WO2012157765A1 - 作動媒体および熱サイクルシステム - Google Patents
作動媒体および熱サイクルシステム Download PDFInfo
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- WO2012157765A1 WO2012157765A1 PCT/JP2012/062844 JP2012062844W WO2012157765A1 WO 2012157765 A1 WO2012157765 A1 WO 2012157765A1 JP 2012062844 W JP2012062844 W JP 2012062844W WO 2012157765 A1 WO2012157765 A1 WO 2012157765A1
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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
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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
- F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
- F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
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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
-
- 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
-
- 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
Definitions
- the present invention relates to a working medium and a heat cycle system using the working medium.
- a working medium for heat cycle such as 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.
- Chlorofluorocarbons (CFC) such as chlorotrifluoromethane and dichlorodifluoromethane
- HCFC hydrochlorofluorocarbons
- chlorodifluoromethane have been used.
- CFCs and HCFCs are now subject to regulation because of their impact on the stratospheric ozone layer.
- HFCs hydrofluorocarbons
- HFC-32 difluoromethane
- tetrafluoroethane tetrafluoroethane
- pentafluoroethane etc.
- HFC may cause global warming. Therefore, there is an urgent need to develop a working medium for heat cycle that has little influence on the ozone layer and has a low global warming potential.
- 1,1,1,2-tetrafluoroethane (HFC-134a) used as a refrigerant for automobile air conditioning equipment has a large global warming potential of 1430 (100-year value).
- HFC-134a 1,1,1,2-tetrafluoroethane
- HFC-152a 1,1-difluoroethane
- Hydrofluoroolefin (HFO) with a carbon-carbon double bond that is easily decomposed by OH radicals in the atmosphere is considered as a working medium for heat cycle that has little effect on the ozone layer and has little effect on global warming. It is done.
- the working medium for HFO thermal cycle for example, the following are known. (1) 3,3,3-trifluoropropene (HFO-1243zf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-fluoropropene (HFO-1261yf), 2,3,3 , 3-tetrafluoropropene (HFO-1234yf), 1,1,2-trifluoropropene (HFO-1243yc) (Patent Document 1).
- HFO-1225ye 1, 2, 3, 3, 3-pentafluoropropene
- HFO-1234ze (E) trans-1,3,3,3-tetrafluoropropene
- HFO-1234ze (Z) cis-1,3, 3,3-tetrafluoropropene
- Patent Document 2 1, 2, 3, 3, 3-pentafluoropropene (HFO-1225ye), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3, 3,3-tetrafluoropropene (HFO-1234ze (Z)), HFO-1234yf
- the present invention relates to a working medium for heat cycle that gives a heat cycle system that has little influence on the ozone layer, little influence on global warming, and excellent cycle performance (efficiency and capacity), and cycle performance (efficiency and capacity) To provide an excellent thermal cycle system.
- the present invention is characterized in that it includes 1,2-difluoroethylene (hereinafter also referred to as HFO-1132) as a thermal cycle working medium (hereinafter also referred to as a working medium).
- the working medium of the present invention preferably further contains a hydrocarbon.
- the working medium of the present invention preferably further contains HFC.
- the working medium of the present invention preferably further comprises hydrochlorofluoroolefin (HCFO) or chlorofluoroolefin (CFO).
- HCFO hydrochlorofluoroolefin
- CFO chlorofluoroolefin
- the working medium of the present invention includes HFO-1132 having a carbon-carbon double bond that is easily decomposed by OH radicals in the atmosphere, the working medium has little influence on the ozone layer and little influence on global warming. Since the thermal cycle system of the present invention includes HFO-1132 and uses the working medium of the present invention having excellent thermodynamic properties, the cycle performance (efficiency and capacity) is excellent. Moreover, since the efficiency is excellent, the power consumption can be reduced, and the ability is excellent, so that the system can be downsized.
- FIG. 3 is a cycle diagram in which a change in state of a working medium in a refrigeration cycle system is described on a temperature-entropy diagram.
- FIG. 3 is a cycle diagram in which a change in state of a working medium in a refrigeration cycle system is described on a pressure-enthalpy diagram.
