WO2015141677A1 - 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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- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with 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
- 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
- F25B31/00—Compressor arrangements
- F25B31/002—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
- 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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- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
- C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/70—Soluble oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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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
- F25B2339/00—Details of evaporators; Details of condensers
- F25B2339/04—Details of condensers
- F25B2339/047—Water-cooled condensers
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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
- F25B2400/121—Inflammable refrigerants using R1234
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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
- F25B25/00—Machines, plants or systems, using a combination of modes of operation covered by two or more of the groups F25B1/00 - F25B23/00
- F25B25/005—Machines, plants or systems, using a combination of modes of operation covered by two or more of the groups F25B1/00 - F25B23/00 using primary and secondary systems
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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
- F25B2500/14—Problems to be solved the presence of moisture in a refrigeration component or 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
- 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 composition for a heat cycle system and a heat cycle system using the composition.
- CFC chlorofluorocarbons
- HCFC hydrochlorofluorocarbons
- HFCs hydrofluorocarbons
- HFC-32 difluoromethane
- HFC-125 pentafluoroethane
- GWP global warming potential
- Patent Document 1 discloses a working medium using 1,1,2-trifluoroethylene (HFO-1123) which has the above-mentioned characteristics and provides excellent cycle performance. The technique concerning is disclosed. Patent Document 1 further attempts to use HFO-1123 in combination with various HFCs and HFOs for the purpose of improving the nonflammability and cycle performance of the working medium.
- HFO-1123 1,1,2-trifluoroethylene
- HFO-1123 may cause a self-decomposition reaction under high temperature and high pressure conditions.
- a composition containing HFO-1123 is put to practical use, there is a problem in improving the durability of the working medium using HFO-1123. There is.
- HFO-1123 is a compound containing an unsaturated bond in the molecule and has a very short lifetime in the atmosphere. Therefore, under conditions where compression and heating are repeated in a thermal cycle, saturation with conventional HFC and HCFC is achieved. There was a problem inferior in stability to HFC and HCFC.
- An object of the present invention is to provide a composition for a heat cycle system and a heat cycle system that have little influence on the ozone layer, have a small GWP, and are excellent in stability and durability.
- the present invention provides a composition for a thermal cycle system and a thermal cycle system having the configurations described in [1] to [12] below.
- a thermal cycle system composition comprising a working medium containing trifluoroethylene and difluoromethane and a phosphate ester, wherein the interaction between the working medium and the phosphate ester determined from the value of the Hansen solubility parameter
- phosphate ester is a phosphate triester, an acid phosphate monoester, or an acid phosphate diester.
- phosphoric acid triester is a trialkyl phosphate or a triaryl phosphate.
- acidic phosphoric acid diester is a dialkyl acid phosphate or a diaryl acid phosphate.
- the mass ratio of trifluoroethylene and difluoromethane (trifluoroethylene / difluoromethane) in the working medium is 1/99 to 99/1, [1] to [6] Composition for thermal cycle system.
- the working medium further includes at least one hydrofluoroolefin selected from 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene.
- the composition for thermal cycle systems in any one of.
- the working medium contains trifluoroethylene, difluoromethane, and 2,3,3,3-tetrafluoropropene, and is based on the total amount of trifluoroethylene, difluoromethane, and 2,3,3,3-tetrafluoropropene.
- the composition for a heat cycle system according to [8], wherein the ratio of these three components is as follows.
- the working medium contains trifluoroethylene, difluoromethane, and 1,3,3,3-tetrafluoropropene, and is based on the total amount of trifluoroethylene, difluoromethane, and 1,3,3,3-tetrafluoropropene.
- the composition for a heat cycle system according to [8], wherein the ratio of these three components is as follows.
- the heat cycle system is a refrigeration / refrigeration device, an air conditioning device, a power generation system, a heat transport device, or a secondary cooler.
- the composition for a heat cycle system of the present invention has little influence on the ozone layer, has a small GWP, and is excellent in stability and durability. Moreover, since the thermal cycle system of the present invention uses the composition for a thermal cycle system of the present invention, there is little influence on the ozone layer, the GWP is small, and the stability and durability are excellent.
- FIG. 2 is a cycle diagram in which a change in state of a working medium in the refrigeration cycle system of FIG. 1 is described on a pressure-enthalpy diagram.
- GWP is a value for 100 years as shown in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (2007) or measured according to the method.
- composition for a heat cycle system of the present invention includes a working medium containing trifluoroethylene (HFO-1123) and difluoromethane (HFC-32), and a specific phosphate ester. Oils, stabilizers, leak detection substances and the like may be included.
- a heat cycle system using a heat exchanger such as a condenser or an evaporator is used without particular limitation.
- a heat cycle system for example, a refrigeration cycle
- a gas working medium is compressed by a compressor, cooled by a condenser to produce a high-pressure liquid, the pressure is reduced by an expansion valve, and vaporized at a low temperature by an evaporator. It has a mechanism that takes heat away with heat.
- HFO-1123 When HFO-1123 is used alone as a working medium in such a heat cycle system, HFO-1123 may undergo a self-decomposing reaction under specific temperature conditions and pressure conditions.
- HFO-1123 In the composition for a thermal cycle system of the present invention, by coexisting HFC-32 and a specific phosphate ester, it is possible to exhibit cycle performance over a long period while suppressing the self-decomposition reaction of HFO-1123. It becomes.
- the working medium in the present invention contains HFO-1123 and HFC-32, and may contain other compounds as necessary.
- HFO-1123 is known to cause a chain self-decomposition reaction accompanied by a rapid temperature and pressure increase when an ignition source is present at high temperature or high pressure.
- the self-decomposition reaction can be suppressed by mixing HFO-1123 with HFC-32 to reduce the content of HFO-1123.
- the pressure condition when the working medium for heat cycle in the present invention is applied to a heat cycle system is usually about 5.0 MPa or less.
- the working medium for heat cycle composed of HFO-1123 and HFC-32 does not have self-decomposability under a pressure condition of 5.0 MPa, so that it can be used under general temperature conditions when applied to a heat cycle system.
- a highly stable working medium can be obtained.
- a highly stable working medium is obtained by using a composition that does not have self-decomposability at about 7.0 MPa. be able to.
- a self-decomposable composition can be used in a heat cycle system with sufficient care depending on the use conditions.
- the mass ratio of HFO-1123 to HFC-32 (HFO-1123 / HFC-32) in the working medium is preferably 1/99 to 99/1 because GWP of the working medium is small and cycle performance is excellent. Furthermore, 10/90 to 60/40 is more preferable, and 20/80 to 50/50 is particularly preferable from the viewpoint of suppressing the self-decomposition reaction of HFO-1123 and excellent compatibility with the phosphate ester.
- the working medium in the present invention has a very small temperature gradient.
- the temperature gradient is an index for measuring the difference in composition between the liquid phase and the gas phase in 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. In the azeotrope, the temperature gradient is zero, and in the pseudoazeotrope, the temperature gradient is very 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 mixture having a large temperature gradient. For this reason, when a mixture is used as a working medium, a working medium having an appropriate temperature gradient is desired.
- the total content of HFO-1123 and HFC-32 is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. If the total content ratio of HFO-1123 and HFC-32 is in the above-mentioned range, a working medium having a very small composition change and a small temperature gradient and excellent balance of various properties such as GWP can be obtained.
