WO2015022959A1 - 熱伝達方法および高温ヒートポンプ装置 - Google Patents
熱伝達方法および高温ヒートポンプ装置 Download PDFInfo
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- WO2015022959A1 WO2015022959A1 PCT/JP2014/071284 JP2014071284W WO2015022959A1 WO 2015022959 A1 WO2015022959 A1 WO 2015022959A1 JP 2014071284 W JP2014071284 W JP 2014071284W WO 2015022959 A1 WO2015022959 A1 WO 2015022959A1
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- WIPO (PCT)
- Prior art keywords
- heat transfer
- mass
- transfer composition
- tetrafluoropropene
- composition
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000005540 biological transmission Effects 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 154
- 238000009833 condensation Methods 0.000 claims abstract description 18
- 230000005494 condensation Effects 0.000 claims abstract description 18
- 230000008016 vaporization Effects 0.000 claims abstract description 6
- 238000012546 transfer Methods 0.000 claims description 189
- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 claims description 60
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 27
- 239000003921 oil Substances 0.000 claims description 18
- -1 polyol ester Chemical class 0.000 claims description 14
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 11
- 229920001289 polyvinyl ether Polymers 0.000 claims description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
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- 239000003381 stabilizer Substances 0.000 claims description 10
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- 150000002148 esters Chemical class 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000002480 mineral oil Substances 0.000 claims description 6
- 235000010446 mineral oil Nutrition 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002828 nitro derivatives Chemical group 0.000 claims description 4
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- 229920013639 polyalphaolefin Polymers 0.000 claims description 4
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 claims description 3
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
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- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 8
- INEMUVRCEAELBK-UHFFFAOYSA-N 1,1,1,2-tetrafluoropropane Chemical compound CC(F)C(F)(F)F INEMUVRCEAELBK-UHFFFAOYSA-N 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- 239000003507 refrigerant Substances 0.000 description 37
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 30
- 238000010586 diagram Methods 0.000 description 27
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 23
- 238000010792 warming Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 238000007906 compression Methods 0.000 description 10
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- 230000006835 compression Effects 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 239000010721 machine oil Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
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- 239000002253 acid Substances 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
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- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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Images
Classifications
-
- 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
- F25B30/00—Heat pumps
- F25B30/02—Heat pumps of the compression type
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a heat transfer method and a high-temperature heat pump apparatus using a refrigerant for a high-temperature heat pump suitable for use at a condensation temperature of 70 ° C. or higher.
- a heat pump In an air conditioner or a hot water supply facility, a heat pump is generally used as a cooling or heating method.
- chlorofluorocarbon CFC
- hydrochlorofluorocarbon HCFC
- fluorine and chlorine has been conventionally used, but from the viewpoint of protection of the ozone layer, its use is being phased out.
- natural refrigerants such as ammonia and carbon dioxide or hydrofluorocarbons (HFC) that do not contain chlorine atoms in the molecule are mainly used.
- Patent Document 1 discloses a refrigerant for a high-temperature heat pump in which the condensation temperature of the refrigerant is 70 to 150 ° C.
- This refrigerant contains 1,1,1,3,3-pentafluoropropane as a main component, and the blending mass ratio of 1,1,1,3,3-pentafluorobutane is 20% or less. Yes.
- HFC is concerned that it has a large global warming potential (GWP) and contributes significantly to global warming.
- GWP global warming potential
- HFO hydrofluoroolefin
- Patent Document 2 discloses that a composition containing 2,3,3,3-tetrafluoropropene (HFO) and a polyalkylene glycol (PAG) lubricant is used as a refrigerant for an automobile air conditioner.
- HFO 2,3,3,3-tetrafluoropropene
- PAG polyalkylene glycol
- Patent Document 3 a mixed composition of tetrafluoropropene such as 2,3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene and difluoromethane is used as a refrigerant for a low-temperature refrigerator. It is disclosed to use.
- Patent Document 1 proposes an HFC mixed refrigerant for a high-temperature heat pump.
- the global warming potential is as large as 794 to 1030, there is a concern about permanent use in the future.
- Patent Documents 2 to 3 air-conditioning apparatuses using a vapor compression cycle using a low GWP working fluid have been proposed. All of them are refrigerants suitable for air-conditioning applications (cooling and heating). There is no description of application examples to heat pump cycles.
- An object of the present invention is to provide a further improved heat transfer composition and high-temperature heat pump apparatus.
- the preferred heat transfer working medium of the present invention does not contribute substantially to global warming compared to many currently used hydrofluorocarbons.
- the step of vaporizing the heat transfer composition, the step of compressing the heat transfer composition, the step of condensing the heat transfer composition, and the step of depressurizing the heat transfer composition A heat transfer method using a high-temperature heat pump system containing the heat transfer composition, wherein the heat transfer composition has a mass ratio of cis-1,3,3,3-tetrafluoropropene. 95.0 mass% or more and 99.9 mass% or less, and the mass ratio of trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene is 0.1 mass% or more
- a heat transfer method is provided that is 5.0% by mass or less and the condensation temperature is 70 ° C. or higher.
- the step of vaporizing the heat transfer composition the step of compressing the heat transfer composition, the step of condensing the heat transfer composition, and depressurizing the heat transfer composition.
