaporization is attempted at 0 ° C. with the evaporator 14, the inlet temperature becomes lower than 0 ° C., causing a problem of frost formation in the evaporator 14. In particular, the larger the temperature gradient, the lower the inlet temperature and the greater the possibility of frost formation.
- the composition of the gas-liquid phase is greatly different, so when the non-azeotropic mixture medium circulating in the system 10 leaks, Before and after that, the composition of the non-azeotropic mixed medium circulating in the system 10 greatly changes.
- composition range of the combination of HFO-1123, HFO-1234yf, and HFC-32 in the working medium of the present invention is a range showing a temperature gradient that can be practically used as the working medium.
- HFO-1123 contained in the working medium of the present invention has self-degradability.
- composition that can be used with durability while maintaining the refrigeration cycle performance of HFO-1123 under temperature and pressure conditions when used as a working medium. Therefore, the present inventors have used the self-degradability of HFO-1123 as a working medium if the content of HFO-1123 in the composition containing HFO-1123 is 70 mol% or less with respect to the total amount of the composition. It was confirmed as follows that self-decomposition can be suppressed under the temperature and pressure conditions.
- the working medium of the present invention can contain an optional component other than HFO-1123, HFO-1234yf, and HFC-32 in a proportion of 10% by mass or less.
- an optional component a compound having no self-decomposability is preferably selected.
- the working medium having the above composition range (S) is a working medium in which the characteristics of HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a well-balanced manner and the defects possessed by each are suppressed.
- the working medium having the composition range (S) has a low GWP, a durability that is ensured, a small temperature gradient when used in a thermal cycle, and a certain ability and efficiency. It is a working medium that can provide good cycle performance.
- each side (P1) to (P5) of the pentagon showing the composition range (P) indicates a boundary line in the following range.
- the abbreviations of the respective compounds are the same for the total amount of the working medium, that is, the total amount of HFO-1123, HFO-1234yf and HFC-32, as in the case of (S1) to (S5) above.
- the ratio (mass%) is shown.
- (P2) to (P5) are the same as (S2) to (S5) in the composition range (S).
- the upper limit of the content of HFC-32 is lower than that of the composition range (S), and the upper limit of GWP is lower.
- the GWP has the highest composition at the upper right corner of the pentagon, that is, HFO-1123: HFO-1234yf: HFC-32 is 10% by mass: 46% by mass: 44% by mass.
- (P2) is preferably 5% by mass ⁇ HFO-1234yf, and more preferably 8% by mass ⁇ HFO-1234yf.
- HFO-1123 has a ratio of 20% by mass to less than 70% by mass
- HFO-1234yf has a ratio of 40% by mass or less
- HFC-32 has a ratio of more than 30% by mass and 75% by mass or less.
- a composition in which the upper limit of the proportion of HFC-32 is 44% by mass can be mentioned.
- a composition in which the lower limit of the proportion of HFO-1234yf in the composition is 5 mass% can be mentioned. This more preferable composition range is demonstrated below as a composition range (M).
- FIG. 5 is a triangular coordinate diagram showing the three sides as the composition (mass%) of HFO-1123, HFO-1234yf, and HFC-32, and is surrounded by a thick solid line near the center of the triangular coordinate diagram.
- the square region is the more preferred working medium composition range (M) of the present invention.
- each side (M1) to (M5) of the pentagon indicating the composition range (M) indicates a boundary line in the following range.
- the abbreviations of the respective compounds are the same for the total amount of the working medium, that is, the total amount of HFO-1123, HFO-1234yf and HFC-32, as in the case of (S1) to (S5) above.
- the ratio (mass%) is shown.
- (M1) to (M5) in the composition range (M), (M1) and (M3) are the same as (P1) and (P3) in the composition range (P).
- the composition range (M) is such that the content range of HFO-1234yf is more than 0 mass% and 50 mass% or less to 5 mass% or more and 40 mass% or less as compared with the composition range (P), and HFO-1123
- the lower limit of the content of is increased from 10% by mass to 20% by mass.
- the upper limit of the temperature gradient is lowered, and the lower limit of the relative coefficient of performance x the relative refrigeration capacity is raised.
- (M2) is more preferably 8% by mass ⁇ HFO-1234yf.
- (M4) is more preferably HFO-1234yf ⁇ 35 mass%.
