WO2015186558A1 - 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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- WO2015186558A1 WO2015186558A1 PCT/JP2015/064942 JP2015064942W WO2015186558A1 WO 2015186558 A1 WO2015186558 A1 WO 2015186558A1 JP 2015064942 W JP2015064942 W JP 2015064942W WO 2015186558 A1 WO2015186558 A1 WO 2015186558A1
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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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- 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
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- 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
- F25B43/00—Arrangements for separating or purifying gases or liquids; Arrangements for vaporising the residuum of liquid refrigerant, e.g. by heat
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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
- C09K2205/32—The mixture being azeotropic
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
- F25B2400/12—Inflammable refrigerants
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- 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
- F25B2500/00—Problems to be solved
- F25B2500/16—Lubrication
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- 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
- F25B2500/00—Problems to be solved
- F25B2500/22—Preventing, detecting or repairing leaks of refrigeration fluids
- F25B2500/222—Detecting refrigerant leaks
Definitions
- the present invention relates to a working medium for heat cycle, a composition for heat cycle system, and a heat cycle system.
- Those using HFC are known.
- R410A an azeotrope-like mixed refrigerant having a mass ratio of 1: 1 of difluoromethane (HFC-32) and pentafluoroethane (HFC-125)
- HFC may cause global warming. Therefore, there is an urgent need to develop a working medium that has little influence on the ozone layer and has a low global warming potential (GWP).
- HFO hydrofluoroolefin
- thermal cycle systems (1) to (3) can be mentioned.
- HFO-1243zf 3,3,3-trifluoropropene
- HFO-1234ze 1,3,3,3-tetrafluoropropene
- 2-fluoropropene HFO-1261yf
- 1,1,2-trifluoropropene HFO-1243yc
- a non-azeotropic composition when used as a working medium, the working medium is charged (transferred) from a pressure vessel accommodated for storage or transfer to a refrigeration air conditioner or the like that is a thermal cycle system device. ) Or when leaking from refrigeration and air-conditioning equipment, the composition may change. Furthermore, when the composition of the working medium changes, it is difficult to restore the working medium to the initial composition. Therefore, when a non-azeotropic composition is used as a working medium, there has been a problem that the manageability of the working medium is poor. In addition, when a non-azeotropic composition is used as a working medium, there is a problem that a temperature gradient becomes large.
- the present invention provides a working medium for a heat cycle and a composition for a heat cycle system that can be substituted for R410A, have a small composition change, a small temperature gradient, and excellent cycle performance (capacity), and a heat cycle system using the composition.
- the purpose is to provide.
- the present invention provides a working medium for heat cycle, a composition for heat cycle system, and a heat cycle system having the following configuration.
- a working medium for heat cycle comprising an azeotrope-like composition comprising HFO-1132 (E) and HFC-32 and / or HFC-125.
- the azeotrope-like composition contains 1 to 99% by mass of the HFO-1132 (E) and 99 to 1% by mass of the total amount of the HFC-32 and HFC-125, [1] or [2 ]
- [7] The working medium for heat cycle according to any one of [1] to [6], wherein the ratio of the azeotropic-like composition to the total amount of the working medium for heat cycle is 50% by mass or more.
- a composition for a heat cycle system comprising the heat cycle working medium according to any one of [1] to [10] and a refrigerating machine oil.
- the thermal cycle system according to [12] which is a refrigeration / refrigeration device, an air conditioning device, a power generation system, a heat transport device, or a secondary cooler.
- Room air conditioner store packaged air conditioner, building packaged air conditioner, facility packaged air conditioner, gas engine heat pump, train air conditioner, automotive air conditioner, built-in showcase, separate showcase, commercial refrigerator / refrigerator
- the heat cycle system according to [13] which is an ice making machine or a vending machine.
- a working medium for a heat cycle and a composition for a heat cycle system that can replace R410A, provide a heat cycle system having a small composition change, a small temperature gradient, and excellent cycle performance (capacity). Can do. Moreover, the thermal cycle system which is excellent in cycle performance (capability) can be provided.
- FIG. 3 is a cycle diagram in which a change in state of a working medium for heat cycle in a refrigeration cycle system is described on a pressure-enthalpy diagram.
- the working medium for heat cycle of the present invention is a working medium for heat cycle containing an azeotrope-like composition comprising HFO-1132 (E) and HFC-32 and / or HFC-125.
- the azeotrope-like composition comprising HFO-1132 (E) and HFC-32 and / or HFC-125 in the present invention is referred to as “the azeotrope-like composition”.
- the azeotrope composition comprising HFO-1132 (E) and HFC-32 and / or HFC-125
- the azeotrope composition is referred to as “the azeotrope composition”.
- an azeotropic composition means a composition in which the composition of the gas phase and the liquid phase is the same in the vapor-liquid equilibrium state of a mixture of two or more components, and the azeotrope-like composition is an azeotropic composition. It refers to a composition that exhibits substantially the same behavior as the aforementioned behavior at the time of vapor-liquid equilibrium.
- an azeotrope-like composition can be handled equivalent to an azeotrope composition, in this specification, an azeotrope-like composition shall contain an azeotrope composition.
- This azeotropic composition has a relative volatility represented by the following formula of 1.00.
- Specific volatility (mass% of HFO-1132 (E) in the gas phase part / total mass% of HFC-32 and HFC-125 in the gas phase part) / (mass% of HFO-1132 (E) in the liquid phase part) / Total mass% of HFC-32 and HFC-125 in the liquid phase part)
- the relative volatility can be obtained by measuring the composition of the gas phase and liquid phase of a mixture of HFO-1132 (E) in a gas-liquid equilibrium state and HFC-32 and / or HFC-125.
- the azeotropic composition of HFO-1132 (E) and HFC-32 is specifically determined by the following method.
- HFO-1132 (E) and HFC-32 having a predetermined concentration were filled in a pressure vessel at 25 ° C., stirred, and allowed to stand until a vapor-liquid equilibrium state was reached. Thereafter, the gas phase and the liquid phase in the pressure vessel were collected, and the composition was analyzed by gas chromatography. Moreover, relative volatility was calculated
- FIG. 1 shows the liquid phase concentration (mass%) and gas phase of HFO-1132 (E) in a vapor-liquid equilibrium state of a mixture of HFO-1132 (E) and HFC-32 prepared by changing the above various compositions. It is a graph which shows the relationship of a phase concentration (mass%).
- the solid line shows the relationship between the liquid phase concentration (mass%) and the gas phase concentration (mass%) of HFO-1132 (E) measured above, and the broken line shows the same composition in the gas phase and liquid phase.
- a straight line having a relative volatility of 1.00 is shown.