- the ratio is 80.0 mass% or more and 99.9 mass% or less, and the mass ratio of trans-1-chloro-3,3,3-trifluoropropene or 1,1,1,3,3-pentafluoropropane is There is provided a heat transfer method that is 0.1% by mass or more and 20.0% by mass or less and that the condensation temperature is 70 ° C. or more.
- the mass ratio of cis-1,3,3,3-tetrafluoropropene in the heat transfer composition is 90.0% by mass or more and 99.9% by mass or less, and 1,1,1,
- the mass ratio of 3,3-pentafluoropropane may be 0.1% by mass or more and 10.0% by mass or less.
- the mass ratio of cis-1,3,3,3-tetrafluoropropene in the heat transfer composition is 90.0% by mass or more and 99.9% by mass or less, and trans-1-chloro-
- the mass ratio of 3,3,3-trifluoropropene may be 0.1% by mass or more and 10.0% by mass or less.
- the heat transfer composition may include a lubricant.
- the lubricant is a mineral oil (paraffinic oil or naphthenic oil) or synthetic oil alkylbenzenes (AB), poly (alpha-olefin), esters, polyol esters (POE), poly It may be selected from alkylene glycols (PAG), polyvinyl ethers (PVE) and combinations thereof.
- the heat transfer composition may further include a stabilizer.
- the heat transfer composition may further include a flame retardant.
- the flame retardant may be selected from phosphates, halogenated aromatic compounds, fluorinated iodocarbons, fluorinated bromocarbons, and combinations thereof.
- hot water of 60 ° C. or higher, pressurized hot water, or superheated steam may be generated.
- hot water of 80 ° C. or higher, pressurized hot water, or superheated steam may be generated.
- pressurized hot water or superheated steam at 100 ° C. or higher may be generated.
- a high-temperature heat pump device using any one of the heat transfer methods described above is provided.
- composition for heat transfer of the present invention it is possible to provide a mixed refrigerant for heat cycle that is nonflammable or slightly flammable, has little influence on the environment, and has excellent heat transfer characteristics. Moreover, the high temperature heat pump apparatus excellent in the heat transfer characteristic can be provided using the composition for heat transfer of this invention.
- the heat transfer method according to the present invention comprises cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene.
- the heat transfer composition is used.
- the heat transfer method according to the present invention includes cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene or 1,1,1,3,
- a heat transfer composition mixed with 3-pentafluoropropane is used.
- the heat transfer composition according to the present invention is nonflammable or slightly flammable, has a low environmental load, and has excellent heat cycle characteristics and heat transfer characteristics. The inventors have found.
- Cis-1,3,3,3-tetrafluoropropene HFO-1234ze (Z) will be described.
- HFO-1234ze (Z) is slightly flammable or flame retardant and has no toxicity.
- HFO-1234ze (Z) has a boiling point of 9.8 ° C. under atmospheric pressure, an atmospheric lifetime of 10 days, and a global warming potential (GWP) of 3 (Chemical Physics Letters 2009, Vol. 473, P233-237) It is.
- the critical temperature is 150.1 ° C. and the critical pressure is 3.54 MPa (4th IIR Conference on Thermophysical Properties and Transfer Processes of Refrigerant Proceedings TP-018).
- HFO-1234ze (E) is slightly flammable or flame retardant and has no toxicity.
- the boiling point of HFO-1234ze (E) is ⁇ 19 ° C. under atmospheric pressure, the atmospheric life is 14 days, and the global warming potential (GWP) is 6 (Chemical Physics Letters 2007, Vol.443, P199-204). is there.
- the critical temperature is 109.4 ° C., and the critical pressure is 3.63 MPa (Journal of Chemical Engineering Data 2010, Vol55, P1594-1597).
- HFO-1234yf contains a carbon-carbon double bond in the molecule and has a high reactivity with a hydroxyl radical. Therefore, the global warming potential (GWP) is extremely small and the environmental load is small.
- HFO-1234yf is slightly flammable and nontoxic.
- HFO-1234yf has a boiling point of ⁇ 29 ° C. under atmospheric pressure, an atmospheric life of 11 days, and a global warming potential (GWP) of 4 (Chemical Physics Letters 2007, Vol. 439, P18-22).
- the critical temperature is 94.7 ° C. and the critical pressure is 3.38 MPa (International Journal of Refrigeration 2010, Vol33, P474-479).
- HCFO-1233zd (E) is slightly flammable or flame retardant and has no toxicity.
- the boiling point of HCFO-1233zd (E) is 18.3 ° C. under atmospheric pressure, the atmospheric lifetime is 26 days, and the global warming potential (GWP) is 7 (Journal of Photochemistry and Photobiology A: Chemistry 2008, Vol.199). , P92-97).
- the critical temperature is 109.4 ° C., and the critical pressure is 3.63 MPa (Journal of Chemical Engineering Data 2012, Vol57, P3581-3586).
- HFC-245fa is nonflammable and has low toxicity.
- HFC-245fa has a boiling point of 15.3 ° C. under atmospheric pressure, an atmospheric lifetime of 7.6 years, and a global warming potential (GWP) of 1030 (IPCC Fourth Assessment Report 2007).