- the working medium having the above composition range (M) is a working medium in which the characteristics of HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a particularly well-balanced manner and the defects possessed by each are suppressed. That is, in the working medium having the composition range (M), the upper limit of GWP is suppressed to 300 or less, durability is ensured, and the temperature gradient is as small as less than 5.8 when used in the thermal cycle. In addition, the relative performance coefficient and the relative refrigeration capacity are close to 1, and the working medium can obtain good cycle performance.
- a compound used as a normal working medium is arbitrarily added in an amount of 10% by mass or less of the total amount of the working medium as long as the effects of the present invention are not impaired. You may contain by a ratio. Even when the working medium of the present invention contains an arbitrary compound (referred to as an optional component) in addition to HFO-1123, HFO-1234yf, and HFC-32, the temperature gradient of the working medium does not become “0”, and a considerable temperature. Has a gradient.
- the temperature gradient of the working medium of the present invention varies depending on the mixing ratio of HFO-1123, HFO-1234yf, HFC-32, and optional components as necessary.
- Optional components include HFCs other than HFC-32, HFOs other than HFO-1123 and HFO-1234yf (HFCs having a carbon-carbon double bond).
- HFC other than HFC-32 As the HFC other than HFC-32 optionally contained in the working medium of the present invention, for example, in combination with HFO-1123, HFO-1234yf and HFC-32, the temperature gradient is lowered and the ability is improved. HFC having the effect of increasing or improving the efficiency is used. When an HFC other than HFC-32 is included, better cycle performance can be obtained.
- HFC is known to have a higher GWP than HFO-1123 and HFO-1234yf. Therefore, in addition to improving the cycle performance as the working medium, an arbitrary component HFC is selected from the viewpoint of keeping the GWP within an allowable range.
- HFCs other than HFC-32 may be linear, branched or cyclic.
- HFCs other than HFC-32 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-152a) has a small influence on the ozone layer and has excellent refrigeration cycle characteristics.
- HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), and HFC-125 are preferred, and HFC-134a and HFC-125 is more preferred.
- HFC-134a and HFC-125 have very high warming coefficients of 1430 and 3500, respectively. When these are used as optional components of the working medium, care should be taken that the GWP of the working medium is not raised beyond an allowable range. HFCs other than HFC-32 may be used alone or in combination of two or more.
- 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-1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye (Z)), trans- 1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)), 3,3,3-trifluoro And propene (HFO-1243zf).
- HFO-1132 1,2-difluoroethylene
- HFO-1261yf 2-fluoropropene
- HFO-1243yc 1,1,2-trifluoropropene
- HFO other than HFO-1123 and HFO-1234yf HFO-1234ze (E) and HFO-1234ze (Z) are preferable from the viewpoint of having a high critical temperature and excellent durability and coefficient of performance. ⁇ 1234ze (E) is more preferred. HFOs other than HFO-1123 and HFO-1234yf may be used alone or in combination of two or more.
- the working medium of the present invention contains an optional component, its content is 10% by mass or less, preferably 8% by mass or less.
- the composition range by HFO-1123, HFO-1234yf and HFC-32 in the working medium of the present invention is already the durability, temperature gradient, refrigeration capacity, coefficient of performance, and global warming coefficient only by the three components. Since the composition is well-balanced, it may be difficult to improve any of the properties without adding any optional components to destroy the balance. In particular, it is more difficult when the working medium is in the above preferred composition range. Therefore, in the present invention, except for the following other optional components which are blended for the purpose of improving the solubility in lubricating oil and making it flame retardant, other than HFO-1123, HFO-1234yf and HFC-32 It is preferable not to contain these components.
- CFO examples include chlorofluoropropene and chlorofluoroethylene.
- CFO 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) can be used because the flammability of the working medium can be easily suppressed without significantly reducing the cycle performance of the working medium of the present invention.
- CFO-1214yb 1,3-dichloro-1,2,3,3-tetrafluoropropene
- CFO-1112 1,2-dichloro-1,2-difluoroethylene
- One type of CFO may be used alone, or two or more types may be used in combination.
- the working medium of the present invention is HFO-1123 that is both HFO that has little influence on global warming and has excellent ability as a working medium, HFO-1234yf that has a balanced ability and efficiency as a working medium, Although it has a relatively high GWP, it is much lower than R410A, has an excellent coefficient of performance and refrigeration capacity, and HFC-32, which forms an azeotropic or pseudo-azeotropic composition with HFO-1123, is a mixed medium when mixing three components. Taking into account the temperature gradient, it is a working medium obtained by combining the two so that the cycle performance is improved compared to when each is used alone, while suppressing the impact on durability and global warming. It has a practically sufficient cycle performance.