- the working medium in the present invention may contain other compounds used as a normal working medium in addition to HFO-1123 and HFC-32 as long as the effects of the present invention are not impaired.
- Other compounds include, for example, HFCs other than HFC-32, HFOs other than HFO-1123 (HFCs having a carbon-carbon double bond), other HFO-1123s other than these, and other vaporized and liquefied with HFC-32 Components and the like.
- HFC other than HFC-32 and HFO other than HFO-1123 are preferable.
- the working medium in the present invention contains other compounds, the content is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
- the content of HFO-1234yf and HFO-1234ze (Z, E) described later is not limited to the above.
- HFCs other than HFC-32 HFCs having 1 to 5 carbon atoms are preferable because they have little influence on the ozone layer and have low GWP.
- the HFC may be linear, branched, or cyclic.
- HFCs other than HFC-32 include difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane (HFC-125), pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane, and the like. Can be mentioned.
- 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,2, and the like have little influence on the ozone layer and have excellent cycle characteristics.
- 2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), and HFC-125 are preferred, HFC-32, HFC-152a, HFC-134a, and HFC -125 is more preferred.
- One HFC may be used alone, or two or more HFCs may be used in combination.
- HFO other than HFO-1123 it is preferable to select HFO as an optional component other than HFO-1123 from the same viewpoint as the above HFC.
- HFO even if it is other than HFO-1123, GWP is much lower than HFC. Therefore, as HFOs other than HFO-1123 combined with HFO-1123, it is particularly noted that the cycle performance as the working medium is improved and the temperature gradient is kept within an appropriate range rather than considering GWP. These are preferably selected as appropriate.
- HFO other than HFO-1123 examples include 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf), 1, 1,2-trifluoropropene (HFO-1243yc), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 3 , 3,3-trifluoropropene (HFO-1243zf) and the like.
- HFO-1225ye and HFO-1234ze have stereoisomers of cis form (Z form) and trans form (E form), respectively, HFO-1225ye will be referred to as HFO-1225ye. (Z), HFO-1225ye (E), HFO-1234ze (Z), and HFO-1234ze (E). Moreover, when not distinguishing both and the mixture of both may be sufficient, it may show by (Z, E).
- HFOs other than HFO-1123 may be used alone or in combination of two or more.
- HFO-1123 and HFC-32 may contain carbon dioxide, hydrocarbons, chlorofluoroolefin (CFO), hydrochlorofluoroolefin (HCFO), and the like.
- hydrocarbon examples include propane, propylene, cyclopropane, butane, isobutane, pentane, and isopentane.
- a hydrocarbon may be used individually by 1 type and may be used in combination of 2 or more type.
- the working medium contains a hydrocarbon, the content ratio is less than 10% by weight with respect to 100% by weight of the working medium, preferably 1 to 5% by weight, and more preferably 3 to 5% by weight. If a hydrocarbon is more than a lower limit, the compatibility of the mineral type lubricating oil to a working medium will become better.
- CFO examples include chlorofluoropropene, chlorofluoroethylene and the like, and 1,1-dichloro-2,3,3, from the viewpoint of easily suppressing the flammability of the working medium without greatly reducing the cycle performance of the working medium.
- 3-tetrafluoropropene CFO-1214ya
- 1,3-dichloro-1,2,3,3-tetrafluoropropene CFO-1214yb
- 1,2-dichloro-1,2-difluoroethylene CFO-1112
- One type of CFO may be used alone, or two or more types may be used in combination.
- the content ratio is less than 10% by weight with respect to 100% by weight of the working medium, preferably 1 to 8% by weight, and more preferably 2 to 5% by weight. If the content ratio of CFO is equal to or higher than the lower limit value, it is easy to suppress the combustibility of the working medium. If the content ratio of CFO is not more than the upper limit value, good cycle performance is easily obtained.
- HCFO examples include hydrochlorofluoropropene and hydrochlorofluoroethylene.
- HCFO 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd)
- 1-chloro can be used because flammability of the working medium can be easily suppressed without greatly reducing the cycle performance of the working medium.
- -1,2-difluoroethylene (HCFO-1122) is preferred.
- HCFO may be used alone or in combination of two or more.
- the content of HCFO in 100% by mass of the working medium is less than 10% by mass, preferably 1 to 8% by mass, and more preferably 2 to 5% by mass. If the content ratio of HCFO is equal to or more than the lower limit value, it is easy to suppress the combustibility of the working medium. If the content ratio of HCFO is not more than the upper limit value, good cycle performance is easily obtained.
- the working medium in the present invention contains HFO-1123, HFO-1234yf and HFC-32
- the following composition ranges are preferable. 10% by mass ⁇ HFO-1123 ⁇ 75% by mass 0% by mass ⁇ HFO-1234yf ⁇ 50% by mass 5 mass% ⁇ HFC-32 ⁇ 75 mass%
- the working medium having the above composition 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.
- this working medium is a working medium that has a very low GWP, has a small temperature gradient, and has a certain capacity and efficiency when used in a thermal cycle, and can obtain good cycle performance.
- the working medium in the present invention As a more preferable composition of the working medium in the present invention, 30 to 70% by mass of HFO-1123 and 4 to 40% by mass of HFO-1234yf with respect to the total amount of HFO-1123, HFO-1234yf and HFC-32, And HFC-32 in a proportion of 5 to 30% by mass, and the content of HFO-1123 with respect to the total amount of the working medium is 70 mol% or less.
- the working medium in the above range is a highly durable working medium in which the above effect is enhanced and the self-decomposition reaction of HFO-1123 is suppressed. From the viewpoint of relative coefficient of performance, the content of HFC-32 is more preferably 8% by mass or more.
- the working medium in the present invention contains HFO-1123, HFO-1234yf and HFC-32
- the content of HFO-1123 with respect to the total amount of the working medium is 70 mol% or less.
- the self-decomposition reaction of HFO-1123 is suppressed, and a highly durable working medium can be obtained.
- a more preferable composition range (R) is shown below. ⁇ Composition range (R)> 10% by mass ⁇ HFO-1123 ⁇ 70% by mass 0% by mass ⁇ HFO-1234yf ⁇ 50% by mass 30% by mass ⁇ HFC-32 ⁇ 75% by mass
- the working medium having the above composition 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. That is, it is a working medium in which good cycle performance can be obtained by having a low temperature gradient and high performance and efficiency when used in a thermal cycle after GWP is kept low and durability is ensured.
- composition range (R) preferred ranges are shown below. 20% by mass ⁇ HFO-1123 ⁇ 70% by mass 0% by mass ⁇ HFO-1234yf ⁇ 40% by mass 30% by mass ⁇ HFC-32 ⁇ 75% by mass
- the working medium having the above composition 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 of them are suppressed. That is, it is a working medium in which GWP is kept low and durability is ensured, and when used in a thermal cycle, the temperature gradient is smaller and the cycle performance is higher by having higher capacity and efficiency. is there.
- composition range (R) In the working medium having the composition range (R), more preferred composition ranges are shown below.
- composition ranges are more preferable.
- the working medium having a more preferable composition range of the above composition range (R) 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. It is.
- this working medium has a GWP with an upper limit of 300 or less, and durability is ensured, and when used in a heat cycle, the temperature gradient is less than 5.8, and the relative coefficient of performance and relative This is a working medium having a refrigerating capacity close to 1 and good cycle performance.