- GWP global warming potential
- HFC-245fa has a high global warming potential (GWP), when HFC-245fa is used, it is preferably contained in an amount of 1% by mass or more and 20% by mass or less, particularly 1% by mass or more and 10% by mass or less. desirable.
- GWP global warming potential
- the heat transfer composition of the present invention has a mass ratio of cis-1,3,3,3-tetrafluoropropene of 80.0% by mass or more and 99.9% by mass or less.
- 1-chloro-3,3,3-trifluoropropene or 1,1,1,3,3-pentafluoropropane is characterized by being 0.1% by mass or more and 20.0% by mass or less.
- the heat transfer composition of the present invention has a global warming potential of the refrigerant of less than 150.
- Cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene or 1,1,1,3,3-pentafluoropropane have a critical temperature relative to each other. Are close to each other, and the heat transfer composition according to the present invention including these has a small influence on the critical temperature of the composition.
- the critical temperature of the composition is close to each other, and the heat transfer composition according to the present invention including these has a small influence on the critical temperature of the composition.
- trans-1, 3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene has a low critical temperature.
- trans 1,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene may be 0.1% by mass or more and 5.0% by mass or less. preferable.
- the mass ratio of cis-1,3,3,3-tetrafluoropropene is 80.0% by mass or more, preferably 90.0% by mass or more and 99.9% by mass or less.
- the mass ratio of chloro-3,3,3-trifluoropropene or 1,1,1,3,3-pentafluoropropane is 0.1 mass% or more and 20.0 mass% or less, preferably 0.1 mass%
- the content is 10.0% by mass or less.
- the lubricating oil used in the compressor sliding portion is a mineral oil (paraffinic oil or naphthenic oil) or a synthetic oil alkylbenzene (AB).
- AB synthetic oil alkylbenzene
- Poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols (PAG) or polyvinyl ethers (PVE) can be used.
- the lubricant used in the expander sliding part is a mineral oil (paraffinic oil or naphthenic oil) or a synthetic oil alkylbenzene (AB). ), Poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols (PAG) or polyvinyl ethers (PVE).
- Alkylbenzenes include n-octylbenzene, n-nonylbenzene, n-decylbenzene, n-undecylbenzene, n-dodecylbenzene, n-tridecylbenzene, 2-methyl-1-phenylheptane, 2-methyl- 1-phenyloctane, 2-methyl-1-phenylnonane, 2-methyl-1-phenyldecane, 2-methyl-1-phenylundecane, 2-methyl-1-phenyldodecane, 2-methyl-1-phenyltridecane Etc.
- Esters include aromatic esters such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and mixtures thereof, dibasic acid esters, polyol esters, complex esters, carbonate esters, etc. It is done.
- alcohols used as starting materials for polyol esters include neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (penta And esters of hindered alcohols such as erythritol and tri- (pentaerythritol).
- carboxylic acids used as starting materials for polyol esters include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2- Examples include ethylhexanoic acid and 3,5,5-trimethylhexanoic acid.
- Polyalkylene glycol is methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, linear or branched hexanol, etc. And a compound obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide, etc. to an aliphatic alcohol having 1 to 18 carbon atoms.
- Polyvinyl ethers include polymethyl vinyl ether, polyethyl vinyl ether, poly n-propyl vinyl ether, polyisopropyl vinyl ether and the like.
- the heat transfer composition of the present invention can use a stabilizer in order to improve thermal stability, oxidation resistance and the like.
- the stabilizer include nitro compounds, epoxy compounds, phenols, imidazoles, amines, hydrocarbons and the like.
- nitro compound examples include known compounds, but include aliphatic and / or aromatic derivatives.
- aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like.
- aromatic nitro compounds for example, nitrobenzene, o-, m- or p-dinitrobenzene, trinitrobenzene, o-, m- or p-nitrotoluene, o-, m- or p-ethylnitrobenzene, 2,3-, 2 , 4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylnitrobenzene, o-, m- or p-nitroacetophenone, o-, m- or p-nitrophenol, o- M- or p-nitroanisole and the like.
- Examples of the epoxy compound include ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, 2 -Monoepoxy compounds such as ethylhexyl glycidyl ether, polyepoxy compounds such as diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane tolglycidyl ether Etc.
- phenols include phenols containing various substituents such as alkyl groups, alkenyl groups, alkoxy groups, carboxyl groups, carbonyl groups, and halogen atoms in addition to hydroxyl groups.
- substituents such as alkyl groups, alkenyl groups, alkoxy groups, carboxyl groups, carbonyl groups, and halogen atoms in addition to hydroxyl groups.
- Monovalent phenol such as eugenol, isoeugenol, butylhydroxyanisole, phenol, xylenol or divalent such as t-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-
- imidazoles examples include 1-methylimidazole, 1-n-butylimidazole having a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or an aryl group as the N-position substituent.
- amines include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, ⁇ -methyl Benzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, diventylamine, triventylamine, 2-ethylhexylamine, aniline N, N-dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetrae Renpentamin, benzylamine, dibenzylamine, dipheny
- hydrocarbons examples include aromatic unsaturated hydrocarbons such as ⁇ -methylstyrene and p-isopropenyltoluene, isoprenes, propadiene, terpenes and the like. These may be used alone or in combination of two or more.