- 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.
- the heat cycle system of the present invention may be a heat transport device.
- a latent heat transport device is preferable.
- Examples of 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.
- the CD process is a process in which isenthalpy 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.)
- 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.
- R410A HFC-32 and Compared to the case of using a mixed medium of HFC-125 having a mass ratio of 1: 1), both the Q and COP are high, that is, a level equal to or higher than R410A while keeping the global warming potential extremely low. Can be set.
- the temperature gradient of the working medium contained in the composition for the heat cycle system to be used is suppressed to a certain value or less, the composition change when filling from the pressure vessel to the refrigeration air conditioner and the refrigerant from the refrigeration air conditioner Changes in the refrigerant composition in the refrigeration and air conditioning equipment when leakage occurs can be suppressed to a low level.
- the working medium of the present invention does not have self-decomposability, a heat cycle system using the working medium can be operated with high durability without taking special measures for durability.
- a zeolitic desiccant is preferable from the viewpoint of the chemical reactivity between the desiccant and the working medium and the moisture absorption capacity of the desiccant.
- 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 lubricating oil to promote decomposition.
- Measurement of the temperature gradient and refrigeration cycle performance is performed by applying a working medium to the refrigeration cycle system 10 shown in FIG. 3 and adiabatic compression by the compressor 11 in the thermal cycle shown in FIG. In the BC process, isobaric cooling by the condenser 12, the isoenthalpy expansion by the expansion valve 13 in the CD process, and the isobaric heating by the evaporator 14 in the DA process.
- Thermodynamic properties required for calculation of cycle performance were calculated based on a generalized equation of state (Soave-Redrich-Kwong equation) based on the corresponding state principle and thermodynamic relational equations. When characteristic values were not available, calculations were performed using an estimation method based on the group contribution method.
- R410A is a working medium that has been used conventionally, in this example, it was evaluated that the cycle performance was practically sufficient if the cycle performance reached an equivalent level on the basis of this. .
- R410A is composed only of HFC and has a high global warming potential.
- Refrigeration capacity of working medium is a factor that determines the size of the device itself. If HFO-1123 is combined with a compound having a lower refrigeration capacity than HFO-1123, for example, HFO-1234yf, the mixture (working medium) after the combination has a lower refrigeration capacity than a working medium having a single composition of HFO-1123. . For this reason, in order to replace such a mixture with R410A, in order to compensate for the low refrigeration capacity, it is necessary to increase the size of the device itself and increase the energy used.
- the tendency of the temperature gradient in the mixed medium of HFO-1123, HFO-1234yf, and HFC-32 is: Since the temperature gradient of the mixed medium of HFO-1123 and HFO-1234yf is the same as that in the working medium within the composition range of the present invention, the temperature gradient can be suppressed to a certain value or less. Can be substituted.
- Examples 1 to 14 and Examples 37 to 56 which are examples of the present invention, have a practically sufficient level of cycle performance based on R410A.
- HFC-32 is a compound having a high GWP.
- the working medium of the present invention has a significantly lower GWP than R410A.
- the working medium of the present invention it is possible to replace only the R410A working medium with the GWP having low GWP and high durability without replacing the equipment as described above. Suitable for current demands.