- the present azeotrope-like composition comprising HFO-1132 (E) and HFC-32 has a mass ratio of HFO-1132 (E) and HFC-32 (HFO-1132 (E) [ Mass%] / HFC-32 [mass%]) is in the range of 1/99 to 99/1, and the relative volatility is in the range of 1.00 ⁇ 0.40.
- Test 2 for determining azeotropic composition
- a composition comprising HFO-1132 (E) and HFC-125 was tested in the same manner as in Test 1 for obtaining the azeotropic composition, and the formula for obtaining the relative volatility described above from the composition ratio of the two.
- the relative volatility was determined by The results are shown in Table 2.
- FIG. 2 shows the liquid phase concentration (mass%) and gas phase of HFO-1132 (E) in a vapor-liquid equilibrium state of a mixture of HFO-1132 (E) and HFC-125 prepared by changing the above various compositions. It is a graph which shows the relationship of a phase concentration (mass%).
- the solid line shows the relationship between the liquid phase concentration (mass%) and the gas phase concentration (mass%) of HFO-1132 (E) measured above, and the broken line shows the same composition in the gas phase and liquid phase.
- a straight line having a relative volatility of 1.00 is shown.
- the intersection of the curve indicated by the solid line and the straight line indicated by the broken line is the azeotropic composition
- HFO-1132 (E): HFC-125 40% by mass: 60% by mass.
- the azeotrope-like composition composed of HFO-1132 (E) and HFC-125 has a mass ratio of HFO-1132 (E) and HFC-125 (HFO-1132 (E) [mass% ] / HFC-32 [mass%]) is in the range of 1/99 to 99/1, and the relative volatility is in the range of 1.00 ⁇ 0.40.
- HFO-1132 (E), HFC-32, and HFC-125 have extremely close boiling points and similar physical properties.
- the temperature gradient of the working medium for heat cycle consisting of three components of HFO-1132 (E), HFC-32 and HFC-125 is shown in the examples below.
- HFO-1132 (E) and HFC-32 or HFC- The trend which approximated the temperature gradient of the working medium for heat cycle which consists of 125 two components is shown.
- the temperature gradient is a factor reflecting the azeotrope-like composition. If the temperature gradient of the composition is 1.50 or less, it can be said that the composition has an azeotrope-like composition.
- the composition comprising HFO-1132 (E), HFC-32 and HFC-125 is similar to the composition comprising HFO-1132 (E) and HFC-32 or HFC-125.
- E) and the mass ratio of HFC-125 and HFC-32 ((HFO-1132 (E) [mass%]) / (HFC-125 [mass%] + HFC-32 [mass%])) is 1 /
- An azeotrope-like composition is formed in the range of 99 to 99/1.
- the boiling points of HFO-1132 (E), HFC-32, and HFC-125 are values measured at a pressure of 1.013 ⁇ 10 5 Pa, and the boiling point of HFO-1132 (E) is ⁇ 50 ° C.
- the azeotrope-like composition has a HFO-1132 (E) content of 1 to 99% by mass, HFC-32 and HFC-125.
- a composition having a total content ratio of 99 to 1% by mass was selected.
- temperature gradient is used as one of the indexes for measuring the properties when a mixture is used as a working medium.
- 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. Since the working medium for heat cycle of the present invention contains this azeotrope-like composition, the temperature gradient is close to zero. Therefore, when this is applied to a thermal cycle system, an energy efficient thermal cycle system can be obtained as described below.
- FIG. 3 is a schematic configuration diagram showing an example of the refrigeration cycle system of the present invention.
- the refrigeration cycle system 10 compresses the working medium vapor A into a high-temperature and high-pressure working medium vapor B, and cools and liquefies the working medium vapor B discharged from the compressor 11 to operate at a low temperature and high pressure.
- the condenser 12 as the medium C, the expansion valve 13 that expands the working medium C discharged from the condenser 12 to form the low-temperature and low-pressure working medium D, and the working medium D discharged from the expansion valve 13 are heated.
- 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 substantially constant.
- the azeotropic composition does not change in composition when the composition is repeatedly evaporated and condensed, when used as a working medium, the azeotropic composition can be handled almost equally as a working medium having a single composition.
- the azeotrope-like composition has a small variation in composition when repeated evaporation and condensation, and can be handled in the same manner as the azeotrope composition. Therefore, even when an azeotropic composition or an azeotrope-like composition is used as the working medium, the temperature difference between the outlet temperature and the inlet temperature of the evaporator 14 is substantially constant.
- the temperature difference is not constant.
- the inlet temperature becomes lower than 0 ° C., which causes a problem of frost formation in the evaporator 14.
- the larger the temperature gradient the lower the inlet temperature and the greater the possibility of frost formation.
- the working medium flowing through the heat exchanger such as the evaporator 14 and the condenser 12 and the heat source fluid such as water and air are always opposed to each other.
- the device is designed to improve the heat exchange efficiency by making it flow.
- the temperature difference of the heat source fluid is small in a stable operation state that is generally operated for a long time apart from the start-up time, the temperature gradient is large in the case of a non-azeotropic composition in which the composition of the gas-liquid phase is greatly different. It is difficult to obtain an energy efficient thermal cycle system.
- an azeotropic composition is used as a working medium, an energy efficient thermal cycle system can be obtained.
- the content of HFO-1132 (E) in the working medium for heat cycle of the present invention is preferably 80% by mass or less with respect to the total amount of the working medium for heat cycle.
- HFO-1132 (E) has a so-called self-decomposition property that, when used alone, explodes when an ignition source is present at high temperature or high pressure.
- HFO-1132 (E) is mixed with HFC-32 and / or HFC-125 to make a mixture in which the content of HFO-1132 (E) is suppressed. Decomposition reaction can be suppressed.
- the content ratio of HFO-1132 (E) in the azeotrope-like composition to 80% by mass or less, the temperature when applied to the thermal cycle system, Since it does not have self-decomposability under pressure conditions, a safer working medium for heat cycle can be obtained.
- the working medium for heat cycle of the present invention further contains an optional component described later in the azeotrope-like composition
- the content ratio of HFO-1132 (E) is 80% by mass or less. Since it does not have self-decomposability under temperature and pressure conditions when applied to a heat cycle system, a highly safe working medium for heat cycle can be obtained. In order to obtain higher safety, the content of HFO-1132 (E) is more preferably 60% by mass or less.
- the working medium for heat cycle of the present invention can be used in a heat cycle system with sufficient care depending on the use conditions even if it has a composition having self-degradability.
- the ratio of HFO-1132 (E) to the total amount of the working medium for heat cycle of the present invention is preferably 20% by mass or more, and more preferably 40% by mass or more.