- the stabilizer may be added in advance to one or both of the refrigerant and the lubricant, or may be added alone in the condenser.
- the usage-amount of a stabilizer is not specifically limited, 0.001 mass% or more and 10 mass% or less are preferable with respect to a main refrigerant
- the heat transfer composition of the present invention can use a flame retardant in order to improve combustibility.
- the flame retardant include phosphates, halogenated aromatic compounds, fluorinated iodocarbons, fluorinated bromocarbons, and the like.
- the condensation temperature of the heat transfer medium of the present invention having such a composition is 70 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher and 140 ° C. or lower.
- the condensation pressure of the heat transfer composition of the present invention having such a composition is determined by the composition of the heat transfer composition and the condensation temperature. That is, the condensation pressure is equal to the saturated vapor pressure of the heat transfer composition at the condensation temperature. Generally, if the condensation pressure exceeds 5.0 MPa, high pressure resistance is required for the compressor, the condenser and the piping parts, and these devices are expensive, which is not preferable.
- a condensation pressure can be made lower than 5.0 Mpa, and a well-known compressor, a condenser, and piping components can be used.
- the heat transfer composition of the present invention is nonflammable, has a low environmental load, and has excellent thermal cycle characteristics. Therefore, heat medium for high-temperature heat pumps used for generating pressurized hot water or superheated steam, etc., working medium for organic Rankine cycle used for power generation systems, refrigerant for vapor compression refrigeration cycle system, absorption heat pump, heat pipe Or a cleaning agent for cycle cleaning of a cooling system or a heat pump system, a metal cleaning agent, a flux cleaning agent, a diluting solvent, a foaming agent, an aerosol, or the like.
- the heat transfer method of the present invention is applicable not only to package-type small devices (such as Rankine cycle systems and heat pump cycle systems), but also to large scale power generation systems, heat pump hot water supply systems, heat pump steam generation systems, etc. Is possible.
- a high-temperature heat pump device moves the heat of an object to be cooled such as air, water, or brine in an evaporator as latent heat of vaporization of the refrigerant, and compresses the generated refrigerant vapor with work in the compressor.
- the condenser heat is discharged and liquefied, and the condensed refrigerant is squeezed and expanded to low pressure and low temperature by an expansion valve, and sent to the evaporator to evaporate.
- the refrigerant when the refrigerant receives the heat energy of the object to be cooled, the refrigerant cools the object to be cooled, and the temperature is lowered to a lower temperature.
- the heat energy of the refrigerant is given to the load fluid.
- the load fluid is heated to raise the temperature to a higher temperature, and can be applied to a known system.
- examples of the fluid to be cooled or the fluid to be heated that exchange heat with the refrigerant include air, water, brine, and silicone oil. These are preferably selected and used according to the cycle operating temperature conditions.
- FIG. 1 is a schematic view showing an example of a high-temperature heat pump apparatus to which the heat transfer composition of the present invention can be applied.
- the configuration and operation (repetition cycle) of the high-temperature heat pump apparatus 100 of FIG. 1 will be described.
- the high-temperature heat pump device 100 of the present invention includes an evaporator 11 that takes in heat and a condenser 13 that supplies heat. Furthermore, the high-temperature heat pump device 100 increases the pressure of the working medium (heat transfer composition) vapor exiting the evaporator 11 and squeezes the compressor 12 that consumes electric power and the working medium supercooled liquid exiting the condenser 13. An expansion valve 13 is provided for expansion.
- step (C) The working medium exiting from the compressor 12 is passed through the condenser 13, and the gaseous working medium is subjected to heat exchange with a fluid to be heated (air, water, etc.) to be liquefied.
- the high-temperature heat pump system containing the refrigerant has at least one evaporator 11, a compressor 12, a condenser 13, an expansion device 14, and a pipe for transporting the refrigerant between these elements.
- the type of the compressor is not particularly limited, but a single-stage or multi-stage centrifugal compressor, rotary piston compressor, rotary vane compressor, scroll compressor, screw compressor or piston / crank compressor is used. it can.
- hot water of 60 ° C or higher is generated.
- pressurized hot water or superheated steam at 80 ° C. or higher is generated.
- pressurized hot water or superheated steam at 110 ° C. or higher can be generated.
- the coefficient of performance is a generally accepted measure of refrigerant performance and the relative thermodynamics of the heat transfer composition during a particular heating or cooling cycle including evaporation or condensation of the heat transfer composition. This is particularly useful for expressing efficiency.
- the ratio of the amount of heat that the refrigerant accepts from the medium to be cooled in the evaporator to the amount of work applied by the compressor during compression is represented by COP R.
- COP R represents the ratio of the heat heat transfer composition in the condenser for the amount of work added by the compressor in compressing the vapor is released into the heated medium at COP H.
- the volume capacity of the heat transfer composition represents the amount of cooling or heating given by the heat transfer composition per unit suction volume of the compressor. That is, for a specific compressor, the greater the volume capacity of the heat transfer composition, the more the heat transfer composition can absorb or dissipate a greater amount of heat.