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Abstract
Description
従来、冷凍機用冷媒、空調機器用冷媒、発電システム(廃熱回収発電等)用作動媒体、潜熱輸送装置(ヒートパイプ等)用作動媒体、二次冷却媒体等の熱サイクル用の作動媒体としては、クロロトリフルオロメタン、ジクロロジフルオロメタン等のクロロフルオロカーボン(CFC)、クロロジフルオロメタン等のヒドロクロロフルオロカーボン(HCFC)が用いられてきた。しかし、CFCおよびHCFCは、成層圏のオゾン層への影響が指摘され、現在、規制の対象となっている。
すなわち、本発明は、以下の[1]~[8]に記載の構成を有する熱サイクル用作動媒体、熱サイクルシステム用組成物および熱サイクルシステムを提供する。
[1]HFO-1123とHFO-1234yfとHFC-32を含む熱サイクル用作動媒体であって、前記作動媒体全量に対するHFO-1123とHFO-1234yfとHFC-32の合計量の割合が90質量%を超え100質量%以下であり、HFO-1123とHFO-1234yfとHFC-32の合計量に対する、HFO-1123の割合が10質量%以上70質量%未満、HFO-1234yfの割合が50質量%以下、かつHFC-32の割合が30質量%を超え75質量%以下であることを特徴とする熱サイクル用作動媒体。
[2]HFO-1123とHFO-1234yfとHFC-32の合計量に対するHFC-32の割合が30質量%を超え44質量%以下である[1]記載の熱サイクル用作動媒体。
[3]HFO-1123とHFO-1234yfとHFC-32の合計量に対するHFO-1123の割合が20質量%以上70質量%未満であり、HFO-1234yfの割合が40質量%以下である、[1]または[2]に記載の熱サイクル用作動媒体。
[4]HFO-1123とHFO-1234yfとHFC-32の合計量に対するHFO-1234yfの割合が5質量%以上40質量%以下である、[1]~[3]に記載の熱サイクル用作動媒体。
[6]前記[5]に記載の熱サイクルシステム用組成物を用いた、熱サイクルシステム。
[7]冷凍・冷蔵機器、空調機器、発電システム、熱輸送装置または二次冷却機である[6]記載の熱サイクルシステム。
[8]ルームエアコン、店舗用パッケージエアコン、ビル用パッケージエアコン、設備用パッケージエアコン、ガスエンジンヒートポンプ、列車用空調装置、自動車用空調装置、内蔵型ショーケース、別置型ショーケース、業務用冷凍・冷蔵庫、製氷機または自動販売機である[6]記載の熱サイクルシステム。
本発明の熱サイクルシステムは、本発明の熱サイクルシステム用組成物を用いることで、地球温暖化への影響を抑えつつ、実用上充分なサイクル性能を有するとともに、耐久性に優れる。
さらに、本発明の熱サイクル用作動媒体は、上記の優れた特徴を有し、かつ従来使用されてきたR410Aの置き換えが可能である。
<熱サイクル用作動媒体>
本発明の作動媒体は、HFO-1123とHFO-1234yfとHFC-32を含む熱サイクル用作動媒体であって、前記作動媒体全量に対するHFO-1123とHFO-1234yfとHFC-32の合計量の割合が90質量%を超え100質量%以下であり、HFO-1123とHFO-1234yfとHFC-32の合計量に対する、HFO-1123の割合が10質量%以上70質量%未満、HFO-1234yfの割合が50質量%以下、かつHFC-32の割合が30質量%を超え75質量%以下である熱サイクル用の作動媒体である。
熱サイクルとしては、凝縮器や蒸発器等の熱交換器による熱サイクルが特に制限なく用いられる。
図1は、本発明の熱サイクル用作動媒体がHFO-1123、HFO-1234yfおよびHFC-32からなり、他の成分を含まない場合の上記組成範囲、すなわち、HFO-1123とHFO-1234yfとHFC-32の合計量に対する、HFO-1123の割合が10質量%以上70質量%未満、HFO-1234yfの割合が50質量%以下、かつHFC-32の割合が30質量%を超え75質量%以下の組成範囲(以下、組成範囲(S)ともいう。)を示す三角座標図である。図1は三辺のそれぞれをHFO-1123、HFO-1234yf、HFC-32の組成(質量%)として示す三角座標図であり、太実線で囲まれた5角形の領域が、本発明の一実施態様の作動媒体の組成範囲(S)である。
(S1)HFC-32≦75質量%
(S2)0質量%<HFO-1234yf
(S3)30質量%<HFC-32
(S4)HFO-1234yf≦50質量%
(S5)10質量%≦HFO-1123
本明細書において、GWPは、特に断りのない限り気候変動に関する政府間パネル(IPCC)第4次評価報告書(2007年)の100年の値とする。また、混合物におけるGWPは、組成質量による加重平均とする。