- Examples of the cycle performance in the working medium include coefficient of performance and refrigeration capacity.
- R410A is a standard (1. 000)
- a cycle performance equal to or higher than the refrigerating capacity can be obtained.
- the content ratio of the azeotrope-like composition in the working medium for heat cycle of the present invention is preferably 50% by weight or more, more preferably 60% by weight or more, based on the total amount of the working medium for heat cycle. % Is more preferable.
- the working medium for heat cycle of the present invention is preferably composed of the azeotrope-like composition.
- the working medium for heat cycle of the present invention contains not less than 50% by mass of the present azeotrope-like composition, so that the cycle performance is excellent and the composition change and the temperature gradient can be further reduced.
- the working medium for heat cycle of the present invention is composed only of the present azeotrope-like composition, it is possible to obtain a working medium for heat cycle whose composition change and temperature gradient are nearly zero.
- the working medium for heat cycle of the present invention may optionally contain a compound that is normally used as a working medium in addition to the azeotrope-like composition as long as the effects of the present invention are not impaired.
- optional component examples of the compound (hereinafter referred to as optional component) which the working medium for heat cycle of the present invention may optionally contain in addition to the azeotrope-like composition include HFO other than HFO-1132 (E), HFC-32 HFCs, hydrocarbons, HCFOs and CFOs having other carbon-carbon double bonds.
- the content of optional components is a total amount, preferably 20% by weight or less, and more preferably 10% by weight or less in the working medium for heat cycle (100% by weight).
- the refrigerant manageability can be improved, for example, when the leakage from the heat cycle equipment occurs in the application of the refrigerant or the like, the composition change of the working medium for the heat cycle may increase. May decrease.
- HFO other than HFO-1132 (E) examples include cis-1,2-difluoroethylene (HFO-1132 (Z)), HFO-1261yf, HFO-1243yc, trans -1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye (Z)), HFO-1234ze (E), HFO-1234ze (Z), HFO-1243zf, and the like.
- HFO may be used individually by 1 type and may be used in combination of 2 or more type.
- the heat cycle working medium of the present invention contains HFO other than HFO-1132 (E)
- the content thereof is preferably 1 to 20% by weight in the heat cycle working medium (100% by weight). More preferred is 10% by mass.
- HFC other than HFC-32 and HFC-125
- HFC is a component that improves the cycle performance (capacity) of a thermal cycle system.
- HFCs other than HFC-32 and HFC-125 that may be included in the working fluid for heat cycle of the present invention include tetrafluoroethane, difluoroethane, trifluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, and pentafluorobutane. And heptafluorocyclopentane.
- One HFC may be used alone, or two or more HFCs may be used in combination.
- HFC-134a 1,1,1,2-tetrafluoroethane
- HFC-152a 1,1-difluoroethane
- the working medium for heat cycle of the present invention contains HFC other than HFC-32, the content thereof is preferably 1 to 20% by weight in the working medium for heat cycle (100% by weight), and 2 to 10% by weight. % Is more preferable.
- the content of these HFCs can be controlled according to the required characteristics of the working medium for heat cycle.
- hydrocarbon examples 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 working medium for heat cycle of the present invention contains hydrocarbon, the content thereof is preferably 1 to 20% by weight, more preferably 2 to 5% by weight in the working medium for heat cycle (100% by weight). . If the hydrocarbon is 1% by mass or more, the solubility of the refrigerating machine oil in the working medium for heat cycle is sufficiently improved. If the hydrocarbon is 20% by mass or less, there is an effect in suppressing the combustibility of the working medium for heat cycle.
- HCFO and CFO are components that improve the solubility of refrigerating machine oil in the working medium for heat cycle.
- HCFO include hydrochlorofluoropropene, hydrochlorofluoroethylene, and the like. From the point of sufficiently suppressing the flammability of the working medium for the heat cycle without greatly reducing the cycle performance (capacity) of the heat cycle system.
- HCFO-1224yd -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-1214ya) and 1,2-dichloro-1,2-difluoroethylene (CFO-1112) are particularly preferred.
- the working medium for heat cycle of the present invention contains HCFO and / or CFO, the total content thereof is preferably 1 to 20% by weight in the working medium for heat cycle (100% by weight).
- Chlorine atoms have the effect of suppressing combustibility, and if the contents of HCFO and CFO are in this range, the cycle performance (capacity) of the thermal cycle system is not greatly reduced, and the thermal cycle working medium Combustibility can be sufficiently suppressed.
- HCFO and CFO HCFO having little influence on the ozone layer and little influence on global warming is preferable.
- the heat cycle working medium of the present invention can be used as a composition for a heat cycle system of the present invention, usually mixed with refrigeration oil when applied to a heat cycle system.
- the composition for thermal cycle systems of this invention may contain well-known additives other than these, such as a stabilizer and a leak detection substance.
- refrigerator oil As refrigerating machine oil, well-known refrigerating machine oil used for the composition for heat cycle systems is used. Examples of the refrigerating machine oil include oxygen-containing synthetic oils (ester-based refrigerating machine oils, ether-based refrigerating machine oils, etc.), fluorine-based refrigerating machine oils, mineral oils, hydrocarbon-based synthetic oils, and the like.
- ester refrigerating machine oils include dibasic acid ester oils, polyol ester oils, complex ester oils, and polyol carbonate oils.
- the dibasic acid ester oil includes a dibasic acid having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and a carbon number having a linear or branched alkyl group.
- Esters with 1 to 15 monohydric alcohols methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc. are preferred.
- ditridecyl glutarate di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, di (3-ethylhexyl) sebacate and the like.
- Polyol ester oils include diols (ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5-pentadiol, neopentyl glycol, 1,7- Heptanediol, 1,12-dodecanediol, etc.) or polyol having 3 to 20 hydroxyl groups (trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, glycerin, sorbitol, sorbitan, sorbitol glycerin condensate, etc.); Fatty acids having 6 to 20 carbon atoms (hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, eicosanoic acid,
- esters of is preferable.
- the polyol ester oil may have a free hydroxyl group.
- Polyol ester oils include esters of hindered alcohols (neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, etc.) (trimethylol propane tripelargonate, pentaerythritol 2-ethylhexanoate). And pentaerythritol tetrapelargonate) are preferred.
- the complex ester oil is an ester of a fatty acid and a dibasic acid, a monohydric alcohol and a polyol.
- fatty acid, dibasic acid, monohydric alcohol, and polyol the same ones as described above can be used.
- the polyol carbonate oil is an ester of carbonic acid and polyol.
- examples of the polyol include the same diol as described above and the same polyol as described above.
- the polyol carbonate oil may be a ring-opening polymer of cyclic alkylene carbonate.