- 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. From the viewpoint of a large relative coefficient of performance, 8% by mass ⁇ HFO-1234yf is more preferable. Further, HFO-1234yf ⁇ 35 mass% is more preferable from the viewpoint of high relative refrigeration capacity.
- composition range (W) 10% by mass ⁇ HFO-1123 ⁇ 80% by mass 5 mass% ⁇ HFC-32 ⁇ 80 mass% 5% by mass ⁇ HFO-1234ze ⁇ 45% by mass
- the working medium having the above composition is a working medium in which the characteristics of HFO-1123, HFO-1234ze, and HFC-32 are exhibited in a particularly well-balanced manner, and the disadvantages of each of them are suppressed. That is, it is a working medium in which GWP is kept low and durability is ensured, and when used in a thermal cycle, the temperature gradient is smaller and the cycle performance is higher by having higher capacity and efficiency. is there.
- the phosphate ester in the present invention has an interaction distance (Ra) with the working medium of 15 or less determined from the value of the Hansen solubility parameter (hereinafter also referred to as HSP).
- HSP is a solubility parameter introduced by Hildebrand, expressed by three types of components consisting of ⁇ D , ⁇ P and ⁇ H under the condition that the following equation (1) holds. Each unit is (MPa) 1/2 .
- [delta] D shows the effect of dispersion interaction force
- [delta] P is the effect of dipole-dipole interaction forces
- [delta] H is the HSP due to the effect of hydrogen bonding interaction forces, respectively.
- the interaction distance (Ra) of two substances is a value calculated by the following equation (2).
- HSP value of the mixture is obtained from the following formulas (3) to (5) from the HSP value of the substance to be mixed and the volume mixing ratio.
- ⁇ indicates the volume fraction at the time of mixing
- subscripts 1 and 2 and MIX indicate the substance 1, the substance 2, and the mixture, respectively.
- Equations (6) to (8) ⁇ represents the volume fraction at the time of mixing, x represents the total number of types of substances to be mixed, and the subscripts n and MIX are the substances n and IX, respectively. The mixture is shown.
- HSP Hansen Solubility Parameters in Practice
- the interaction distance (Ra) between the working medium and the phosphate ester in the present invention is preferably 13 or less, more preferably 12 or less, and particularly preferably 10 or less.
- the phosphate ester in the present invention can be appropriately selected according to the composition of the working medium as long as the interaction distance (Ra) is 15 or less.
- Examples of the phosphoric acid ester include at least one selected from phosphoric acid triester, acidic phosphoric acid monoester, acidic phosphoric acid diester, phosphorous acid ester, and acidic phosphorous acid ester.
- phosphoric acid triester As phosphate ester, phosphoric acid triester, acidic phosphoric acid monoester, and acidic phosphoric acid diester are preferable.
- the phosphate ester preferably has a hydrocarbon group having 1 to 30 carbon atoms in the molecule.
- the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group.
- the alkyl group and alkenyl group may be linear, branched, or cyclic. Specific examples include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group.
- Tert-butyl group various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups, allyl groups, propenyl groups, Examples include various butenyl groups, various hexenyl groups, various octenyl groups, various decenyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecenyl groups, cyclopentenyl groups, and cyclohexenyl groups.
- a part of hydrogen atoms of the alkyl group may be substituted with a halogen atom such as a chlorine atom.
- aryl group examples include phenyl, tolyl, xylyl, naphthyl, and aralkyl groups such as benzyl, phenethyl, naphthylmethyl, methylbenzyl, methylphenethyl, and methylnaphthylmethyl.
- a part of hydrogen atoms bonded to the ring of the aryl group or a hydrogen atom outside the ring may be substituted with a halogen atom such as a chlorine atom.
- Examples of phosphoric acid triesters include trialkyl phosphates, triaryl phosphates, trialkylaryl phosphates, triarylalkyl phosphates, and trialkenyl phosphates.
- As the phosphoric acid triester trialkyl phosphate and triaryl phosphate are preferable.
- Examples of the acidic phosphoric acid monoester include monoalkyl acid phosphate and monoaryl acid phosphate. Specifically, monoethyl acid phosphate, mono n-propyl acid phosphate, mono-n-butyl acid phosphate, mono-2-ethylhexyl acid phosphate, monododecyl acid phosphate, monotetradecyl acid phosphate, monohexadecyl acid phosphate, Examples include monooctadecyl acid phosphate and monooctadecenyl acid phosphate.
- acidic phosphoric acid diesters include dialkyl acid phosphates and diaryl acid phosphates. Specifically, di-n-butyl acid phosphate, di-2-ethylhexyl acid phosphate, didecyl acid phosphate, didodecyl acid phosphate, di (tridecyl) acid phosphate, dioctadecyl acid phosphate, di-9-octadecede Nyl acid phosphate, di (4-methylphenyl) acid phosphate, di (4-chlorophenyl) acid phosphate and the like can be mentioned.
- phosphites examples include acidic phosphite diesters and phosphite triesters.
- Acid phosphite diesters include di-n-butyl hydrogen phosphite, di-2-ethylhexyl hydrogen phosphite, didecyl hydrogen phosphite, didodecyl hydrogen phosphite, dioctadecyl hydrogen phosphite, di -9-octadecenyl hydrogen phosphite, diphenyl hydrogen phosphite, di (4-methylphenyl) hydrogen phosphite, di (4-chlorophenyl) hydrogen phosphite and the like.
- Phosphorous acid triesters include triethyl phosphite, tri n-butyl phosphite, triphenyl phosphite, tricresyl phosphite, tri (nonylphenyl) phosphite, tri (2-ethylhexyl) phosphite, tri Examples include decyl phosphite, trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, and trioleyl phosphite.
- the phosphate ester is preferably a phosphate triester because it is highly compatible with the working medium in the present invention, more preferably a trialkyl phosphate having 1 to 4 carbon atoms, triphenyl phosphate, or tricresyl phosphate.
- a phosphoric ester when a phosphoric ester produces a compound having a phenol group by hydrolysis, the effect of capturing the radical by the generated phenol group can be expected, so that the effect on the stability of the composition for a heat cycle system can be expected.
- the phosphate ester triphenyl phosphate and tricresyl phosphate are particularly preferable.
- phosphate ester 1 type may be used independently and 2 or more types may be used in combination.
- the content of the phosphate ester is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and particularly preferably 0.1 to 3% by mass with respect to the working medium (100% by mass). If the content rate of phosphate ester is the said range, it is excellent in compatibility with a working medium, without reducing cycling performance.
- composition for a heat cycle system of the present invention has a possibility that decomposition occurs because HFO-1123 contains an unsaturated bond in the molecule when water or oxygen in the atmosphere is mixed in the heat cycle system. As a result, an acid may be generated.
- the phosphate ester in the present invention is hydrolyzed by an acid, it is considered that the acid generated in the heat cycle system can be trapped and the stability of the composition for the heat cycle system can be improved.
- the phosphate ester according to the present invention is particularly excellent in compatibility with a working medium containing HFO-1123 and HFC-32, so that it can effectively enhance stability even when compression and heating are repeated. It is thought that you can.
- the working medium described above may be used by mixing with a lubricating oil.
- a lubricating oil a known lubricating oil used in a heat cycle system can be employed.