- the working medium of the present invention contains 1,2-difluoroethylene.
- the working medium of the present invention may include other working media that vaporize and liquefy with CFO 1132, such as hydrocarbons, HFC, HCFO, CFO, and other HFOs, as necessary.
- the working medium of the present invention can be used in combination with components other than the working medium used together with the working medium (hereinafter, a composition containing the working medium and components other than the working medium is referred to as a working medium-containing composition).
- components other than the working medium include lubricants, stabilizers, leak detection substances, desiccants, and other additives.
- HFO-1132 As HFO-1132, there are two types of stereoisomers, trans-1,2-difluoroethylene (HFO-1132 (E)) and cis-1,2-difluoroethylene (HFO-1132 (Z)). In the present invention, HFO-1132 (E) may be used alone, HFO-1132 (Z) may be used alone, or a mixture of HFO-1132 (E) and HFO-1132 (Z) is used. May be.
- the content of HFO-1132 is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 100% by mass in the working medium (100% by mass).
- Hydrocarbon is a working medium component that improves the solubility of the working medium in mineral-based lubricating oil.
- the hydrocarbon preferably has 3 to 5 carbon atoms, and may be linear or branched. Specifically, propane, propylene, cyclopropane, butane, isobutane, pentane and isopentane are preferable as the hydrocarbon.
- a hydrocarbon may be used individually by 1 type and may be used in combination of 2 or more type.
- the hydrocarbon content is preferably 1 to 30% by mass, more preferably 2 to 30% by mass in the working medium (100% by mass). When the hydrocarbon content is 1% by mass or more, the solubility of the lubricating oil in the working medium is sufficiently improved.
- HFC HFC
- Capacity a working medium component that improves the cycle performance (capacity) of a thermal cycle system.
- HFC an HFC that has little influence on the ozone layer and little influence on global warming is preferable.
- the HFC preferably has 1 to 5 carbon atoms, and may be linear or branched.
- Specific examples of the HFC include difluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane, and the like.
- difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), 1,1,2,2-tetra have little impact on the ozone layer and little impact on global warming.
- HFC-134 1,1,1,2-tetrafluoroethane
- HFC-134a 1,1,1,2-tetrafluoroethane
- HFC-125 pentafluoroethane
- One HFC may be used alone, or two or more HFCs may be used in combination.
- the content of HFC in the working medium (100% by mass) is preferably 1 to 99% by mass, and more preferably 1 to 60% by mass.
- the HFC is HFC-125
- the reduction of the coefficient of performance is suppressed in the range of 1 to 60% by mass, and the refrigerating capacity can be greatly improved.
- the refrigerating capacity can be improved without causing a decrease in the coefficient of performance in the range of 1 to 40% by mass.
- HFC-32 a decrease in the coefficient of performance is suppressed in the range of 1 to 99% by mass, and the refrigerating capacity can be greatly improved. It can be improved according to the required characteristics of the working medium.
- HCFO and CFO are working medium components that suppress the combustibility of the working medium. Further, it is a component that improves the solubility of the lubricating oil in the working medium. As HCFO and CFO, HCFO having little influence on the ozone layer and little influence on global warming is preferable.
- HCFO preferably has 2 to 5 carbon atoms, and may be linear or branched.
- Specific examples of HCFO include hydrochlorofluoropropene and hydrochlorofluoroethylene.
- 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) is used from the viewpoint of sufficiently suppressing the flammability of the working medium without greatly reducing the cycle performance (capacity) of the thermal cycle system.
- 1-chloro-1,2-difluoroethylene HCFO-1122
- HCFO may be used alone or in combination of two or more.
- CFO preferably has 2 to 5 carbon atoms, and may be linear or branched.
- Specific examples of CFO include chlorofluoropropene and chlorofluoroethylene.
- 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO--) is used from the viewpoint of sufficiently suppressing the flammability of the working medium without greatly degrading the cycle performance (capacity) of the thermal cycle system. 1214ya) and 1,2-dichloro-1,2-difluoroethylene (CFO-1112) are particularly preferred.