- ether refrigerating machine oil examples include polyvinyl ether oil and polyoxyalkylene oil.
- polyvinyl ether oil examples include a polymer of a vinyl ether monomer, a copolymer of a vinyl ether monomer and a hydrocarbon monomer having an olefinic double bond, and a copolymer of a vinyl ether monomer and a vinyl ether monomer having a polyoxyalkylene chain. It is done.
- alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether are preferable.
- the vinyl ether monomer having a polyoxyalkylene chain include compounds in which one of the hydroxyl groups of polyoxyalkylene diol is alkyl etherified and the other is vinyl etherified.
- 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 examples 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.
- polyoxyalkylene oil examples include polyoxyalkylene monools, polyoxyalkylene polyols, alkyl etherified products of polyoxyalkylene monools and polyoxyalkylene polyols, and esterified products of polyoxyalkylene monools and polyoxyalkylene polyols.
- Polyoxyalkylene monools and polyoxyalkylene polyols are used to open a C 2-4 alkylene oxide (ethylene oxide, propylene oxide, etc.) in an initiator such as water or a hydroxyl group-containing compound in the presence of a catalyst such as an alkali hydroxide. Examples thereof include those obtained by a method of addition polymerization.
- the oxyalkylene units in the polyalkylene chain 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.
- hydroxyl group-containing compound examples include monovalent or polyhydric alcohols (methanol, butanol, ethylene glycol, propylene glycol, 1,4-butanediol, glycerol, pentaerythritol and the like.
- polyoxyalkylene oil what is called polyalkylene glycol oil (PAG) obtained by alkyl etherifying all the hydroxyl groups of polyoxyalkylene monool or polyoxyalkylene diol is preferable.
- fluorinated refrigerating machine oil examples include compounds obtained by substituting hydrogen atoms of synthetic oils (such as mineral oils and hydrocarbon synthetic oils described later) with fluorine atoms, perfluoropolyether oils, and fluorinated silicone oils.
- the refrigerating machine oil fraction obtained by subjecting crude oil to atmospheric distillation or vacuum distillation is refined (solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, And paraffinic mineral oils, naphthenic mineral oils, etc., which are refined by appropriately combining white clay treatment and the like.
- hydrocarbon synthetic oil examples include poly ⁇ -olefin, alkylbenzene, alkylnaphthalene and the like.
- Refrigerating machine oil may be used individually by 1 type, and may be used in combination of 2 or more type.
- a polyol ester oil and a polyoxyalkylene oil are preferable from the viewpoint of compatibility with the working medium for the heat cycle, and a polyalkylene glycol oil is particularly preferable because a remarkable antioxidant effect is obtained by the stabilizer. preferable.
- the content of the refrigerating machine oil in the composition for the heat cycle system may be within a range that does not significantly reduce the effect of the present invention, and varies depending on the use, the type of the compressor, etc., but the heat cycle working medium (100 parts by mass) ) Is usually 10 to 100 parts by mass, preferably 20 to 50 parts by mass.
- the content of HFO-1132 (E) is preferably 5% by weight or more, more preferably 20% by weight or more, in the heat cycle composition (100% by weight), 30% by weight. % Or more is more preferable, and 40 mass% or more is particularly preferable.
- Stabilizers are components that improve the stability of the thermal cycle working medium against heat and oxidation.
- examples of the stabilizer include an oxidation resistance improver, a heat resistance improver, and a metal deactivator.
- oxidation resistance improver and heat resistance improver examples include N, N′-diphenylphenylenediamine, p-octyldiphenylamine, p, p′-dioctyldiphenylamine, N-phenyl-1-naphthylamine, and N-phenyl-2-naphthylamine.
- the oxidation resistance improver and the heat resistance improver may be used alone or in combination of two or more.
- Metal deactivators include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimercaptothiadiazole, salicyridin-propylenediamine, pyrazole, benzotriazole, toltriazole, 2-methylbenzimidazole, 3,5-dimethyl Of pyrazole, methylenebis-benzotriazole, organic acids or their esters, primary, secondary or tertiary aliphatic amines, amine salts of organic or inorganic acids, heterocyclic nitrogen-containing compounds, alkyl acid phosphates Examples thereof include amine salts and derivatives thereof.
- the content of the stabilizer may be in a range that does not significantly reduce the effect of the present invention, and is usually 5% by mass or less and preferably 1% by mass or less in the composition for a heat cycle system (100% by mass).
- leak detection substance examples include ultraviolet fluorescent dyes, 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.
- known ultraviolet fluorescent dyes examples include known fragrances such as those described in JP-T-2008-500337 and JP-T-2008-531836.
- solubilizer which improves the solubility of the leak detection substance to the working medium for thermal cycles.
- solubilizer include those described in JP-T-2007-511645, JP-T-2008-500437, JP-T-2008-531836.
- the content of the leak detection substance may be in a range that does not significantly reduce the effect of the present invention, and is usually 2% by mass or less and 0.5% by mass or less in the composition for a heat cycle system (100% by mass). preferable.
- composition for heat cycle of the present invention may contain a compound used as a conventional working medium, refrigerant, or heat transfer medium (hereinafter referred to as other compound).
- other compounds include the following compounds.
- Fluorine-containing ether (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-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF 2 HCF 2 OCH 2 CF 3 , manufactured by Asahi Glass Co., Ltd., AE-3000).
- the content of the other compound may be in a range that does not significantly reduce the effect of the present invention, and is usually 30% by mass or less, preferably 20% by mass or less in the composition for a heat cycle system (100% by mass), 15 mass% or less is more preferable.
- the working medium for heat cycle and the composition for heat cycle system of the present invention replace R410A by containing HFO-1132 (E) and an azeotrope-like composition comprising HFC-32 and / or HFC-125.
- the composition change is extremely small, the temperature gradient is small, and a better cycle performance (capacity) can be obtained.
- a heat cycle system using a heat exchanger such as a condenser or an evaporator
- a heat cycle system using a heat exchanger such as a condenser or an evaporator
- 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.
- a refrigeration cycle system which is an example of a thermal cycle system, will be described with reference to FIG.
- the working medium vapor A discharged from the evaporator 14 is compressed by the compressor 11 to obtain a high-temperature and high-pressure working medium vapor B.
- the working medium vapor B discharged from the compressor 11 is cooled by the fluid F in the condenser 12 and liquefied to obtain a low temperature and high pressure working medium C.
- the fluid F is heated to become a fluid F ′ and discharged from 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.
- 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 diagram, it can be expressed as a trapezoid having A, B, C, and D as apexes as shown in FIG.
- 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 the high-temperature and high-pressure working medium vapor B, which is indicated by an AB line in FIG.