- Lubricating oils include oxygen-containing synthetic oils (ester-based lubricating oils, ether-based lubricating oils, etc.), fluorine-based lubricating oils, mineral oils, hydrocarbon-based synthetic oils, and the like.
- ester-based lubricating oil examples include dibasic acid ester oil, polyol ester oil, complex ester oil, and polyol carbonate oil.
- 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,
- 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 more preferable.
- hindered alcohols neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, etc.
- trimel propane tripelargonate pentaerythritol 2-ethylhexanoate
- pentaerythritol tetrapelargonate are more preferable.
- the complex ester oil is an ester of a fatty acid and a dibasic acid, a monohydric alcohol and a polyol.
- Examples of the fatty acid, dibasic acid, monohydric alcohol, and polyol include the same as those mentioned for the dibasic acid ester oil and polyol ester oil.
- 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 lubricants include polyvinyl ether and polyoxyalkylene oil.
- examples of the polyvinyl ether 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.
- the vinyl ether monomer is preferably an alkyl vinyl ether, and the alkyl group is preferably an alkyl group having 6 or less carbon atoms. Moreover, a vinyl ether monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
- hydrocarbon monomers having an olefinic double bond include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, ⁇ -methylstyrene, various alkyl-substituted styrenes, etc. Is mentioned.
- the hydrocarbon monomer which has an olefinic double bond may be used individually by 1 type, and may be used in combination of 2 or more type.
- 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.
- the initiator used for the reaction examples include water, monohydric alcohols such as methanol and butanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, pentaerythritol, and glycerol.
- the polyoxyalkylene oil is preferably an alkyl etherified product or an esterified product of polyoxyalkylene monool or polyoxyalkylene polyol.
- the polyoxyalkylene polyol is preferably polyoxyalkylene glycol.
- an alkyl etherified product of polyoxyalkylene glycol having a terminal hydroxyl group of polyoxyalkylene glycol capped with an alkyl group such as a methyl group, called polyalkylene glycol oil is preferable.
- fluorine-based lubricating oils include compounds in which hydrogen atoms of synthetic oils (described later, such as mineral oils, poly ⁇ -olefins, alkylbenzenes, and alkylnaphthalenes) are substituted with fluorine atoms, perfluoropolyether oils, fluorinated silicone oils, and the like.
- a lubricating 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, 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.
- a lubricating oil may be used individually by 1 type, and may be used in combination of 2 or more type.
- a polyol ester oil and / or a polyglycol oil are preferable from the viewpoint of compatibility with the working medium, and a polyalkylene glycol oil is particularly preferable from the viewpoint that a remarkable antioxidant effect can be obtained by the stabilizer described later.
- Kinematic viscosity at 40 ° C. of the lubricating oil is preferably 1 ⁇ 750mm 2 / s, 1 ⁇ 400mm 2 / s is more preferable. Further, the kinematic viscosity is preferably 1 ⁇ 100mm 2 / s at 100 °C, 1 ⁇ 50mm 2 / s is more preferable.
- the mass ratio of the working medium to the lubricating oil may be in a range that does not significantly reduce the effect of the present invention, and varies depending on the application, the type of the compressor, and the like. 1/10 to 10/1 is preferable, 1/3 to 3/1 is more preferable, and 2/3 to 3/2 is particularly preferable.
- a stabilizer is a component that improves the stability of the working medium against heat and oxidation.
- the stabilizer include an oxidation resistance improver, a heat resistance improver, and a metal deactivator.
- Examples of the oxidation resistance improver and heat resistance improver include N, N′-diphenylphenylenediamine, p-octyldiphenylamine, p, p′-dioctyldiphenylamine, N-phenyl-1-naphthylamine, and N-phenyl-2-naphthylamine.
- 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).
- a stabilizer may be used individually by 1 type and may be used in combination of 2 or more type.
- Examples of leak detection substances 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.
- odor masking agent examples include known fragrances used in heat cycle systems, together with working media composed of halogenated hydrocarbons, such as those described in JP-T-2008-500337 and JP-A-2008-531836. Can be mentioned.
- a solubilizing agent that improves the solubility of the leak detection substance in the working medium may be used.
- solubilizer examples include those described in JP-T-2007-511645, JP-T-2008-500437, JP-T-2008-531836.
- the content ratio of the leak detection substance in the composition for a heat cycle system may be in a range that does not significantly reduce the effect of the present invention, and is preferably 2 parts by mass or less, based on 100 parts by mass of the working medium, Part or less is more preferable.
- the composition for a heat cycle system of the present invention has a small influence on the ozone layer, a small GWP, and a stability by coexisting a working medium containing HFO-1123 and HFC-32 and a specific phosphate ester. And excellent in durability.
- the thermal cycle system of the present invention is a system using the composition for a thermal cycle system of the present invention.
- the heat cycle system of the present invention may be a heat pump system that uses warm heat obtained by a condenser, or may be a refrigeration cycle system that uses cold heat obtained by an evaporator.
- thermal cycle system of the present invention include refrigeration / refrigeration equipment, air conditioning equipment, power generation systems, heat transport devices, and secondary coolers.
- air conditioners include room air conditioners, packaged air conditioners (store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, etc.), gas engine heat pumps, train air conditioners, automobile air conditioners, and the like.
- refrigeration / refrigeration equipment include showcases (built-in showcases, separate showcases, etc.), commercial freezers / refrigerators, vending machines, ice makers, and the like.
- a power generation system using a Rankine cycle system is preferable.
- the working medium is heated by geothermal energy, solar heat, waste heat in the middle to high temperature range of about 50 to 200 ° C in the evaporator, and the working medium turned into high-temperature and high-pressure steam is expanded.
- An example is a system in which power is generated by adiabatic expansion by a machine, and a generator is driven by work generated by the adiabatic expansion.
- the thermal cycle system of the present invention can efficiently exhibit thermal cycle performance even in a higher temperature operating environment, it is preferably used as an air conditioner that is often installed outdoors.
- the thermal cycle system of the present invention is also preferably used as a refrigeration / refrigeration apparatus.
- the heat cycle system of the present invention may be a heat transport device.
- a latent heat transport device is preferable.
- the latent heat transport device include a heat pipe and a two-phase sealed thermosyphon device that transport latent heat using phenomena such as evaporation, boiling, and condensation of a working medium enclosed in the device.
- the heat pipe is applied to a relatively small cooling device such as a cooling device for a heat generating part of a semiconductor element or an electronic device. Since the two-phase closed thermosyphon does not require a wig and has a simple structure, it is widely used for a gas-gas heat exchanger, for promoting snow melting on roads, and for preventing freezing.
- the refrigeration cycle system is a system that uses cold heat obtained by an evaporator.
- a refrigeration cycle system 10 shown in FIG. 1 cools and liquefies a compressor 11 that compresses the working medium vapor A into a high-temperature and high-pressure working medium vapor B and the working medium vapor B discharged from the compressor 11.
- the condenser 12 as a low-temperature and high-pressure working medium C
- the expansion valve 13 that expands the working medium C discharged from the condenser 12 to form a low-temperature and low-pressure working medium D
- the working medium D discharged from the expansion valve 13 Is composed of an evaporator 14 that heats the working medium vapor A to a high-temperature and low-pressure working medium vapor A, a pump 15 that supplies a load fluid E to the evaporator 14, and a pump 16 that supplies a fluid F to the condenser 12.