- the total content of HCFO and CFO is preferably 1 to 60% by mass and more preferably 1 to 40% by mass in the working medium (100% by mass). If the total content of HCFO and CFO is 1 to 40% by mass, the flammability of the working medium can be sufficiently suppressed without greatly reducing the cycle performance (capacity) of the thermal cycle system.
- HFO which has little influence on the ozone layer and has little influence on global warming is preferable.
- HFOs include HFO-1224ye, HFO-1234ze, HFO-1243zf, and the like.
- the lubricating oil used in the working medium-containing composition a known lubricating oil used in a heat cycle system is used.
- the lubricating oil include oxygen-containing synthetic oils (such as ester-based lubricating oils and ether-based lubricating oils), fluorine-based lubricating oils, mineral oils, and hydrocarbon-based synthetic oils.
- 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.
- examples of 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 lubricant examples include polyvinyl ether oil and polyoxyalkylene lubricant.
- polyvinyl ether oil include those obtained by polymerizing vinyl ether monomers such as alkyl vinyl ether, and copolymers obtained by copolymerizing vinyl ether monomers and hydrocarbon monomers having olefinic double bonds.
- 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. A polyvinyl ether may be used individually by 1 type, and may be used in combination of 2 or more type.
- polyoxyalkylene-based lubricating oil examples include polyoxyalkylene monool, polyoxyalkylene polyol, polyoxyalkylene monool and alkyl etherified product of polyoxyalkylene polyol, polyoxyalkylene monool and esterified product of polyoxyalkylene polyol, and the like. Can be mentioned. 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 include water, monohydric alcohols such as methanol and butanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, pentaerythritol, and glycerol.
- polyoxyalkylene-based lubricating oil an alkyl etherified product or an esterified product of polyoxyalkylene monool or polyoxyalkylene polyol is preferable.
- the polyoxyalkylene polyol is preferably polyoxyalkylene glycol.
- an alkyl etherified product of polyoxyalkylene glycol in which the terminal hydroxyl group of polyoxyalkylene glycol is capped with an alkyl group such as a methyl group, called polyglycol oil is preferable.
- fluorine-based lubricating oils include compounds in which hydrogen atoms of synthetic oils (mineral oils, poly ⁇ -olefins, alkylbenzenes, alkylnaphthalenes, etc. described later) 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 significant antioxidant effect can be obtained by the stabilizer.
- the content of the lubricating oil may be in a range that does not significantly reduce the effects of the present invention, and varies depending on the application, the type of the compressor, etc.
- the amount is preferably 20 to 50 parts by mass.
- the stabilizer used in the working medium-containing composition 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.
- 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 examples include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimethylcaptothiadiazole, salicyridin-propylenediamine, pyrazole, benzotriazole, toltriazole, 2-methylbenzamidazole, 3,5- Imethylpyrazole, 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 acids Examples thereof include an amine salt of phosphate or a derivative thereof.
- the content of the stabilizer may be in a range that does not significantly reduce the effect of the present invention, and is preferably 5% by mass or less, more preferably 1% by mass or less in the working medium-containing composition (100% by mass).
- leak detection substance examples of leak detection substances used in the working medium-containing composition 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 of the odor masking agent include known fragrances such as those described in JP-T-2008-500337 and JP-T-2008-531836.
- a solubilizing agent that improves the solubility of the leak detection substance in the working medium may be used.
- the 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 preferably 2% by mass or less, more preferably 0.5% by mass or less in the working medium-containing composition (100% by mass). .
- the working medium or the working medium-containing composition of the present invention is an alcohol having 1 to 4 carbon atoms, or a compound used as a conventional working medium, refrigerant, or heat transfer medium (hereinafter, the alcohol and the compound are collectively referred to as May be included as other 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 other compounds may be in a range that does not significantly reduce the effect of the present invention, and is preferably 30% by mass or less, more preferably 20% by mass or less, in the working medium-containing composition (100% by mass), 15 A mass% or less is particularly preferred.
- the thermal cycle system of the present invention is a system using the working medium of the present invention.
- Examples of the heat cycle system include a Rankine cycle system, a heat pump cycle system, a refrigeration cycle system, and a heat transport system.