- the working medium vapor A is introduced into the compressor 11 in an overheated state, and the obtained working medium vapor B is also an overheated vapor.
- 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 when the working medium is a non-azeotropic composition is shown as the difference between T 1 and T 2 .
- 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. Incidentally, if Shimese the temperature in the working medium C of low temperature and high pressure at T 3, T 2 -T 3 is (i) ⁇ supercooling degree of the working medium in the cycle of (iv) (SC).
- the DA process is a process in which isobaric heating is performed by the evaporator 14 to return the low temperature / low pressure working medium D to the high temperature / low pressure working medium vapor A, which is indicated by a DA line in FIG.
- 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) (SH).
- T 4 indicates the temperature of the working medium D.
- the cycle performance of the working medium for heat cycle is, for example, the refrigeration capacity of the working medium for heat cycle (hereinafter referred to as “Q” as necessary) and the coefficient of performance (hereinafter referred to as “COP” as necessary). It can be evaluated by.
- Q and COP of the heat cycle working medium are A (after evaporation, high temperature and low pressure), B (after compression, high temperature and high pressure), C (after condensation, low temperature and high pressure), and D (low temperature after expansion).
- each enthalpy, h A , h B , h C , h D in each state of low pressure is used, it can be obtained from the following equations (1) and (2).
- Q indicated by (h A -h D ) corresponds to the output (kW) of the refrigeration cycle, and is required for operating the compression work indicated by (h B -h A ), for example, the compressor.
- the amount of electric power corresponds to the consumed power (kW).
- Q means the ability to freeze the load fluid, and the higher Q means that more work can be done in the same system. In other words, a large Q indicates that the target performance can be obtained with a small amount of working medium, and the system can be miniaturized.
- a method for suppressing the water concentration in the heat cycle system a method using a desiccant (silica gel, activated alumina, zeolite, etc.) can be mentioned.
- a desiccant sica gel, activated alumina, zeolite, etc.
- a zeolitic desiccant is preferable from the viewpoint of chemical reactivity between the desiccant and the heat cycle working medium and the moisture absorption capacity of the desiccant.
- the main component is a compound represented by the following formula (3) from the viewpoint of excellent 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 the valence of M
- x and y are values determined by the crystal structure.
- pore size and fracture strength are particularly important.
- a desiccant having a pore size larger than the molecular diameter of the heat cycle working medium is used, the heat cycle working medium is adsorbed in the desiccant, and as a result, a chemical reaction between the heat cycle working medium and the desiccant.
- undesirable phenomena such as generation of non-condensable gas, decrease in the strength of the desiccant, and decrease in adsorption ability 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 heat cycle working medium only moisture in the heat cycle system is selectively absorbed without adsorbing the heat cycle working medium. Can be removed by adsorption.
- the heat cycle working medium is less likely to be adsorbed to the desiccant, thermal decomposition is less likely to occur, and as a result, deterioration of materials constituting the heat cycle system and generation of contamination can be suppressed.
- the shape is preferably granular or cylindrical.
- the zeolitic desiccant can be formed into an arbitrary shape by solidifying powdered zeolite with a binder (such as bentonite). As long as the zeolitic desiccant is mainly used, other desiccants (silica gel, activated alumina, etc.) may be used in combination.
- the use ratio of the zeolitic desiccant with respect to the working medium for heat cycle is not particularly limited.
- the presence of chlorine in the heat cycle system has undesirable effects such as deposit formation due to reaction with metals, wear of bearings, decomposition of heat cycle working medium and refrigeration oil.
- the chlorine concentration in the heat cycle system is preferably 100 ppm or less, and particularly preferably 50 ppm or less in terms of a mass ratio with respect to the heat cycle working medium.
- Non-condensable gas concentration If a non-condensable gas is mixed in the heat cycle system, it adversely affects the heat transfer in the condenser or the evaporator and the operating pressure rises. Therefore, it is necessary to suppress the mixing as much as possible.
- oxygen which is one of non-condensable gases, reacts with a heat cycle working medium and refrigeration oil, and promotes 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 the volume ratio with respect to the thermal cycle working medium in the gas phase portion of the thermal cycle working medium.
- the thermal cycle working medium of the present invention having excellent cycle performance and small composition change and temperature gradient is used, and therefore the system can be miniaturized. Moreover, since the working medium for heat cycle of the present invention that can be substituted for R410A is used, the cycle performance is excellent.
- a working medium for heat cycle in which HFO-1132 (E) and HFC-32 or HFC-125 are mixed in various proportions in a spherical pressure vessel having an internal volume of 650 cm 3 controlled to a predetermined temperature from the outside. After sealing up to a predetermined pressure, an energy of about 30 J was applied by fusing a platinum wire installed inside. The presence or absence of self-decomposability was confirmed by measuring temperature and pressure changes in the pressure-resistant container generated after application. When pressure increase and temperature increase were observed, it was judged that there was self-degradability. The results are shown in Table 3. The pressure in Table 3 is a gauge pressure.
- Example 1 Evaluation of refrigeration cycle performance
- the cycle performance was evaluated as follows. 3 are applied to the refrigeration cycle system 10 shown in FIG. 3, respectively, and the thermal cycle shown in FIG. 3, ie, adiabatic compression by the compressor 11 in the AB process, and isobaric pressure by the condenser 12 in the BC process.
- the refrigeration cycle performance was evaluated as the cycle performance (capacity and efficiency) when cooling, isoenthalpy expansion by the expansion valve 13 in the CD process, and isobaric heating by the evaporator 14 in the DA process.
- the average evaporation temperature of the working medium for heat cycle in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium for heat cycle in the condenser 12 is 40 ° C.
- the degree of supercooling of the working medium for heat cycle in the condenser 12 is evaluated.
- the degree of superheat of the working medium for heat cycle in the evaporator 14 was 5 ° C.
- the refrigeration capacity and the coefficient of performance are A (after evaporation, high temperature and low pressure), B (after compression, high temperature and high pressure), C (after condensation, low temperature and high pressure), and D (after expansion, low temperature and low pressure).
- 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
- Thermodynamic properties necessary for calculation of the refrigeration 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.
- the relative performance (respective heat cycle working medium / R410A) of the refrigerating cycle performance (refrigeration capacity and coefficient of performance) of the working medium for heat cycle 1 to 28 with respect to R410A was determined.
- the results are shown in Tables 4 to 6 together with the compositions of the heat cycle working media 1 to 28.
- Table 7 shows the global warming potential (GWP) by value. Note that the GWP of HFO-1132 (E) is a value assumed to be measured according to the IPCC Fourth Evaluation Report.