- the working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to obtain a low-temperature and low-pressure working medium D (hereinafter referred to as “CD process”).
- the working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to obtain high-temperature and low-pressure working medium vapor A. At this time, the load fluid E is cooled to become the load fluid E ′ and discharged from the evaporator 14 (hereinafter referred to as “DA process”).
- the refrigeration cycle system 10 is a cycle system including adiabatic / isoentropic change, isoenthalpy change, and isopressure change.
- the state change of the working medium is described on the pressure-enthalpy line (curve) diagram shown in FIG. 2, it can be expressed as a trapezoid having A, B, C, and D as apexes.
- the AB process is a process in which adiabatic compression is performed by the compressor 11 to convert the high-temperature and low-pressure working medium vapor A into a high-temperature and high-pressure working medium vapor B, which is indicated by an AB line in FIG.
- the BC process is a process in which the condenser 12 performs isobaric cooling to convert the high-temperature and high-pressure working medium vapor B into a low-temperature and high-pressure working medium C, and is indicated by a BC line in FIG.
- the pressure at this time is the condensation pressure.
- Pressure - an intersection T 1 of the high enthalpy side condensing temperature of the intersection of the enthalpy and BC line, the low enthalpy side intersection T 2 is the condensation boiling temperature.
- the temperature gradient when the mixed medium is a non-azeotropic mixed medium 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.
- T 2 -T 3 is (i) ⁇ supercooling degree of the working medium in the cycle of (iv) (hereinafter, optionally in the "SC" It is shown.)
- the DA process is a process of performing isobaric heating in the evaporator 14 to return the low-temperature and low-pressure working medium D to the high-temperature and low-pressure working medium vapor A, and is indicated by a DA line in FIG.
- T 6 The pressure at this time is the evaporation pressure.
- Pressure - intersection T 6 of the high enthalpy side of the intersection of the enthalpy and DA line is evaporating temperature. If Shimese the temperature of the working medium vapor A in T 7, T 7 -T 6 is (i) ⁇ superheat of the working medium in the cycle of (iv) a (hereinafter,. Indicated by "SH", if necessary) .
- T 4 indicates the temperature of the working medium D.
- the cycle performance of the working medium is evaluated by, for example, the refrigerating capacity of the working medium (hereinafter, indicated as “Q” as necessary) and the coefficient of performance (hereinafter, indicated as “COP” as necessary).
- Q and COP of the working medium in each state of A after evaporation, high temperature and low pressure
- B after compression, high temperature and high pressure
- C after condensation, low temperature and high pressure
- D after expansion, low temperature and low pressure.
- COP efficiency in the refrigeration cycle system.
- the higher the COP value the smaller the input, for example, the amount of power required to operate the compressor, and the larger the output, for example, Q can be obtained. It represents what you can do.
- Q means the ability to freeze the load fluid, and the higher the Q, the 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.
- the water concentration in the heat cycle system is preferably less than 10,000 ppm, more preferably less than 1000 ppm, and particularly preferably less than 100 ppm in terms of mass ratio with respect to the working medium.
- 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 the chemical reactivity between the desiccant and the working medium and the moisture absorption capacity of the desiccant.
- the main component is a compound represented by the following formula (9) because of its superior 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.
- the working medium When a desiccant having a pore size larger than the molecular diameter of the working medium is used, the working medium is adsorbed in the desiccant, resulting in a chemical reaction between the working medium and the desiccant, and generation of a non-condensable gas. Undesirable phenomena such as a decrease in the strength of the desiccant and a decrease in the adsorption capacity will 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 mm or less is preferable.
- sodium / potassium A-type synthetic zeolite having a pore size smaller than the molecular diameter of the working medium only moisture in the heat cycle system can be selectively adsorbed and removed without adsorbing the heat cycle working medium. .
- thermal decomposition is difficult to occur, and as a result, deterioration of materials constituting the thermal cycle system and generation of contamination can be suppressed.
- the size of the zeolitic desiccant is preferably 0.5 to 5 mm because if it is too small, it will cause clogging of the valves and piping details of the heat cycle system, and if it is too large, the drying ability will decrease.
- 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.
- a binder such as bentonite
- Oxygen may be mixed in the thermal cycle system. Since mixing of oxygen also causes deterioration of the working medium and the like, it is necessary to suppress the oxygen concentration in the heat cycle system.
- the oxygen concentration in the heat cycle system is preferably less than 10,000 ppm, more preferably less than 1000 ppm, and particularly preferably less than 100 ppm in terms of mass ratio with respect to the working medium.
- chlorine concentration If chlorine is present in the thermal cycle system, there is a concern that undesirable effects such as formation of deposits due to reaction with metal, wear of bearings, decomposition of working medium and lubricating oil may be exerted.
- 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 the working medium and lubricating oil to promote decomposition.
- the non-condensable gas concentration is preferably 1.5% by volume or less, particularly preferably 0.5% by volume or less in terms of the volume ratio with respect to the working medium in the gas phase part of the working medium.
- HSPiP Hansen solubility parameter
- phosphate ester The HSP values of phosphate esters shown in Table 5 were also determined by the above method. Table 5 shows the symbols, compound names, and HSP values of each phosphate ester. In addition, Tables 6 to 8 show the values of the interaction distances (Ra) between the phosphate esters (A to M) and the working media (Nos. 3 to 115).
- Example 1 In a 200 ml stainless steel pressure vessel with a 150 ml glass tube inside, 50 g of a mixture of HFO-1123 and HFC-32 in mass ratio (50/50) as working medium, and both ends of methyl ether as lubricating oil 50 g of the converted polypropylene glycol (carbon / oxygen molar ratio 2.7) and 0.5 g of tributyl phosphate as a phosphate ester (1% by mass with respect to the working medium) were added. Furthermore, the air which adjusted oxygen concentration to 18 volume% was put, and it sealed.
- the sealed pressure vessel was stored in a thermostatic chamber (Perfect Oven PHH-202, manufactured by ESPEC Corporation) at 175 ° C. for 14 days, and the acid content of the working medium and the total acid value of the refrigerating machine oil were analyzed. The results are shown in Table 9.
- Example 1 Except that the phosphate ester in Example 1 was not added, the acid content of the working medium and the total acid value of the refrigerating machine oil were analyzed in the same manner as in Example 1. The acid content was 12 ppm in terms of HCl concentration.
- the acid content of the working medium after the test was measured according to JIS K1560 (1,1,1,2-tetrafluoroethane (HFC-134a)).
- the pressure vessel after the test was allowed to stand until it reached room temperature. 100 ml of pure water was put in each of four absorption bottles, and a series of pipes connected in series was prepared. Connect a pressure vessel at room temperature to which an absorption bottle containing pure water is connected, and gradually open the valve of the pressure vessel to introduce refrigerant gas into the water in the absorption bottle. Minutes were extracted.
- the water in the absorption bottle after extraction was added with 1 drop of an indicator (BTB: bromothymol blue) for the first and second bottles, and titrated with a 1/100 N-NaOH alkaline standard solution.
- BTB bromothymol blue
- the third and fourth water in the absorption bottle were combined and titrated in the same manner to obtain a measurement blank. From these measurement values and measurement blank values, the acid content in the refrigerant after the test was determined as the HCl concentration.