- Refrigeratoration cycle system A refrigeration cycle system will be described as an example of a heat cycle system.
- the refrigeration cycle system is a system that cools the load fluid to a lower temperature by removing the thermal energy from the load fluid in the evaporator in the evaporator.
- FIG. 1 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 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 composed of adiabatic / isentropic change, isenthalpy change and isobaric change, and the state change of the working medium can be expressed as shown in FIG. 2 on a temperature-entropy diagram.
- the AB process is a process in which adiabatic compression is performed by the compressor 11 and the high-temperature and low-pressure working medium vapor A is converted into a high-temperature and high-pressure working medium vapor B.
- the BC process is a process in which isobaric cooling is performed by the condenser 12 and the high-temperature and high-pressure working medium vapor B is converted into a low-temperature and high-pressure working medium C.
- 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.
- the DA process is a process in which isobaric heating is performed by the evaporator 14 and the low-temperature and low-pressure working medium D is returned to the high-temperature and low-pressure working medium vapor A.
- the water concentration of the working medium in the heat cycle system is preferably 100 ppm or less, and more preferably 20 ppm or less.
- 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.
- a zeolitic desiccant when a lubricating oil having a higher moisture absorption than conventional mineral-based lubricating oils is used, the compound represented by the following formula (1) is used as a main component 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 a valence of M
- x and y are values determined by a crystal structure.
- pore diameter and breaking strength are important.
- 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. Therefore, it is preferable to use 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.
- 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 is not particularly limited.
- the presence of chlorine in the thermal cycle system has undesirable effects such as deposit formation due to reaction with metals, bearing wear, and degradation of working media and lubricants.
- the chlorine concentration in the heat cycle system is preferably 100 ppm or less, and particularly preferably 50 ppm or less in terms of mass ratio to the 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.
- the refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated as the cycle performance (capacity and efficiency) when the working medium was applied to the refrigeration cycle system 10 of FIG.
- the evaluation sets the average evaporation temperature of the working medium in the evaporator 14, the average condensation temperature of the working medium in the condenser 12, the degree of supercooling of the working medium in the condenser 12, and the degree of superheating of the working medium in the evaporator 14, respectively. Carried out. In addition, it was assumed that there was no pressure loss in equipment efficiency and piping and heat exchanger.
- the refrigeration capacity Q and the coefficient of performance ⁇ can be obtained from the following equations (2) and (3) when the enthalpy h of each state (where the subscript h represents the state of the working medium).
- Q h A ⁇ h D (2).
- the coefficient of performance means the efficiency in the refrigeration cycle system, and the higher the coefficient of performance, the larger the output (refrigeration capacity) with less input (the amount of power required to operate the compressor). It shows that you can do it.
- the refrigerating capacity means the ability to cool the load fluid, and the higher the refrigerating capacity, the more work can be done in the same system. In other words, when having a large refrigeration capacity, it means that the target performance can be obtained with a small amount of working medium, and the system can be downsized.
- 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.
- Example 1 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated when HFO-1132 (Z) and HFO-1132 (E) were applied as working media in the ratio shown in Table 1 to the refrigeration cycle system 10 of FIG.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the operation in the evaporator 14 is performed.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 1 for every working medium.
- Example 2 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) when a working medium composed of HFO-1132 (Z) and HFC shown in Table 2 was applied to the refrigeration cycle system 10 of FIG. 1 was evaluated.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (each working medium / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium with respect to HFC-134a was determined. It shows in Table 2 for every working medium.
- Example 3 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated when a working medium composed of HFO-1132 (E) and HFC shown in Table 3 was applied to the refrigeration cycle system 10 of FIG.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the operation in the evaporator 14 is performed.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 3 for every working medium.
- Example 4 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated when the working medium composed of HFO-1132 (Z) and HFO shown in Table 4 or 5 was applied to the refrigeration cycle system 10 of FIG.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the operation in the evaporator 14 is performed.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 4 and Table 5 for every working medium.
- HFO-1132 (Z) has a higher refrigeration capacity than conventional HFO.