- the thermal cycle working medium composed of the azeotrope-like composition comprising HFO-1132 (E) and HFC-32 and / or HFC-125 has a small temperature gradient. It can also be seen that a coefficient of performance and a refrigerating capacity equal to or higher than those of the working medium made of R410A can be obtained.
- the GWP in the mixture can be shown as a weighted average by the composition mass.
- the GWP of the thermal cycle working medium of each composition in Tables 4 to 6 can be calculated from the values shown in Table 7.
- the thermal cycle working medium of the present invention can select R410A by selecting the composition. It can be seen that the GWP can be made smaller than the working medium consisting of
- the working medium for heat cycle of the present invention includes a refrigerant for a refrigerator, a refrigerant for an air conditioner, a working fluid 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. It is useful as a working medium.
- a refrigerant for a refrigerator a refrigerant for an air conditioner
- a working fluid for a power generation system waste heat recovery power generation, etc.
- a working medium for a latent heat transport device heat pipe, etc.
- secondary cooling medium etc.
Abstract
Description
(1)3,3,3-トリフルオロプロペン(HFO-1243zf)、1,3,3,3-テトラフルオロプロペン(HFO-1234ze)、2-フルオロプロペン(HFO-1261yf)、2,3,3,3-テトラフルオロプロペン(HFO-1234yf)、1,1,2-トリフルオロプロペン(HFO-1243yc)等を含む作動媒体を用いた熱サイクルシステム(例えば、特許文献1参照)。
(2)1,2,3,3,3-ペンタフルオロプロペン(HFO-1225ye)、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))、HFO-1234yf等を含む作動媒体を用いた熱サイクルシステム(例えば、特許文献2参照)。
(3)トランス-1,2-ジフルオロエチレン(HFO-1132(E))、シス-1,2-ジフルオロエチレン(HFO-1132(Z))を含む作動媒体を用いた熱サイクルシステム(例えば、特許文献3参照)。
[2]前記共沸様組成物が、比揮発度が1.00±0.40の範囲にある組成物である、[1]に記載の熱サイクル用作動媒体。
[3]前記共沸様組成物が、前記HFO-1132(E)を1~99質量%、前記HFC-32およびHFC-125の合計量を99~1質量%含む、[1]または[2]に記載の熱サイクル用作動媒体。
[4]前記共沸様組成物が、HFO-1132(E)とHFC-32とからなる、[1]~[3]のいずれかに記載の熱サイクル用作動媒体。
[5]前記共沸様組成物が、HFO-1132(E)とHFC-125とからなる、[1]~[3]のいずれかに記載の熱サイクル用作動媒体。
[6]前記共沸様組成物が、HFO-1132(E)とHFC-32とHFC-125とからなる、[1]~[3]のいずれかに記載の熱サイクル用作動媒体。
[8]前記熱サイクル用作動媒体の全量に対する前記HFO-1132(E)の割合が80質量%以下である、[1]~[7]のいずれかに記載の熱サイクル用作動媒体。
[9]前記熱サイクル用作動媒体の全量に対する前記HFO-1132(E)の割合が20質量%以上である、[1]~[8]のいずれかに記載の熱サイクル用作動媒体。
[10]前記熱サイクル用作動媒体が前記共沸様組成物からなる、[1]~[9]のいずれかに記載の熱サイクル用作動媒体。
[12]前記[11]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。
[13]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、[12]に記載の熱サイクルシステム。
[14]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、[13]に記載の熱サイクルシステム。
[熱サイクル用作動媒体]
本発明の熱サイクル用作動媒体は、HFO-1132(E)と、HFC-32および/またはHFC-125とからなる共沸様組成物を含む熱サイクル用の作動媒体である。
以下、本発明における「HFO-1132(E)と、HFC-32および/またはHFC-125とからなる共沸様組成物」を「本共沸様組成物」という。また、本共沸様組成物のうち、「HFO-1132(E)と、HFC-32および/またはHFC-125とからなる共沸組成物」を「本共沸組成物」という。
本共沸組成物は、以下の式で示される比揮発度が1.00である。
(比揮発度を求める式)
比揮発度=(気相部におけるHFO-1132(E)の質量%/気相部におけるHFC-32およびHFC-125の合計質量%)/(液相部におけるHFO-1132(E)の質量%/液相部におけるHFC-32およびHFC-125の合計質量%)
所定の濃度のHFO-1132(E)とHFC-32とを、25℃で耐圧容器内に充填し、撹拌した後、気液平衡状態となるまで静置した。その後、耐圧容器内の気相および液相を採取し、それぞれガスクロマトグラフによって組成の分析を行った。また、両者の組成比から、上に説明した比揮発度を求める式により比揮発度を求めた。結果を表1に示す。
また、図1より、HFO-1132(E)とHFC-32とからなる組成物においては、HFO-1132(E)が1~99質量%の範囲で気液平衡状態における液相濃度(質量%)と気相濃度(質量%)の関係が、上記破線で示す比揮発度1.00の直線に近似していることがわかる。上記測定結果によれば、HFO-1132(E)とHFC-32とからなる本共沸様組成物は、HFO-1132(E)とHFC-32との質量比(HFO-1132(E)[質量%]/HFC-32[質量%])が1/99~99/1の範囲で、比揮発度が1.00±0.40の範囲である。
また、HFO-1132(E)とHFC-125とからなる組成物について、上記共沸組成を求める試験1と同様に試験を行い、両者の組成比から、上に説明した比揮発度を求める式により比揮発度を求めた。結果を表2に示す。
また、図2より、HFO-1132(E)とHFC-125とからなる組成物においては、HFO-1132(E)が1~99質量%の範囲で気液平衡状態における液相濃度(質量%)と気相濃度(質量%)の関係が、上記破線で示す比揮発度1.00の直線に近似していることがわかる。上記測定結果によれば、HFO-1132(E)とHFC-125とからなる共沸様組成物は、HFO-1132(E)とHFC-125の質量比(HFO-1132(E)[質量%]/HFC-32[質量%])が1/99~99/1の範囲で、比揮発度が1.00±0.40の範囲である。
上記の結果を勘案して、本発明の熱サイクル用作動媒体においては、本共沸様組成物として、HFO-1132(E)の含有割合が1~99質量%、HFC-32およびHFC-125の合計の含有割合が99~1質量%の組成物を選択することとした。