- Example 1 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane>
- the conditions shown in Table 1 The coefficient of performance was calculated.
- the physical property values of the heat transfer composition were determined by REFPROP ver. 9.0 of the National Institute of Standards and Technology (NIST).
- Table 1 shows the high-temperature heat pump cycle calculation condition 1 below.
- Heat pump cycle condition 1 assumes the generation of 80 ° C. hot water by heat exchange between the heat transfer composition and the heat source water in the condenser.
- COP H high-temperature heat pump cycle performance
- the equation for calculating the high-temperature heat pump cycle performance (COP H ) will be described in detail below.
- FIG. 2 shows a Ph diagram in Example 1 (cis-1,3,3,3-tetrafluoropropene: 1,1,1,3,3-pentafluoropropane having a mass ratio of 95: 5).
- cycle points 1, 2, 3, 4 indicate vapor compression cycle calculation condition 1.
- Example 2 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene> Table 1 shows the performance evaluation of a high-temperature heat pump cycle using a mixed heat transfer composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene. The coefficient of performance was calculated under the conditions shown. In FIG. 3, the Ph line in Example 2 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1-chloro-3,3,3-trifluoropropene is 95: 5) The figure is shown.
- Example 3 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane>
- the conditions shown in Table 2 The coefficient of performance was calculated.
- the Ph diagram in Example 3 cis-1,3,3,3-tetrafluoropropene: 1,1,1,3,3-pentafluoropropane has a mass ratio of 95: 5) Show.
- Table 2 shows high-temperature heat pump cycle calculation conditions 2 below.
- Heat pump cycle condition 2 assumes the production
- Example 4 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene> Table 2 shows the performance evaluation of a high-temperature heat pump cycle using a mixed heat transfer composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene. The coefficient of performance was calculated under the conditions shown. In FIG. 5, the Ph line in Example 4 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1-chloro-3,3,3-trifluoropropene is 95: 5) The figure is shown.
- Example 5 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane>
- the conditions shown in Table 3 The coefficient of performance was calculated.
- FIG. 6 a Ph diagram in Example 5 (mass ratio of cis-1,3,3,3-tetrafluoropropene: 1,1,1,3,3-pentafluoropropane is 95: 5) is shown. Show.
- Table 3 shows the high temperature heat pump cycle calculation condition 3 below.
- Heat pump cycle condition 3 assumes the generation of 130 ° C. hot water by heat exchange between the heat transfer composition and the heat source water in the condenser.
- Example 6 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene>
- Table 3 shows The coefficient of performance was calculated under the conditions shown.
- the Ph line in Example 6 mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1-chloro-3,3,3-trifluoropropene is 95: 5
- the figure is shown.
- Example 7 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene>
- the conditions shown in Table 1 The coefficient of performance was calculated.
- the Ph diagram in Example 7 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1,3,3,3-tetrafluoropropene is 95: 5) is shown. Show.
- Example 8 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene>
- the conditions shown in Table 2 The coefficient of performance was calculated.
- the Ph diagram in Example 8 the mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1,3,3,3-tetrafluoropropene is 95: 5) Show.
- Example 9 ⁇ Combined heat transfer composition of cis-1,3,3,3-tetrafluoropropene and trans-1,3,3,3-tetrafluoropropene>
- the conditions shown in Table 3 The coefficient of performance was calculated.
- the Ph diagram in Example 9 (mass ratio of cis-1,3,3,3-tetrafluoropropene: trans-1,3,3,3-tetrafluoropropene is 95: 5) Show.
- Example 10 ⁇ Composition for mixed heat transfer of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene>
- Table 1 The coefficient was calculated.
- FIG. 11 shows a Ph diagram in Example 10 (mass ratio of cis-1,3,3,3-tetrafluoropropene: 2,3,3,3-tetrafluoropropene is 95: 5).
- Example 11 ⁇ Composition for mixed heat transfer of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene>
- results were obtained under the conditions shown in Table 2. The coefficient was calculated.
- the Ph diagram in Example 11 mass ratio of cis-1,3,3,3-tetrafluoropropene: 2,3,3,3-tetrafluoropropene is 95: 5) is shown.
- Example 12 ⁇ Composition for mixed heat transfer of cis-1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene>
- Table 3 The coefficient was calculated.
- FIG. 13 shows a Ph diagram in Example 12 (cis-1,3,3,3-tetrafluoropropene: mass ratio of 2,3,3,3-tetrafluoropropene is 95: 5).
- HFC-365mfc ⁇ 1,1,1,3,3-pentafluorobutane
- HFC-365mfc is flammable and has low toxicity.
- HFC-365mfc has a boiling point of 40.2 ° C. under atmospheric pressure, an atmospheric lifetime of 8.6 years, and a global warming potential (GWP) of 794 (IPCC Fourth Assessment Report 2007).
- GWP global warming potential
- Example 1 to 12 and Comparative Examples 1 to 3 the values of the first component and the second component of the heat transfer composition are expressed as mass percentages.
- the first component of the mixed heat transfer composition is cis-1,3,3,3-tetrafluoropropene and the second component is 1,1,1,3,3- Pentafluoropropane.