作動媒体におけるサイクル性能としては、成績係数、冷凍能力が挙げられる。
本発明の作動媒体が含有するHFO-1123、HFO-1234yfおよびHFC-32の成績係数および冷凍能力について、後述の実施例により測定した、R410Aを基準(1.000)とする相対性能として表1に示す。
作動媒体として混合物を用いる場合、共沸またはR410Aのような擬似共沸の混合物であることが好ましい。非共沸組成物は、圧力容器から冷凍空調機器へ充てんされる際に組成変化を生じる問題点を有している。さらに、冷凍空調機器からの冷媒漏えいが生じた場合、冷凍空調機器内の冷媒組成が変化する可能性が極めて大きく、初期状態への冷媒組成の復元が困難である。一方、共沸または擬似共沸の混合物であれば上記問題が回避できる。
本発明の作動媒体が含有するHFO-1123は自己分解性を有することが知られている。しかしながら、作動媒体として使用する場合の温度や圧力条件下で、HFO-1123の冷凍サイクル性能を維持しながら耐久性をもって使用できる組成は知られていない。そこで、本発明者らは、HFO-1123の自己分解性については、HFO-1123を含む組成物において、組成物全量に対するHFO-1123の含有量を70モル%以下とすれば、作動媒体として使用する場合の温度や圧力条件下で自己分解を抑制できることを以下のとおり確認した。
自己分解性の評価は、高圧ガス保安法における個別通達においてハロゲンを含むガスを混合したガスにおける燃焼範囲を測定する設備として推奨されているA法に準拠した設備を用い実施した。
(P1)HFC-32≦44質量%
(P2)0質量%<HFO-1234yf
(P3)30質量%<HFC-32
(P4)HFO-1234yf≦50質量%
(P5)10質量%≦HFO-1123
(M1)HFC-32≦44質量%
(M2)5質量%≦HFO-1234yf
(M3)30質量%<HFC-32
(M4)HFO-1234yf≦40質量%
(M5)20質量%≦HFO-1123
本発明の作動媒体は、本発明の効果を損なわない範囲でHFO-1123、HFO-1234yfおよびHFC-32以外に、通常作動媒体として用いられる化合物を任意に、作動媒体全量の10質量%以下の割合で含有してもよい。本発明の作動媒体がHFO-1123、HFO-1234yfおよびHFC-32以外に任意の化合物(任意成分という)を含有する場合においても、作動媒体の温度勾配は「0」とはならず相当の温度勾配を有する。本発明の作動媒体の温度勾配は、HFO-1123とHFO-1234yfとHFC-32、および必要に応じて任意成分の混合割合により異なる。
本発明の作動媒体が任意に含有するHFC-32以外のHFCとしては、例えばHFO-1123、HFO-1234yfおよびHFC-32と組み合わせて熱サイクルに用いた際に、温度勾配を下げる、能力を向上させるまたは効率をより高める作用を有するHFCが用いられる。HFC-32以外のHFCが含まれると、より良好なサイクル性能が得られる。
HFC-32以外のHFCは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
HFO-1123およびHFO-1234yf以外のHFOとしては、1,2-ジフルオロエチレン(HFO-1132)、2-フルオロプロペン(HFO-1261yf)、1,1,2-トリフルオロプロペン(HFO-1243yc)、トランス-1,2,3,3,3-ペンタフルオロプロペン(HFO-1225ye(E))、シス-1,2,3,3,3-ペンタフルオロプロペン(HFO-1225ye(Z))、トランス-1,3,3,3-テトラフルオロプロペン(HFO-1234ze(E))、シス-1,3,3,3-テトラフルオロプロペン(HFO-1234ze(Z))、3,3,3-トリフルオロプロペン(HFO-1243zf)等が挙げられる。
HFO-1123およびHFO-1234yf以外のHFOは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本発明の作動媒体は、上記任意成分以外に、二酸化炭素、炭化水素、クロロフルオロオレフィン(CFO)、ヒドロクロロフルオロオレフィン(HCFO)等を含有してもよい。その他の任意成分としてはオゾン層への影響が少なく、かつ地球温暖化への影響が小さい成分が好ましい。
炭化水素は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
CFOは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
HCFOは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
<熱サイクルシステム用組成物>