また、共沸組成物は、該組成物を繰り返し蒸発、凝縮させた場合、組成変化がないため、作動媒体として用いる場合に、単一組成の作動媒体とほぼ等しく取り扱える。また、共沸様組成物は、蒸発、凝縮を繰り返した場合の組成の変動が小さく、共沸組成物と同等に取り扱える。したがって、共沸組成物または共沸様組成物を作動媒体として用いた場合にも、蒸発器14の出口温度と入口温度との温度差がほぼ一定となる。
本発明の熱サイクル用作動媒体は、本発明の効果を損なわない範囲で上記共沸様組成物以外に、通常作動媒体として用いられる化合物を任意に含有してもよい。
本発明の熱サイクル用作動媒体において、任意成分の含有量は合量で、熱サイクル用作動媒体(100質量%)中、20質量%以下が好ましく、10質量%以下が好ましい。任意成分の含有量が20質量%を超えると、冷媒等の用途において、熱サイクル機器からの漏えいが生じた場合、熱サイクル用作動媒体の組成変化が大きくなるおそれがある等、冷媒管理性が低下することがある。
本発明の熱サイクル用作動媒体が含んでもよいHFO-1132(E)以外のHFOとしては、シス-1,2-ジフルオロエチレン(HFO-1132(Z))、HFO-1261yf、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))、HFO-1234ze(E)、HFO-1234ze(Z)、HFO-1243zf等が挙げられる。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。
本発明の熱サイクル用作動媒体が、HFO-1132(E)以外のHFOを含む場合には、その含有量は熱サイクル用作動媒体(100質量%)中、1~20質量%が好ましく、2~10質量%がより好ましい。
HFCは、熱サイクルシステムのサイクル性能(能力)を向上させる成分である。本発明の熱サイクル用作動媒体が含んでもよいHFC-32およびHFC-125以外のHFCとしては、テトラフルオロエタン、ジフルオロエタン、トリフルオロエタン、ペンタフルオロプロパン、ヘキサフルオロプロパン、ヘプタフルオロプロパン、ペンタフルオロブタン、ヘプタフルオロシクロペンタン等が挙げられる。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。
HFC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点から、1,1,1,2-テトラフルオロエタン(HFC-134a)、1,1-ジフルオロエタン(HFC-152a)が特に好ましい。
本発明の熱サイクル用作動媒体が、HFC-32以外のHFCを含む場合には、その含有量は熱サイクル用作動媒体(100質量%)中、1~20質量%が好ましく、2~10質量%がより好ましい。これらHFCの含有量は、熱サイクル用作動媒体の要求特性に応じて制御を行うことができる。
炭化水素としては、プロパン、プロピレン、シクロプロパン、ブタン、イソブタン、ペンタン、イソペンタン等が挙げられる。
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。
本発明の熱サイクル用作動媒体が、炭化水素を含む場合には、その含有量は熱サイクル用作動媒体(100質量%)中、1~20質量%が好ましく、2~5質量%がより好ましい。炭化水素が1質量%以上であれば、熱サイクル用作動媒体への冷凍機油の溶解性が充分に向上する。炭化水素が20質量%以下であれば、熱サイクル用作動媒体の燃焼性を抑制するのに効果がある。
HCFO、CFOは、熱サイクル用作動媒体への冷凍機油の溶解性を向上させる成分である。HCFOとしては、ヒドロクロロフルオロプロペン、ヒドロクロロフルオロエチレン等が挙げられ、熱サイクルシステムのサイクル性能(能力)を大きく低下させることなく、熱サイクル用作動媒体の燃焼性を充分に抑える点から、1-クロロ-2,3,3,3-テトラフルオロプロペン(HCFO-1224yd)、1-クロロ-1,2-ジフルオロエチレン(HCFO-1122)が特に好ましい。
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。
本発明の熱サイクル用作動媒体が、HCFOおよび/またはCFOを含有する場合には、それの含有量は合計で、熱サイクル用作動媒体(100質量%)中、1~20質量%が好ましい。塩素原子は燃焼性を抑制する効果を有しており、HCFOとCFOの含有量がこの範囲にあると、熱サイクルシステムのサイクル性能(能力)を大きく低下させることなく、熱サイクル用作動媒体の燃焼性を充分に抑えることができる。HCFO、CFO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HCFOが好ましい。
本発明の熱サイクル用作動媒体は、熱サイクルシステムへの適用に際して、通常、冷凍機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。また、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。
冷凍機油としては、熱サイクルシステム用組成物に用いられる公知の冷凍機油が用いられる。
冷凍機油としては、含酸素系合成油(エステル系冷凍機油、エーテル系冷凍機油等)、フッ素系冷凍機油、鉱物油、炭化水素系合成油等が挙げられる。
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。
ポリオールエステル油としては、ヒンダードアルコール(ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ペンタエリスルトール等)のエステル(トリメチロールプロパントリペラルゴネート、ペンタエリスリトール2-エチルヘキサノエート、ペンタエリスリトールテトラペラルゴネート等)が好ましい。
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。
オレフィン性二重結合を有する炭化水素モノマーとしては、エチレン、プロピレン、各種ブテン、各種ペンテン、各種ヘキセン、各種ヘプテン、各種オクテン、ジイソブチレン、トリイソブチレン、スチレン、α-メチルスチレン、各種アルキル置換スチレン等が挙げられる。オレフィン性二重結合を有する炭化水素モノマーは、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。
ポリビニルエーテル共重合体は、ブロックまたはランダム共重合体のいずれであってもよい。
水酸基含有化合物としては、1価または多価アルコール(メタノール、ブタノール、エチレングリコール、プロピレングリコール、1,4-ブタンジオール、グリセロール、ペンタエリスリトール等が挙げられる。
ポリオキシアルキレン油としては、ポリオキシアルキレンモノオールまたはポリオキシアルキレンジオールの水酸基のすべてをアルキルエーテル化して得られる、ポリアルキレングリコール油(PAG)と呼ばれているものが好ましい。
冷凍機油としては、熱サイクル用作動媒体との相溶性の点から、ポリオールエステル油およびポリオキシアルキレン油が好ましく、安定化剤によって顕著な酸化防止効果が得られる点から、ポリアルキレングリコール油が特に好ましい。
安定剤は、熱および酸化に対する熱サイクル用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、耐酸化性向上剤、耐熱性向上剤、金属不活性剤等が挙げられる。
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、公知の紫外線蛍光染料が挙げられる。
臭いマスキング剤としては、特表2008-500437号公報、特表2008-531836号公報に記載されたもの等、公知の香料が挙げられる。
可溶化剤としては、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が挙げられる。
本発明の熱サイクル用組成物は、従来の作動媒体、冷媒、熱伝達媒体として用いられている化合物(以下、他の化合物と記す。)を含んでいてもよい。
他の化合物としては、下記の化合物が挙げられる。
本発明の熱サイクル用作動媒体および熱サイクルシステム用組成物は、HFO-1132(E)と、HFC-32および/またはHFC-125からなる共沸様組成物を含有することで、R410Aに代替可能で、組成変化が極めて小さく、温度勾配が小さく、さらに良好なサイクル性能(能力)が得られるものである。
本発明の熱サイクルシステム用組成物が適用される熱サイクルシステムとしては、凝縮器や蒸発器等の熱交換器による熱サイクルシステムが特に制限なく用いられる。熱サイクルシステム、例えば、冷凍サイクルにおいては、気体の作動媒体を圧縮機で圧縮し、凝縮器で冷却して圧力が高い液体をつくり、膨張弁で圧力を下げ、蒸発器で低温気化させて気化熱で熱を奪う機構を有する。