- Table 9 an acid content of more than 10 ppm is indicated by “x”, 5-10 ppm is indicated by “ ⁇ ”, and less than 5 ppm is indicated by “ ⁇ ”.
- Total acid value analysis of refrigerating machine oil The total acid value of the refrigeration oil after the working medium gas recovery was measured by the method based on the JIS-K2211 (refrigeration oil) total acid value analysis method as follows. Refrigeration oil remaining in the pressure vessel after the above test is weighed and dissolved in a toluene / isopropanol / water mixed solution, and p-naphthol benzein is used as an indicator, and a 1/100 N KOH / ethanol solution is used. The total acid value of the refrigerating machine oil (mg ⁇ KOH / g) was measured from the titration. In Table 9, “ ⁇ ” indicates that the total oxidation exceeds 10 mg ⁇ KOH / g, “ ⁇ ” indicates 5-10 mg ⁇ KOH / g, and “ ⁇ ” indicates less than 5 mg ⁇ KOH / g.
- the composition for a heat cycle system of the present invention and the heat cycle system using the composition are refrigeration / refrigeration equipment (built-in showcase, separate-type showcase, commercial refrigeration / refrigerator, vending machine, ice maker, etc.) , Air conditioners (room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.), power generation systems (waste heat recovery power generation, etc.), heat transport It can be used for equipment (heat pipe, etc.).
- refrigeration / refrigeration equipment built-in showcase, separate-type showcase, commercial refrigeration / refrigerator, vending machine, ice maker, etc.
- Air conditioners room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.
- power generation systems waste heat recovery power generation, etc.
- heat transport It can be used for equipment (heat pipe, etc.).
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Abstract
Description
こで、熱サイクルシステム用の作動媒体としては、オゾン層への影響が少ない、ジフルオロメタン(HFC-32)、テトラフルオロエタン、ペンタフルオロエタン(HFC-125)等のヒドロフルオロカーボン(HFC)が用いられてきた。しかしながら、HFCは、オゾン層への影響は少ない一方で、地球温暖化係数(以下、GWPという。)が高いため地球温暖化の原因となる可能性が指摘されている。そのため、熱サイクルシステム用の作動媒体としては、オゾン層への影響が少なく、かつGWPの小さい作動媒体の開発が急務となっている。
[1]トリフルオロエチレンとジフルオロメタンとを含む作動媒体と、リン酸エステルとを含む熱サイクルシステム用組成物であって、ハンセン溶解度パラメータの値から求められる作動媒体とリン酸エステルとの相互作用距離(Ra)が、15以下であることを特徴とする熱サイクルシステム用組成物。
[3]リン酸エステルが、リン酸トリエステル、酸性リン酸モノエステルまたは酸性リン酸ジエステルである、[1]または[2]に記載の熱サイクルシステム用組成物。
[4]リン酸トリエステルがトリアルキルホスフェートまたはトリアリールホスフェートである、[3]に記載の熱サイクルシステム用組成物。
[5]酸性リン酸モノエステルがモノアルキルアシッドホスフェートまたはモノアリールアシッドホスフェートである、[3]に記載の熱サイクルシステム用組成物。
[6]酸性リン酸ジエステルがジアルキルアシッドホスフェートまたはジアリールアシッドホスフェートである、[3]に記載の熱サイクルシステム用組成物。
[7]前記作動媒体におけるトリフルオロエチレンとジフルオロメタンとの質量比(トリフルオロエチレン/ジフルオロメタン)が、1/99~99/1である、[1]~[6]のいずれかに記載の熱サイクルシステム用組成物。
[8]前記作動媒体がさらに2,3,3,3-テトラフルオロプロペンおよび1,3,3,3-テトラフルオロプロペンから選ばれる少なくとも1種のヒドロフルオロオレフィンを含む、[1]~[7]のいずれかに記載の熱サイクルシステム用組成物。
10質量%≦トリフルオロエチレン<75質量%
5質量%≦ジフルオロメタン≦75質量%
0質量%<2,3,3,3-テトラフルオロプロペン≦50質量%
[10]前記作動媒体がトリフルオロエチレンとジフルオロメタンと1,3,3,3-テトラフルオロプロペンを含み、トリフルオロエチレンとジフルオロメタンと1,3,3,3-テトラフルオロプロペンの合計量に対するこれら3成分の割合が以下のとおりである、[8]に記載の熱サイクルシステム用組成物。
10質量%≦トリフルオロエチレン≦80質量%
5質量%≦ジフルオロメタン≦80質量%
5質量%≦1,3,3,3-テトラフルオロプロペン≦45質量%
[11][1]~[10]のいずれか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。
[12]前記熱サイクルシステムが、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、[11]に記載の熱サイクルシステム。
また、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ていることから、オゾン層への影響が少なく、GWPが小さく、安定性、かつ耐久性に優れる。
本発明の熱サイクルシステム用組成物は、トリフルオロエチレン(HFO-1123)とジフルオロメタン(HFC-32)とを含む作動媒体と、特定のリン酸エステルとを含み、必要に応じてさらに、潤滑油、安定剤、漏れ検出物質等を含んでいてもよい。
<作動媒体>
本発明における作動媒体は、HFO-1123とHFC-32とを含み、必要に応じ、その他の化合物を含んでいてもよい。
HFO-1123は、高温または高圧下で着火源があると、急激な温度、圧力上昇を伴う連鎖的な自己分解反応を起こすことが知られている。本発明における作動媒体においては、HFO-1123を、HFC-32と混合してHFO-1123の含有割合を抑えた混合物とすることで自己分解反応を抑えることができる。
ここで、本発明における熱サイクル用作動媒体を、熱サイクルシステムに適用する場合の圧力条件は、通常、5.0MPa以下程度である。そのため、HFO-1123とHFC-32からなる熱サイクル用作動媒体が、5.0MPaの圧力条件下で自己分解性を有しないことで、熱サイクルシステムに適用する場合の一般的な温度条件下において安定性の高い作動媒体を得ることができる。
なお、本発明における作動媒体においては、自己分解性を有する組成物であっても使用条件によっては取り扱いを十分に注意することで熱サイクルシステムに使用することが可能である。
なお、HFO-1225yeとHFO-1234zeには、それぞれ、シス体(Z体)とトランス体(E体)との立体異性体が存在することより、以下、両者を区別する場合は、HFO-1225ye(Z)、HFO-1225ye(E)、HFO-1234ze(Z)、HFO-1234ze(E)と記す。また、両者を区別せずかつ両者の混合物であってもよい場合は、(Z,E)で示すこともある。