- HFO-1225ye (E) or HFO-1225ye (Z) maintained the coefficient of performance without a significant decrease in refrigeration capacity.
- Example 5 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) when a working medium composed of HFO-1132 (E) and HFO shown in Table 6 or 7 was applied to the refrigeration cycle system 10 of FIG. 1 was evaluated.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the operation in the evaporator 14 is performed.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 6 and Table 7 for every working medium.
- HFO-1132 (E) has a higher refrigeration capacity than conventional HFO.
- HFO-1132 (E) and HFO-1225ye (E) or HFO-1225ye (Z) maintained the coefficient of performance without a significant decrease in refrigeration capacity.
- Example 6 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated when a working medium composed of HFO-1132 (E) and the hydrocarbons shown in Table 8 was applied to the refrigeration cycle system 10 of FIG.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 8 for every working medium.
- Example 7 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) when a working medium composed of HFO-1132 (Z) and hydrocarbons shown in Table 9 was applied to the refrigeration cycle system 10 of FIG. 1 was evaluated.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the operation in the evaporator 14 is performed.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 9 for every working medium.
- Example 8 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) when a working medium composed of HFO-1132 (Z) and HCFO shown in Table 10 was applied to the refrigeration cycle system 10 of FIG. 1 was evaluated.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the operation in the evaporator 14 is performed.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 10 for every working medium.
- Example 9 The refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated when a working medium composed of HFO-1132 (E) and HCFO shown in Table 11 was applied to the refrigeration cycle system 10 of FIG.
- the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C.
- the average condensation temperature of the working medium in the condenser 12 is 50 ° C.
- the degree of supercooling of the working medium in the condenser 12 is 5 ° C.
- the operation in the evaporator 14 is performed.
- the medium was heated at a degree of superheat of 5 ° C.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 11 for every working medium.
- Refrigeration cycle performance (refrigeration capacity and refrigeration capacity when HFO-1132 (E), HFO-1132 (Z), or 1,1-difluoroethylene (HFO-1132a) is applied as the working medium to the refrigeration cycle system 10 of FIG.
- the coefficient of performance was evaluated.
- the evaporation temperature of the working medium in the evaporator 14, the condensation temperature of the working medium in the condenser 12, the degree of supercooling of the working medium in the condenser 12, and the degree of superheating of the working medium in the evaporator 14 were the temperatures shown in Table 12.