本発明の作動媒体は、熱サイクルシステムへの適用に際して、通常、潤滑油と混合して本発明の熱サイクルシステム用組成物として使用することができる。本発明の作動媒体と潤滑油を含む本発明の熱サイクルシステム用組成物は、これら以外にさらに、安定剤、漏れ検出物質等の公知の添加剤を含有してもよい。
潤滑油としては、従来からハロゲン化炭化水素からなる作動媒体とともに、熱サイクルシステム用組成物に用いられる公知の潤滑油が特に制限なく採用できる。潤滑油として具体的には、含酸素系合成油(エステル系潤滑油、エーテル系潤滑油等)、フッ素系潤滑油、鉱物系潤滑油、炭化水素系合成油等が挙げられる。
なお、これらのポリオールエステル油は、遊離の水酸基を有していてもよい。
ポリオールとしては、上述と同様のジオールや上述と同様のポリオールが挙げられる。また、ポリオール炭酸エステル油としては、環状アルキレンカーボネートの開環重合体であってもよい。
ビニルエーテルモノマーは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
潤滑油としては、作動媒体との相溶性の点から、ポリオールエステル油、ポリビニルエーテル油およびポリグリコール油から選ばれる1種以上が好ましい。
安定剤は、熱および酸化に対する作動媒体の安定性を向上させる成分である。安定剤としては、従来からハロゲン化炭化水素からなる作動媒体とともに、熱サイクルシステムに用いられる公知の安定剤、例えば、耐酸化性向上剤、耐熱性向上剤、金属不活性剤等が特に制限なく採用できる。
漏れ検出物質としては、紫外線蛍光染料、臭気ガスや臭いマスキング剤等が挙げられる。
紫外線蛍光染料としては、米国特許第4249412号明細書、特表平10-502737号公報、特表2007-511645号公報、特表2008-500437号公報、特表2008-531836号公報に記載されたもの等、従来、ハロゲン化炭化水素からなる作動媒体とともに、熱サイクルシステムに用いられる公知の紫外線蛍光染料が挙げられる。
本発明の熱サイクルシステムは、本発明の作動媒体を用いたシステムである。本発明の作動媒体を熱サイクルシステムに適用するにあたっては、通常、上記熱サイクルシステム用組成物に作動媒体を含有させるかたちで適用する。本発明の熱サイクルシステムは、凝縮器で得られる温熱を利用するヒートポンプシステムであってもよく、蒸発器で得られる冷熱を利用する冷凍サイクルシステムであってもよい。
発電システムとして、具体的には、蒸発器において地熱エネルギー、太陽熱、50~200℃程度の中~高温度域廃熱等により作動媒体を加熱し、高温高圧状態の蒸気となった作動媒体を膨張機にて断熱膨張させ、該断熱膨張によって発生する仕事によって発電機を駆動させ、発電を行うシステムが例示される。
(i)蒸発器14から排出された作動媒体蒸気Aを圧縮機11にて圧縮して高温高圧の作動媒体蒸気Bとする(以下、「AB過程」という。)。
(ii)圧縮機11から排出された作動媒体蒸気Bを凝縮器12にて流体Fによって冷却し、液化して低温高圧の作動媒体Cとする。この際、流体Fは加熱されて流体F’となり、凝縮器12から排出される(以下、「BC過程」という。)。
(iv)膨張弁13から排出された作動媒体Dを蒸発器14にて負荷流体Eによって加熱して高温低圧の作動媒体蒸気Aとする。この際、負荷流体Eは冷却されて負荷流体E’となり、蒸発器14から排出される(以下、「DA過程」という。)。
COP=Q/圧縮仕事=(hA-hD)/(hB-hA) …(2)
ただし、Mは、Na、K等の1族の元素またはCa等の2族の元素であり、nは、Mの原子価であり、x、yは、結晶構造にて定まる値である。Mを変化させることにより細孔径を調整できる。
作動媒体の分子径よりも大きい細孔径を有する乾燥剤を用いた場合、作動媒体が乾燥剤中に吸着され、その結果、作動媒体と乾燥剤との化学反応が生じ、不凝縮性気体の生成、乾燥剤の強度の低下、吸着能力の低下等の好ましくない現象を生じることとなる。
作動媒体に対するゼオライト系乾燥剤の使用割合は、特に限定されない。
例1~32、例37~56において、HFO-1123、HFO-1234yfおよびHFC-32を表6および表7に示す割合で混合した作動媒体を作製し、以下の方法で、温度勾配および冷凍サイクル性能(冷凍能力Qおよび成績係数COP)を測定した。例33、34、35は、HFO-1123、HFO-1234yfおよびHFC-32の単一組成の作動媒体、例36はHFO-1123とHFO-1234yfの質量比1:1組成の作動媒体であり上記同様に温度勾配および冷凍サイクル性能(冷凍能力Qおよび成績係数COP)を測定した。
温度勾配、冷凍サイクル性能(冷凍能力および成績係数)の測定は、図3に示す冷凍サイクルシステム10に作動媒体を適用して、図6に示す熱サイクル、すなわちAB過程で圧縮機11による断熱圧縮、BC過程で凝縮器12による等圧冷却、CD過程で膨張弁13による等エンタルピ膨張、DA過程で蒸発器14による等圧加熱を実施した場合について行った。