10質量%≦HFO-1123<75質量%
0質量%<HFO-1234yf≦50質量%
5質量%≦HFC-32≦75質量%
70質量%≦HFO-1123+HFO-1234yf
30質量%≦HFO-1123≦80質量%
HFO-1234yf≦40質量%
5質量%≦HFC-32≦30質量%
HFO-1123/HFO-1234yf≦95/5質量%
上記別の好ましい組成のうち、さらに好ましい組成範囲(R)を、以下に示す。
<組成範囲(R)>
10質量%≦HFO-1123<70質量%
0質量%<HFO-1234yf≦50質量%
30質量%<HFC-32≦75質量%
20質量%≦HFO-1123<70質量%
0質量%<HFO-1234yf≦40質量%
30質量%<HFC-32≦75質量%
<組成範囲(L)>
20質量%≦HFO-1123<70質量%
0質量%<HFO-1234yf≦40質量%
30質量%<HFC-32≦44質量%
<組成範囲(M)>
20質量%≦HFO-1123<70質量%
5質量%≦HFO-1234yf≦40質量%
30質量%<HFC-32≦44質量%
<組成範囲(W)>
10質量%≦HFO-1123≦80質量%
5質量%≦HFC-32≦80質量%
5質量%≦HFO-1234ze≦45質量%
上記組成を有する作動媒体は、HFO-1123、HFO-1234zeおよびHFC-32がそれぞれ有する特性が特にバランスよく発揮され、かつそれぞれが有する欠点が抑制された作動媒体である。すなわち、GWPが低く抑えられ、耐久性が確保されたうえで、熱サイクルに用いた際に、温度勾配がより小さく、より高い能力と効率を有することで良好なサイクル性能が得られる作動媒体である。
本発明におけるリン酸エステルは、ハンセン溶解度パラメータ(以下、HSPともいう。)の値から求められる前記作動媒体との相互作用距離(Ra)が、15以下である。本明細書において、HSPとは、ヒルブランド(Hildebrand)によって導入された溶解度パラメータを、下記(1)式が成立する条件でδD、δPおよびδHからなる3種類の成分別に表現にしたものであり、単位はいずれも(MPa)1/2である。δDは分散相互作用力による効果、δPは双極子間相互作用力による効果、δHは水素結合相互作用力による効果に起因するHSPをそれぞれ示している。
Charles M. Hansen著、Hansen Solubility Parameters: A Users Handbook(CRCプレス、2007年)。
上記論文によると、混合物のHSPの値は、混合する物質のHSPの値と体積混合率から、下記の式(3)~(5)によって求まる。
式(3)~(5)から、本明細書におけるリン酸エステルが2種類以上の成分からなる混合物である場合には、下記の式(6)でリン酸エステルのHSP値を計算する。
具体的には、トリメチルホスフェート、トリエチルホスフェート、トリプロピルホスフェート、トリブチルホスフェート、トリヘキシルホスフェート、トリ(2-エチルヘキシル)ホスフェート、トリデシルホスフェート、トリドデシルホスフェート、トリテトラデシルホスフェート、トヘキサデシルホスフェート、トリオクタデシルホスフェート、トリオクタデセニルホスフェート、エチルジブチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、ベンジルジフェニルホスフェート、エチルジフェニルホスフェート、クレジルジフェニルホスフェート、ジクレジルフェニルホスフェート、エチルフェニルジフェニルホスフェート、ジ(エチルフェニル)フェニルホスフェート、プロピルフェニルジフェニルホスフェート、ジ(プロピルフェニル)フェニルホスフェート、トリエチルフェニルホスフェート、トリプロピルフェニルホスフェート、ブチルフェニルジフェニルホスフェート、ジ(ブチルフェニル)フェニルホスフェート、トリブチルフェニルホスフェートなどを挙げることができる。
リン酸エステルとしては、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システムでは、前記した作動媒体を潤滑油と混合して使用してもよい。潤滑油としては、熱サイクルシステムに用いられる公知の潤滑油を採用できる。
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。
ポリビニルエーテルとしては、ビニルエーテルモノマーの重合体、ビニルエーテルモノマーとオレフィン性二重結合を有する炭化水素モノマーとの共重合体、ビニルエーテルモノマーとポリオキシアルキレン鎖を有するビニルエーテル系モノマーとの共重合体等が挙げられる。
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。
潤滑油は、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。
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、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。
耐酸化性向上剤および耐熱性向上剤としては、N,N’-ジフェニルフェニレンジアミン、p-オクチルジフェニルアミン、p,p’-ジオクチルジフェニルアミン、N-フェニル-1-ナフチルアミン、N-フェニル-2-ナフチルアミン、N-(p-ドデシル)フェニル-2-ナフチルアミン、ジ-1-ナフチルアミン、ジ-2-ナフチルアミン、N-アルキルフェノチアジン、6-(t-ブチル)フェノール、2,6-ジ-(t-ブチル)フェノール、4-メチル-2,6-ジ-(t-ブチル)フェノール、4,4’-メチレンビス(2,6-ジ-t-ブチルフェノール)等が挙げられる。
安定剤は、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。
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。
漏れ検出物質を用いる場合には、作動媒体への漏れ検出物質の溶解性を向上させる可溶化剤を用いてもよい。
熱サイクルシステム用組成物における、漏れ検出物質の含有割合は、本発明の効果を著しく低下させない範囲であればよく、作動媒体100質量部に対して、2質量部以下が好ましく、0.5質量部以下がより好ましい。
本発明の熱サイクルシステム用組成物は、HFO-1123とHFC-32とを含む作動媒体と、特定のリン酸エステルを共存させることで、オゾン層への影響が少なく、GWPが小さく、安定性、かつ耐久性に優れる。
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たシステムである。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。
冷凍・冷蔵機器として、具体的には、ショーケース(内蔵型ショーケース、別置型ショーケース等)、業務用冷凍・冷蔵庫、自動販売機、製氷機等が挙げられる。
(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。)。
(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(以下、「CD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。)。
BC過程は、凝縮器12で等圧冷却を行い、高温高圧の作動媒体蒸気Bを低温高圧の作動媒体Cとする過程であり、図2においてBC線で示される。この際の圧力が凝縮圧である。圧力-エンタルピ線とBC線の交点のうち高エンタルピ側の交点T1が凝縮温度であり、低エンタルピ側の交点T2が凝縮沸点温度である。ここで、混合媒体が非共沸混合媒体である場合の温度勾配はT1とT2の差として示される。
DA過程は、蒸発器14で等圧加熱を行い、低温低圧の作動媒体Dを高温低圧の作動媒体蒸気Aに戻す過程であり、図2においてDA線で示される。この際の圧力が蒸発圧である。圧力-エンタルピ線とDA線の交点のうち高エンタルピ側の交点T6は蒸発温度である。作動媒体蒸気Aの温度をT7で示せば、T7-T6が(i)~(iv)のサイクルにおける作動媒体の過熱度(以下、必要に応じて「SH」で示す。)となる。なお、T4は作動媒体Dの温度を示す。
一方、Qは負荷流体を冷凍する能力を意味しており、Qが高いほど同一のシステムにおいて、多くの仕事ができることを意味している。言い換えると、大きなQを有する場合は、少量の作動媒体で目的とする性能が得られることを表しており、システムの小型化が可能となる。