(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。
(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。
(iii)凝縮器12から排出された作動媒体Cを膨張弁13にて膨張させて低温低圧の作動媒体Dとする。
(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。
COP=Q/圧縮仕事=(hA-hD)/(hB-hA) …(2)
熱サイクルシステム内に水分が混入する問題がある。水分の混入は、キャピラリーチューブ内での氷結、熱サイクル用作動媒体や冷凍機油の加水分解、熱サイクル内で発生した酸成分による材料劣化、コンタミナンツの発生等により発生する。特に、上述したポリアルキレングリコール油、ポリオールエステル油等は、吸湿性が極めて高く、また、加水分解反応を生じやすく、冷凍機油としての特性が低下し、圧縮機の長期信頼性を損なう大きな原因となる。また、自動車空調機器においては、振動を吸収する目的で使用されている冷媒ホースや圧縮機の軸受け部から水分が混入しやすい傾向にある。したがって、冷凍機油の加水分解を抑えるためには、熱サイクルシステム内の水分濃度を抑制する必要がある。
M2/nO・Al2O3・xSiO2・yH2O ・・・(3)。
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。
熱サイクル用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、熱サイクル用作動媒体が乾燥剤中に吸着され、その結果、熱サイクル用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。
ゼオライト系乾燥剤は、粉末状のゼオライトを結合剤(ベントナイト等)で固めることにより任意の形状とすることができる。ゼオライト系乾燥剤を主体とするかぎり、他の乾燥剤(シリカゲル、活性アルミナ等)を併用してもよい。
熱サイクル用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。
熱サイクルシステム内に塩素が存在すると、金属との反応による堆積物の生成、軸受け部の磨耗、熱サイクル用作動媒体や冷凍機油の分解等、好ましくない影響をおよぼす。
熱サイクルシステム内の塩素濃度は、熱サイクル用作動媒体に対する質量割合で100ppm以下が好ましく、50ppm以下が特に好ましい。
熱サイクルシステム内に不凝縮性気体が混入すると、凝縮器や蒸発器における熱伝達の不良、作動圧力の上昇という悪影響をおよぼすため、極力混入を抑制する必要がある。特に、不凝縮性気体の一つである酸素は、熱サイクル用作動媒体や冷凍機油と反応し、分解を促進する。
不凝縮性気体濃度は、熱サイクル用作動媒体の気相部において、熱サイクル用作動媒体に対する容積割合で1.5体積%以下が好ましく、0.5体積%以下が特に好ましい。
以上説明した熱サイクルシステムにあっては、サイクル性能に優れ、組成変化および温度勾配の小さい本発明の熱サイクル用作動媒体を用いているため、システムを小型化できる。
また、R410Aに代替可能な本発明の熱サイクル用作動媒体を用いているため、サイクル性能に優れる。
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。
(冷凍サイクル性能の評価)
表4~6に示す割合の本共沸様組成物からなる熱サイクル用作動媒体1~28について、サイクル性能の評価を次のように行った。図3の冷凍サイクルシステム10に、熱サイクル用作動媒体1~28をそれぞれ適用して、図3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のサイクル性能(能力および効率)として冷凍サイクル性能(冷凍能力および成績係数)を評価した。
なお、2014年6月6日に出願された日本特許出願2014-118164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 (14)
- トランス-1,2-ジフルオロエチレンと、ジフルオロメタンおよび/またはペンタフルオロエタンとからなる共沸様組成物を含むことを特徴とする熱サイクル用作動媒体。
- 前記共沸様組成物が、比揮発度が1.00±0.40の範囲にある組成物である、請求項1に記載の熱サイクル用作動媒体。
- 前記共沸様組成物が、前記トランス-1,2-ジフルオロエチレンを1~99質量%、前記ジフルオロメタンおよびペンタフルオロエタンの合計量を99~1質量%含む、請求項1または2に記載の熱サイクル用作動媒体。
- 前記共沸様組成物が、トランス-1,2-ジフルオロエチレンとジフルオロメタンとからなる、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。
- 前記共沸様組成物が、トランス-1,2-ジフルオロエチレンとペンタフルオロエタンとからなる、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。
- 前記共沸様組成物が、トランス-1,2-ジフルオロエチレンとジフルオロメタンとペンタフルオロエタンとからなる、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。
- 前記熱サイクル用作動媒体の全量に対する前記共沸様組成物の割合が50質量%以上である、請求項1~6のいずれか1項に記載の熱サイクル用作動媒体。
- 前記熱サイクル用作動媒体の全量に対する前記トランス-1,2-ジフルオロエチレンの割合が80質量%以下である、請求項1~7のいずれか1項に記載の熱サイクル用作動媒体。
- 前記熱サイクル用作動媒体の全量に対する前記トランス-1,2-ジフルオロエチレンの割合が20質量%以上である、請求項1~8のいずれか1項に記載の熱サイクル用作動媒体。
- 前記熱サイクル用作動媒体が前記共沸様組成物からなる、請求項1~9のいずれか1項に記載の熱サイクル用作動媒体。
- 請求項1~10のいずれか1項に記載の熱サイクル用作動媒体と、冷凍機油とを含む、熱サイクルシステム用組成物。
- 請求項11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12に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13に記載の熱サイクルシステム。
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CN106029821B (zh) * | 2014-01-31 | 2020-06-02 | Agc株式会社 | 热循环用工作介质、热循环系统用组合物以及热循环系统 |
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JP2020111742A (ja) * | 2019-01-11 | 2020-07-27 | ダイキン工業株式会社 | トランス−1,2−ジフルオロエチレンを含む組成物 |
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JP2021095412A (ja) * | 2019-04-19 | 2021-06-24 | ダイキン工業株式会社 | トランス−1,2−ジフルオロエチレン(hfo−1132(e))及び/又はシス−1,2−ジフルオロエチレン(hfo−1132(z))と水とを含有する精製物 |
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Also Published As
Publication number | Publication date |
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EP3153560A1 (en) | 2017-04-12 |
CN106414655A (zh) | 2017-02-15 |
EP3153560A4 (en) | 2018-01-10 |
JPWO2015186558A1 (ja) | 2017-04-20 |
US20170058171A1 (en) | 2017-03-02 |
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