- the relative performance (respective working media / HFC-134a) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium relative to HFC-134a was determined. It shows in Table 12 for every working medium.
- HFO-1132 has a higher coefficient of performance than HFO-1132a. Since the critical temperature of HFO-1132a was too low, evaluation was not performed because a supercritical cycle was formed at a condensation temperature of 20 ° C. or higher.
- the working medium 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.
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Abstract
Description
しかし、二酸化炭素は、HFC-134aに比べて機器圧力が極めて高くなるため、全ての自動車へ適用するためには、多くの解決すべき課題を有する。HFC-152aは、燃焼範囲を有しており、安全性を確保するための課題を有する。
HFOの熱サイクル用作動媒体としては、たとえば、下記のものが知られている。
(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)(特許文献1)。
(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(特許文献2)。
(2)のHFOも、いずれもサイクル性能(能力)が不充分である。
本発明の作動媒体は、炭化水素をさらに含むのが好ましい。
本発明の作動媒体は、HFCをさらに含むのが好ましい。
本発明の作動媒体は、ヒドロクロロフルオロオレフィン(HCFO)またはクロロフルオロオレフィン(CFO)をさらに含むのが好ましい。
本発明の熱サイクルシステムは、本発明の作動媒体を用いたものであることを特徴とする。
本発明の熱サイクルシステムは、HFO-1132を含むため、熱力学性質に優れる本発明の作動媒体を用いているため、サイクル性能(効率および能力)に優れる。また、効率が優れていることから、消費電力の低減が図れるともに、能力が優れていることから、システムを小型化できる。
本発明の作動媒体は、1,2-ジフルオロエチレンンを含むものである。
本発明の作動媒体は、必要に応じて、炭化水素、HFC、HCFO、CFO、他のHFOなどの、CFO1132とともに気化、液化する他の作動媒体を含んでもよい。また、本発明の作動媒体は、作動媒体とともに使用される作動媒体以外の成分と併用することができる(以下、作動媒体と作動媒体以外の成分を含む組成物を作動媒体含有組成物という)。作動媒体以外の成分としては、潤滑油、安定剤、漏れ検出物質、乾燥剤、その他の添加剤等が挙げられる。
HFO-1132としては、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))の2種類の立体異性体が存在する。本発明においては、HFO-1132(E)を単独で用いてもよく、HFO-1132(Z)を単独で用いてもよく、HFO-1132(E)およびHFO-1132(Z)の混合物を用いてもよい。
HFO-1132の含有量は、作動媒体(100質量%)中、60質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上がさらに好ましく、100質量%が特に好ましい。
炭化水素は、鉱物系潤滑油に対する作動媒体の溶解性を向上させる作動媒体成分である。
炭化水素としては、炭素数が3~5であるのが好ましく、直鎖状であっても、分岐状であってもよい。
炭化水素としては、具体的には、プロパン、プロピレン、シクロプロパン、ブタン、イソブタン、ペンタンおよびイソペンタンが好ましい。
炭化水素は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
HFCは、熱サイクルシステムのサイクル性能(能力)を向上させる作動媒体成分である。
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HFCが好ましい。
HFCとしては、具体的には、ジフルオロメタン、ジフルオロエタン、トリフルオロエタン、テトラフルオロエタン、ペンタフルオロエタン、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。なかでも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、ジフルオロメタン(HFC-32)、1,1-ジフルオロエタン(HFC-152a)、1,1,2,2-テトラフルオロエタン(HFC-134)、1,1,1,2-テトラフルオロエタン(HFC-134a)およびペンタフルオロエタン(HFC-125)が特に好ましい。
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。
HCFOおよびCFOは、作動媒体の燃焼性を抑える作動媒体成分である。また、作動媒体への潤滑油の溶解性を向上させる成分である。
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。
HCFOとしては、具体的には、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る。なかでも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、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)および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。