- the first component of the mixed heat transfer composition is cis-1,3,3,3-tetrafluoropropene and the second component is trans-1-chloro-3,3, 3-trifluoropropene.
- the first component of the mixed heat transfer composition is cis-1,3,3,3-tetrafluoropropene and the second component is trans-1,3,3,3-tetrafluoro. Propen.
- the first component of the mixed heat transfer composition is cis-1,3,3,3-tetrafluoropropene and the second component is 2,3,3,3-tetrafluoropropene. is there.
- the first component of the mixed heat transfer composition is 1,1,1,3,3-pentafluoropropane
- the second component is 1,1,1,3,3- Pentafluorobutane
- the relative COP and relative CAP of Example 1, Example 2, Example 7 and Example 10 shown in Table 4, Table 5, Table 10, and Table 13 are for mixed heat transfer of Comparative Example 1 shown in Table 16.
- COP and CAP in the case of each component ratio of the composition were calculated as relative values with 1.00.
- the relative COP and relative CAP of Example 3, Example 4, Example 8, and Example 11 shown in Table 6, Table 7, Table 11, and Table 14 are the same as that of Comparative Example 2 shown in Table 17.
- the relative values were calculated with COP and CAP at 1.00 for each component ratio of the heat transfer composition.
- Example 5, Example 6, Example 9, and Example 12 shown in Table 8, Table 9, Table 12, and Table 15, the relative COP and the relative CAP of Comparative Example 3 are the same as those of Comparative Example 3 shown in Table 18.
- COP and CAP in each component ratio of the mixed heat transfer composition were calculated as relative values with 1.00.
- the mixed heat transfer composition of the present invention has 1,1,1,3,3-pentafluoropropane and 1,1 described in JP-A-2013-525720. It can be seen that the coefficient of performance and volume capacity when applied to a high-temperature heat pump are higher than those of the mixed heat transfer composition of 1,1,3,3-pentafluorobutane.
- Example 13 A SUS316 autoclave was filled with 30 g of the working medium, heated to 150 ° C. and held for 5 weeks. The presence or absence of a decomposition product of the working medium and an isomer product of the working medium was evaluated using gas chromatography. The obtained results are shown in Table 19.
- Example 14 A thermal stability test was conducted using cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)).
- HFO-1234ze Z
- 1.0 g of heat transfer composition and metal pieces iron, copper, and aluminum test pieces
- the heating temperature was 175, 200 or 250 ° C.
- Exterior heat transfer composition after 2 weeks, purity, acid content - the (F ions) were measured to evaluate the thermal stability. The results obtained are shown in Table 20.
- Example 15 A thermal stability test was conducted using 1,1,1,3,3-pentafluoropropane (HFC-245fa).
- HFC-245fa 1,1,1,3,3-pentafluoropropane
- 1.0 g of heat transfer composition and metal pieces iron, copper, and aluminum test pieces
- the heating temperature was 175, 200 or 250 ° C.
- Exterior heat transfer composition after 2 weeks, purity, acid content - the (F ions) were measured to evaluate the thermal stability. The results obtained are shown in Table 21.
- Example 16 In accordance with the compatibility test between the heat transfer composition of JIS-K-2211 “refrigeration oil” and the refrigerating machine oil, 1.7 g of the heat transfer composition and 0.3 g of the refrigerating machine oil were added to a thick glass test tube. The mixture of the composition for heat transfer and the refrigerating machine oil was solidified by cooling with liquid nitrogen. After the mixture of the heat transfer composition and the refrigerating machine oil was solidified, the upper part of the test tube and a vacuum pump were connected to remove the remaining air, and the upper part of the test tube was sealed with a gas burner. The sealed thick glass test tube was placed in a thermostat cooled to ⁇ 20 ° C.
- any of the heat transfer compositions had good compatibility with POE as a synthetic oil.
- HCFO-1233zd containing a chlorine atom had good compatibility with both minerals and trans isomers and cis isomers.
- the present invention is a heat transfer method to a fluid to be heated by a condensation process of a heat transfer composition that is nonflammable or slightly flammable and has a low environmental load.
- This method can be suitably used when the heat transfer temperature condition is 70 ° C. or higher as compared with the conventional heat transfer method using the condensation process of the hydrofluorocarbon heat transfer composition.
- the excellent coefficient of performance and volume capacity can greatly contribute to the reduction of power consumption.
- the method of the present invention can be used as high-grade warm water, pressurized hot water, or superheated steam by heating warm water in a medium / low temperature range that has not been sufficiently utilized until now.