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、作動媒体や潤滑油の加水分解、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、潤滑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、自動車用空調装置においては、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、潤滑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。熱サイクルシステム内の水分濃度は、作動媒体に対する質量割合で、10000ppm未満が好ましく、1000ppm未満がさらに好ましく、100ppm未満が特に好ましい。
乾燥剤の選定においては、細孔径および破壊強度が特に重要である。
熱サイクルシステム内には酸素が混入することもある。酸素の混入は、作動媒体等の劣化の原因にもなるので、熱サイクルシステム内の酸素濃度を抑制する必要がある。熱サイクルシステム内の酸素濃度は、作動媒体に対する質量割合で、10000ppm未満が好ましく、1000ppm未満がさらに好ましく、100ppm未満が特に好ましい。
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、作動媒体や潤滑油の分解等、好ましくない影響をおよぼす懸念がある。
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、作動媒体や潤滑油と反応し、分解を促進する。
不凝縮性気体濃度は、作動媒体の気相部において、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、本発明の熱サイクルシステム用組成物を用いているため、オゾン層への影響が少なく、GWPが小さく、安定性かつ耐久性に優れる。
HFO-1123、HFC-32、HFO-1234yfおよびリン酸エステルのHSP(δD、δP、δH)は、コンピュータソフトウエア Hansen Solubility Parameters in Practice(HSPiP)を用いた。HSPiPバージョン4.1.04のデータベースに登録されている物質に関してはその値を使用し、データベースに無い溶媒に関しては、HSPiPバージョン4.1.04により推算される値を使用した。
HFO-1123、HFC-32、およびHFO-1234yfを表1,表2に示す割合(質量%)で含む作動媒体No.1~61について、それぞれHSPの値を上記の方法によって求めた。結果を表1および表2に示す。表1および表2には、作動媒体No.とその作動媒体の組成、およびその作動媒体のHSP(δD、δP、δH)を示した。
表5に示すリン酸エステルのHSPの値も同様に上記の方法によって求めた。各リン酸エステルの記号、化合物名およびHSPの値を表5に示す。
また、各リン酸エステル(A~M)と各作動媒体(No.3~115)との相互作用距離(Ra)の値を表6~8に示す。
[実施例1]
内部に150mlのガラス筒を入れた200mlのステンレス鋼製の耐圧容器に、作動媒体としてHFO-1123とHFC-32の質量比(50/50)の混合物を50g、潤滑油として両末端がメチルエーテル化されたポリプロピレングリコール(炭素/酸素のモル比が2.7)を50g、リン酸エステルとしてトリブチルホスフェートを0.5g(作動媒体に対して1質量%)加えた。さらに、酸素濃度を18体積%になるように調整した空気を入れて密閉した。次いで、密閉した耐圧容器を恒温槽(パーフェクトオーブンPHH-202、エスペック株式会社製)中に175℃で14日間保存し、作動媒体の酸分量および冷凍機油の全酸価分析を行った。結果を表9に示す。
実施例1におけるリン酸エステルを加えない以外は、実施例1と同様にして作動媒体の酸分量および冷凍機油の全酸価分析を行った。酸分量は、HCl濃度で12ppmであった。
試験後の作動媒体の酸分量測定は、JIS K1560(1,1,1,2-テトラフルオロエタン(HFC-134a))に準拠して試験を実施した。
上記試験後の耐圧容器を室温になるまで静置した。吸収瓶4本にそれぞれ純水を100ml入れ、導管で直列に連結したものを準備した。室温になった耐圧容器に、純水を加えた吸収瓶を連結したものをつなぎ、徐々に耐圧容器の弁を開放して、冷媒ガスを吸収瓶の水中に導入し、冷媒ガスに含まれる酸分を抽出した。
JIS-K2211(冷凍機油)の全酸価分析方法に準拠した方法で、作動媒体ガス回収後の冷凍機油全酸価値の測定を次のように行った。上記試験後の耐圧容器内に残った冷凍機油を秤りとり、トルエン/イソプロパノール/水混合溶液に溶解させ、指示薬としてp-ナフトールベンゼインを用いて、1/100N-KOH・エタノール溶液にて中和滴定し、滴定量から冷凍機油の全酸価値(mg・KOH/g)を測定した。
なお、表9において、全酸化が10mg・KOH/g超を「×」、5~10mg・KOH/gを「△」、5mg・KOH/g未満を「○」で示す。
なお、2014年3月18日に出願された日本特許出願2014-054590号、2014年6月20日に出願された日本特許出願2014-127746号および2014年7月18日に出願された日本特許出願2014-148349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 (12)
- トリフルオロエチレンとジフルオロメタンとを含む作動媒体と、リン酸エステルとを含む熱サイクルシステム用組成物であって、ハンセン溶解度パラメータの値から求められる作動媒体とリン酸エステルとの相互作用距離(Ra)が、15以下であることを特徴とする熱サイクルシステム用組成物。
- リン酸エステルの含有割合が、作動媒体(100質量%)に対して0.01~10質量%である、請求項1に記載の熱サイクルシステム用組成物。
- リン酸エステルが、リン酸トリエステル、酸性リン酸モノエステルまたは酸性リン酸ジエステルである、請求項1または2に記載の熱サイクルシステム用組成物。
- リン酸トリエステルがトリアルキルホスフェートまたはトリアリールホスフェートである、請求項3に記載の熱サイクルシステム用組成物。
- 酸性リン酸モノエステルがモノアルキルアシッドホスフェートまたはモノアリールアシッドホスフェートである、請求項3に記載の熱サイクルシステム用組成物。
- 酸性リン酸ジエステルがジアルキルアシッドホスフェートまたはジアリールアシッドホスフェートである、請求項3に記載の熱サイクルシステム用組成物。
- 前記作動媒体におけるトリフルオロエチレンとジフルオロメタンとの質量比(トリフルオロエチレン/ジフルオロメタン)が、1/99~99/1である、請求項1~6のいずれか1項に記載の熱サイクルシステム用組成物。
- 前記作動媒体がさらに2,3,3,3-テトラフルオロプロペンおよび1,3,3,3-テトラフルオロプロペンから選ばれる少なくとも1種のヒドロフルオロオレフィンを含む、請求項1~7のいずれか1項に記載の熱サイクルシステム用組成物。
- 前記作動媒体がトリフルオロエチレンとジフルオロメタンと2,3,3,3-テトラフルオロプロペンを含み、トリフルオロエチレンとジフルオロメタンと2,3,3,3-テトラフルオロプロペンの合計量に対するこれら3成分の割合が以下のとおりである、請求項8に記載の熱サイクルシステム用組成物。
10質量%≦トリフルオロエチレン<75質量%
5質量%≦ジフルオロメタン≦75質量%
0質量%<2,3,3,3-テトラフルオロプロペン≦50質量% - 前記作動媒体がトリフルオロエチレンとジフルオロメタンと1,3,3,3-テトラフルオロプロペンを含み、トリフルオロエチレンとジフルオロメタンと1,3,3,3-テトラフルオロプロペンの合計量に対するこれら3成分の割合が以下のとおりである、請求項8に記載の熱サイクルシステム用組成物。
10質量%≦トリフルオロエチレン≦80質量%
5質量%≦ジフルオロメタン≦80質量%
5質量%≦1,3,3,3-テトラフルオロプロペン≦45質量% - 請求項1~10のいずれか1項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。
- 前記熱サイクルシステムが、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11に記載の熱サイクルシステム。
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EP3121241A4 (en) | 2017-11-22 |
CN106133109A (zh) | 2016-11-16 |
CN106133109B (zh) | 2021-05-04 |
US20160369146A1 (en) | 2016-12-22 |
EP3121241B1 (en) | 2019-10-30 |
BR112016020985A2 (ja) | 2017-08-15 |
BR112016020985B1 (pt) | 2022-09-20 |
JP6399086B2 (ja) | 2018-10-03 |
JPWO2015141677A1 (ja) | 2017-04-13 |
US9725632B2 (en) | 2017-08-08 |
EP3121241A1 (en) | 2017-01-25 |
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