CFOとしては、具体的には、クロロフルオロプロペン、クロロフルオロエチレン等が挙げられる。なかでも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、作動媒体の燃焼性を充分に抑える点から、1,1-ジクロロ-2,3,3,3-テトラフルオロプロペン(CFO-1214ya)および1,2-ジクロロ-1,2-ジフルオロエチレン(CFO-1112)が特に好ましい。
他のHFO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HFOが好ましい。
作動媒体含有組成物に使用される潤滑油としては、熱サイクルシステムに用いられる公知の潤滑油が用いられる。
潤滑油としては、含酸素系合成油(エステル系潤滑油、エーテル系潤滑油等)、フッ素系潤滑油、鉱物油、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。
ポリビニルエーテル油としては、アルキルビニルエーテルなどのビニルエーテルモノマーを重合して得られたもの、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を共重合して得られた共重合体がある。
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。
ポリビニルエーテルは、1種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。
開始剤としては、水、メタノールやブタノール等の1価アルコール、エチレンギリコール、プロピレングリコール、ペンタエリスリトール、グリセロール等の多価アルコールが挙げられる。
潤滑油としては、作動媒体との相溶性の点から、ポリオールエステル油および/またはポリグリコール油が好ましく、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。
作動媒体含有組成物に使用される安定剤は、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。
作動媒体含有組成物に使用さ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。
本発明の作動媒体や作動媒体含有組成物は、炭素数1~4のアルコール、または、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、該アルコールおよび化合物をまとめて、他の化合物と記す。)を含んでいてもよい。
含フッ素エーテル:ペルフルオロプロピルメチルエーテル(C3F7OCH3)、ペルフルオロブチルメチルエーテル(C4F9OCH3)、ペルフルオロブチルエチルエーテル(C4F9OC2H5)、1,1,2,2-テトラフルオロエチル-2,2,2-トリフルオロエチルエーテル(CF2HCF2OCH2CF3、旭硝子社製、AE-3000)等。
本発明の熱サイクルシステムは、本発明の作動媒体を用いたシステムである。
熱サイクルシステムとしては、ランキンサイクルシステム、ヒートポンプサイクルシステム、冷凍サイクルシステム、熱輸送システム等が挙げられる。
熱サイクルシステムの一例として、冷凍サイクルシステムについて説明する。
冷凍サイクルシステムとは、蒸発器において作動媒体が負荷流体より熱エネルギーを除去することにより、負荷流体を冷却し、より低い温度に冷却するシステムである。
(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。
図2中、AB過程は、圧縮機11で断熱圧縮を行い、高温低圧の作動媒体蒸気Aを高温高圧の作動媒体蒸気Bとする過程である。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とする過程である。CD過程は、膨張弁13で等エンタルピ膨張を行い、低温高圧の作動媒体Cを低温低圧の作動媒体Dとする過程である。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の原因となる。特に、上述したエーテル系潤滑油、エステル系潤滑油等は、吸湿性が極めて高く、また、加水分解反応を生じやすく、水分の混入は、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、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作動媒体の水分濃度は、100ppm以下が好ましく、20ppm以下がより好ましい。
M2/nO・Al2O3・xSiO2・yH2O ・・・(1)。
ただし、Mは、Na、K等の1族の元素またはCa等の2族の元素であり、nは、Mの原子価であり、x、yは、結晶構造にて定まる値である。Mを変化させることにより細孔径を調整できる。
作動媒体の分子径よりも大きい細孔径を有する乾燥剤を用いた場合、作動媒体が乾燥剤中に吸着され、その結果、作動媒体と乾燥剤との化学反応が生じ、不凝縮性気体の生成、乾燥剤の強度の低下、吸着能力の低下等の好ましくない現象を生じることとなる。
したがって、乾燥剤としては、細孔径の小さいゼオライト系乾燥剤を用いることが好ましい。特に、細孔径が3.5Å以下である、ナトリウム・カリウムA型の合成ゼオライトが好ましい。作動媒体の分子径よりも小さい細孔径を有するナトリウム・カリウムA型合成ゼオライトを適用することによって、作動媒体を吸着することなく、熱サイクルシステム内の水分のみを選択的に吸着除去できる。言い換えると、作動媒体の乾燥剤への吸着が起こりにくいことから、熱分解が起こりにくくなり、その結果、熱サイクルシステムを構成する材料の劣化やコンタミナンツの発生を抑制できる。
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。
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、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。
熱サイクルシステム内の塩素濃度は、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。
図1の冷凍サイクルシステム10に、作動媒体を適用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。
評価は、蒸発器14における作動媒体の平均蒸発温度、凝縮器12における作動媒体の平均凝縮温度、凝縮器12における作動媒体の過冷却度、蒸発器14における作動媒体の過熱度をそれぞれ設定し、実施した。また、機器効率および配管、熱交換器における圧力損失はないものとした。
Q=hA-hD ・・・(2)。
η=冷凍能力/圧縮仕事
=(hA-hD)/(hB-hA) ・・・(3)。