例57として、上記例1~56の相対比較の対象となる、R410A(HFC-32とHFC-125の質量比1:1の混合媒体)について、上記と同様の方法で、温度勾配および冷凍サイクル性能(冷凍能力Qおよび成績係数COP)を測定した。冷凍能力および成績係数は表8のとおり1.000である。温度勾配およびGWPの計算結果を表8に示す。
なお、2014年1月31日に出願された日本特許出願2014-017031号および2014年7月18日に出願された日本特許出願2014-148350号の明細書、特許請求の範囲、要約書および図面の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (8)
- トリフルオロエチレンと2,3,3,3-テトラフルオロプロペンとジフルオロメタンを含む熱サイクル用作動媒体であって、前記作動媒体全量に対するトリフルオロエチレンと2,3,3,3-テトラフルオロプロペンとジフルオロメタンの合計量の割合が90質量%を超え100質量%以下であり、トリフルオロエチレンと2,3,3,3-テトラフルオロプロペンとジフルオロメタンの合計量に対する、トリフルオロエチレンの割合が10質量%以上70質量%未満、2,3,3,3-テトラフルオロプロペンの割合が50質量%以下、かつジフルオロメタンの割合が30質量%を超え75質量%以下であることを特徴とする熱サイクル用作動媒体。
- トリフルオロエチレンと2,3,3,3-テトラフルオロプロペンとジフルオロメタンの合計量に対するジフルオロメタンの割合が30質量%を超え44質量%以下である請求項1記載の熱サイクル用作動媒体。
- トリフルオロエチレンと2,3,3,3-テトラフルオロプロペンとジフルオロメタンの合計量に対するトリフルオロエチレンの割合が20質量%以上70質量%未満であり、2,3,3,3-テトラフルオロプロペンの割合が40質量%以下である、請求項1または2に記載の熱サイクル用作動媒体。
- トリフルオロエチレンと2,3,3,3-テトラフルオロプロペンとジフルオロメタンの合計量に対する2,3,3,3-テトラフルオロプロペンの割合が5質量%以上40質量%以下である請求項1~3のいずれか1項に記載の熱サイクル用作動媒体。
- 請求項1~4のいずれか1項に記載の熱サイクル用作動媒体と、潤滑油とを含む熱サイクルシステム用組成物。
- 請求項5に記載の熱サイクルシステム用組成物を用いた、熱サイクルシステム。
- 冷凍・冷蔵機器、空調機器、発電システム、熱輸送装置または二次冷却機である請求項6記載の熱サイクルシステム。
- ルームエアコン、店舗用パッケージエアコン、ビル用パッケージエアコン、設備用パッケージエアコン、ガスエンジンヒートポンプ、列車用空調装置、自動車用空調装置、内蔵型ショーケース、別置型ショーケース、業務用冷凍・冷蔵庫、製氷機または自動販売機である請求項6記載の熱サイクルシステム。
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US20200079986A1 (en) | 2020-03-12 |
BR112016016341B1 (pt) | 2022-01-11 |
US20230257640A1 (en) | 2023-08-17 |
BR112016016341A2 (ja) | 2017-08-08 |
CN105940079A (zh) | 2016-09-14 |
MY181760A (en) | 2021-01-06 |
JP2016028119A (ja) | 2016-02-25 |
EP3101081B1 (en) | 2019-12-18 |
CN105940079B (zh) | 2020-06-16 |
US10519355B2 (en) | 2019-12-31 |
US11746272B2 (en) | 2023-09-05 |
US11220619B2 (en) | 2022-01-11 |
EP3101081A4 (en) | 2017-09-27 |
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US20160333244A1 (en) | 2016-11-17 |
US9862868B2 (en) | 2018-01-09 |
US20220081600A1 (en) | 2022-03-17 |
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US20180086959A1 (en) | 2018-03-29 |
EP3101081A1 (en) | 2016-12-07 |
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