図1の冷凍サイクルシステム10に、作動媒体としてHFO-1132(Z)およびHFO-1132(E)を表1に示す割合で適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、HFO-1132(Z)と表2に示すHFCとからなる作動媒体を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、HFO-1132(E)と表3に示すHFCとからなる作動媒体を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、HFO-1132(Z)と表4または表5に示すHFOとからなる作動媒体を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、HFO-1132(E)と表6または表7に示すHFOとからなる作動媒体を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、HFO-1132(E)と表8に示す炭化水素とからなる作動媒体を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、HFO-1132(Z)と表9に示す炭化水素とからなる作動媒体を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、HFO-1132(Z)と表10に示すHCFOとからなる作動媒体を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、HFO-1132(E)と表11に示すHCFOとからなる作動媒体を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
評価は、蒸発器14における作動媒体の平均蒸発温度を0℃、凝縮器12における作動媒体の平均凝縮温度を50℃、凝縮器12における作動媒体の過冷却度を5℃、蒸発器14における作動媒体の過熱度を5℃として実施した。
図1の冷凍サイクルシステム10に、作動媒体としてHFO-1132(E)、HFO-1132(Z)、または1,1-ジフルオロエチレン(HFO-1132a)を適用した場合の冷凍サイクル性能(冷凍能力および成績係数)を評価した。
蒸発器14における作動媒体の蒸発温度、凝縮器12における作動媒体の凝縮温度、凝縮器12における作動媒体の過冷却度、蒸発器14における作動媒体の過熱度は、表12に示す温度とした。
なお、2011年5月19日に出願された日本特許出願2011-112416号の明細書、特許請求の範囲、図面及び要約書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 (13)
- 1,2-ジフルオロエチレンを含むことを特徴とする熱サイクル用作動媒体。
- 炭化水素をさらに含む、請求項1に記載の熱サイクル用作動媒体。
- ヒドロフルオロカーボンをさらに含む、請求項1または2に記載の熱サイクル用作動媒体。
- ヒドロクロロフルオロオレフィンまたはクロロフルオロオレフィンをさらに含む、請求項1~3のいずれか一項に記載の熱サイクル用作動媒体。
- 1,2-ジフルオロエチレンを、熱サイクル用作動媒体(100質量%)中、60質量%以上含む、請求項1~4のいずれか一項に記載の熱サイクル用作動媒体。
- 炭化水素を、熱サイクル用作動媒体(100質量%)中、1~30質量%含む、請求項2~5のいずれかに記載の熱サイクル用作動媒体。
- ヒドロフルオロカーボンを、熱サイクル用作動媒体(100質量%)中、1~99質量%含む、請求項3~6のいずれか一項に記載の熱サイクル用作動媒体。
- ヒドロクロロフルオロオレフィンおよびクロロフルオロオレフィンの合計の含有量が、熱サイクル用作動媒体(100質量%)中、1~60質量%である、請求項4~7のいずれか一項に記載の熱サイクル用作動媒体。
- 炭化水素が、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、またはイソペンタンである、請求項2~8のいずれか一項に記載の熱サイクル用作動媒体。
- ヒドロフルオロカーボンが、ジフルオロメタン、1,1-ジフルオロエタン、1,1,2,2-テトラフルオロエタン、1,1,1,2-テトラフルオロエタンまたはペンタフルオロエタンである、請求項3~9のいずれか一項に記載の熱サイクル用作動媒体。
- ヒドロクロロフルオロオレフィンが、1-クロロ-2,3,3,3-テトラフルオロプロペン、または1-クロロ-1,2-ジフルオロエチレンである、請求項4~10のいずれか一項に記載の熱サイクル用作動媒体。
- クロロフルオロオレフィンが、1,1-ジクロロ-2,3,3,3-テトラフルオロプロペン、または1,2-ジクロロ-1,2-ジフルオロエチレンである、請求項4~10のいずれか一項に記載の熱サイクル用作動媒体。
- 請求項1~12のいずれか一項に記載の熱サイクル用作動媒体を用いた、熱サイクルシステム。
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US10836941B2 (en) | 2020-11-17 |
CN103547652B (zh) | 2016-06-29 |
US10392544B2 (en) | 2019-08-27 |
EP2711407A1 (en) | 2014-03-26 |
JPWO2012157765A1 (ja) | 2014-07-31 |
RU2636152C2 (ru) | 2017-11-21 |
US20190330507A1 (en) | 2019-10-31 |
US20140077123A1 (en) | 2014-03-20 |
US20230183537A1 (en) | 2023-06-15 |
JP5935799B2 (ja) | 2016-06-15 |
US20210095176A1 (en) | 2021-04-01 |
US9790412B2 (en) | 2017-10-17 |
EP2711407A4 (en) | 2014-11-12 |
US20230183536A1 (en) | 2023-06-15 |
RU2013156342A (ru) | 2015-06-27 |
DE112012002162T5 (de) | 2014-02-27 |
CN103547652A (zh) | 2014-01-29 |
US20180002585A1 (en) | 2018-01-04 |
BR112013029408A2 (pt) | 2017-01-31 |
US20220380647A1 (en) | 2022-12-01 |
EP2711407B1 (en) | 2018-11-07 |
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