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Abstract
Description
HFO-1234ze(Z)は、分子内に炭素-炭素間の二重結合を含み、水酸基ラジカルとの反応性が高いため、地球温暖化係数(GWP)が極めて小さく環境負荷が小さい。また、HFO-1234ze(Z)は微燃性又は難燃性であり、毒性がない。なお、HFO-1234ze(Z)の沸点は、大気圧下において9.8℃、大気寿命は10日、地球温暖化係数(GWP)は3(Chemical Physics Letters 2009, Vol.473, P233-237)である。また、臨界温度は150.1℃、臨界圧力は3.54MPa(4th IIR Conference on Thermophysical Properties and Transfer Processes of Refrigerant予稿集TP-018)である。
HFO-1234ze(E)は、分子内に炭素-炭素間の二重結合を含み、水酸基ラジカルとの反応性が高いため、地球温暖化係数(GWP)が極めて小さく環境負荷が小さい。また、HFO-1234ze(E)は微燃性又は難燃性であり、毒性がない。なお、HFO-1234ze(E)の沸点は、大気圧下において-19℃、大気寿命は14日、地球温暖化係数(GWP)は6(Chemical Physics Letters 2007, Vol.443, P199-204)である。また、臨界温度は109.4℃、臨界圧力は3.63MPa(Journal of Chemical Engineering Data 2010, Vol55, P1594-1597)である。
HFO-1234yfは、分子内に炭素-炭素間の二重結合を含み、水酸基ラジカルとの反応性が高いため、地球温暖化係数(GWP)が極めて小さく環境負荷が小さい。また、HFO-1234yfは微燃性であり、毒性がない。なお、HFO-1234yfの沸点は、大気圧下において-29℃、大気寿命は11日、地球温暖化係数(GWP)は4(Chemical Physics Letters 2007, Vol.439, P18-22)である。また、臨界温度は94.7℃、臨界圧力は3.38MPa(International Journal of Refrigeration 2010, Vol33, P474-479)である。
HCFO-1233zd(E)は、分子内に炭素-炭素間の二重結合を含み、水酸基ラジカルとの反応性が高いため、地球温暖化係数(GWP)が極めて小さく環境負荷が小さい。また、HCFO-1233zd(E)は微燃性又は難燃性であり、毒性がない。なお、HCFO-1233zd(E)の沸点は、大気圧下において18.3℃、大気寿命は26日、地球温暖化係数(GWP)は7(Journal of Photochemistry and Photobiology A: Chemistry 2008, Vol.199, P92-97)である。また、臨界温度は109.4℃、臨界圧力は3.63MPa(Journal of Chemical Engineering Data 2012, Vol57, P3581-3586)である。
HFC-245faは、不燃性であり、毒性が低い。なお、HFC-245faの沸点は、大気圧下において15.3℃、大気寿命は7.6年、地球温暖化係数(GWP)は1030(IPCC4次評価報告書 2007)である。
また、本発明の熱伝達組成物を高温ヒートポンプの冷媒に用いる場合、圧縮機摺動部で使用する潤滑油は、鉱物油(パラフィン系油またはナフテン系油)または合成油のアルキルベンゼン類(AB)、ポリ(アルファ-オレフィン)、エステル類、ポリオールエステル類(POE)、ポリアルキレングリコール類(PAG)またはポリビニルエーテル類(PVE)を用いることができる。
また、本発明の熱伝達組成物は、熱安定性、耐酸化性等を改善するために安定化剤を用いることができる。安定化剤としては、ニトロ化合物、エポキシ化合物、フェノール類、イミダゾール類、アミン類、炭化水素類等が挙げられる。
また、本発明の熱伝達組成物は、燃焼性を改善するために難燃剤を用いることができる。難燃剤としては、ホスフェート類、ハロゲン化芳香族化合物、フッ素化ヨードカーボン、フッ素化ブロモカーボン等が挙げられる。
<高温ヒートポンプ装置>
高温ヒートポンプ装置とは、蒸発器で空気、水またはブラインなどの被冷却物のもっている熱を、冷媒の蒸発潜熱としてそれに移動させ、発生した冷媒蒸気を、圧縮機において、仕事を加えて圧縮し、凝縮器で凝縮熱を排出して液化し、凝縮した冷媒を膨張弁で低圧・低温に絞り膨張させ、蒸発器に送り込んで蒸発させるシステムである。蒸発器において、被冷却物のもっている熱エネルギーを冷媒が受け取ることにより、被冷却物を冷却し、より低い温度へ降温するシステムであり、また、凝縮器において冷媒の熱エネルギーを負荷流体に与えることにより、負荷流体を加熱し、より高い温度に昇温するシステムであり、公知のシステムに適用できる。
(a)熱交換器(蒸発器11)内で液体状態の作動媒体を被冷却流体(空気、水など)と熱交換させ、気化させる。
(b)熱交換器から気化した冷媒を取り出し、気化した作動媒体を圧縮機12に通し、高圧の過熱蒸気を供給する。
(c)圧縮機12から出た作動媒体を凝縮器13へ通し、気体状態の作動媒体を被加熱流体(空気、水など)と熱交換させ、液化させる。
(d)液化した冷媒を膨張弁14により、絞り膨張させ、低圧の湿り蒸気を供給し、工程(a)へ再循環させる。
<シス-1,3,3,3-テトラフルオロプロペンおよび1,1,1,3,3-ペンタフルオロプロパンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよび1,1,1,3,3-ペンタフルオロプロパンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表1に示す条件で成績係数を算出した。熱伝達用組成物の物性値は、米国国立標準技術研究所(NIST)のREFPROP ver.9.0により求めた。
(A)圧縮機の圧縮過程は等エントロピー圧縮とする。
(B)膨張弁における絞り膨張過程は等エンタルピー膨張とする。
(C)配管および熱交換器における熱損失、圧力損失は無視する。
(D)圧縮機効率ηを0.7とする。
QEVA=G×(h1-h4)・・・(1)
であり,凝縮器における放熱量QCONは、
QCON=G×(h2-h3)・・・(2)
となる。
h2=h1+(h2th-h1)/η・・・(3)
となる。
W=G×(h2-h1)・・・(4)
となる。
COPH=QGC/W=(h2-h3)/(h2-h1)・・・(5)
となる。
CAP=ρ2×QGC=ρ2×(h2-h3)・・・(6)
となる。
G :熱伝達用組成物循環量
W :圧縮仕事
QEVA :入熱量
QCON :放熱量
COPH :成績係数(加熱)
CAP :体積能力(加熱)
h :比エンタルピー
1,2,3,4:サイクルポイント
2th :等エントロピー圧縮後のサイクルポイント
<シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1-クロロ-3,3,3-トリフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1-クロロ-3,3,3-トリフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表1に示す条件で成績係数を算出した。なお、図3において、実施例2(シス-1,3,3,3-テトラフルオロプロペン:トランス-1-クロロ-3,3,3-トリフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよび1,1,1,3,3-ペンタフルオロプロパンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよび1,1,1,3,3-ペンタフルオロプロパンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表2に示す条件で成績係数を算出した。なお、図4において、実施例3(シス-1,3,3,3-テトラフルオロプロペン:1,1,1,3,3-ペンタフルオロプロパンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1-クロロ-3,3,3-トリフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1-クロロ-3,3,3-トリフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表2に示す条件で成績係数を算出した。なお、図5において、実施例4(シス-1,3,3,3-テトラフルオロプロペン:トランス-1-クロロ-3,3,3-トリフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよび1,1,1,3,3-ペンタフルオロプロパンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよび1,1,1,3,3-ペンタフルオロプロパンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表3に示す条件で成績係数を算出した。なお、図6において、実施例5(シス-1,3,3,3-テトラフルオロプロペン:1,1,1,3,3-ペンタフルオロプロパンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1-クロロ-3,3,3-トリフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1-クロロ-3,3,3-トリフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表3に示す条件で成績係数を算出した。なお、図7において、実施例6(シス-1,3,3,3-テトラフルオロプロペン:トランス-1-クロロ-3,3,3-トリフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表1に示す条件で成績係数を算出した。なお、図8において、実施例7(シス-1,3,3,3-テトラフルオロプロペン:トランス-1,3,3,3-テトラフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表2に示す条件で成績係数を算出した。なお、図9において、実施例8(シス-1,3,3,3-テトラフルオロプロペン:トランス-1,3,3,3-テトラフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよびトランス-1,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表3に示す条件で成績係数を算出した。なお、図10において、実施例9(シス-1,3,3,3-テトラフルオロプロペン:トランス-1,3,3,3-テトラフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよび2,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよび2,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表1に示す条件で成績係数を算出した。なお、図11において、実施例10(シス-1,3,3,3-テトラフルオロプロペン:2,3,3,3-テトラフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよび2,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよび2,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表2に示す条件で成績係数を算出した。なお、図12において、実施例11(シス-1,3,3,3-テトラフルオロプロペン:2,3,3,3-テトラフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<シス-1,3,3,3-テトラフルオロプロペンおよび2,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物>
シス-1,3,3,3-テトラフルオロプロペンおよび2,3,3,3-テトラフルオロプロペンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表3に示す条件で成績係数を算出した。なお、図13において、実施例12(シス-1,3,3,3-テトラフルオロプロペン:2,3,3,3-テトラフルオロプロペンの質量比が95:5)におけるPh線図を示す。
<1,1,1,3,3-ペンタフルオロプロパンおよび1,1,1,3,3-ペンタフルオロブタン>
本発明の熱伝達用組成物の代わりに、1,1,1,3,3-ペンタフルオロプロパンおよび1,1,1,3,3-ペンタフルオロブタンの混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表1に示す条件で成績係数を算出した。なお、図14において、比較例1(1,1,1,3,3-ペンタフルオロプロパン:1,1,1,3,3-ペンタフルオロブタンの質量比が95:5)におけるPh線図を示す。
HFC-365mfcは、可燃性であり、毒性が低い。なお、HFC-365mfcの沸点は、大気圧下において40.2℃、大気寿命は8.6年、地球温暖化係数(GWP)は794(IPCC4次評価報告書 2007)である。
<1,1,1,3,3-ペンタフルオロプロパンおよび1,1,1,3,3-ペンタフルオロブタン>
本発明の熱伝達用組成物の代わりに、1,1,1,3,3-ペンタフルオロプロパンおよび1,1,1,3,3-ペンタフルオロブタン混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表2に示す条件で成績係数を算出した。なお、図15において、比較例2(1,1,1,3,3-ペンタフルオロプロパン:1,1,1,3,3-ペンタフルオロブタンの質量比が95:5)におけるPh線図を示す。
<1,1,1,3,3-ペンタフルオロプロパンおよび1,1,1,3,3-ペンタフルオロブタン>
本発明の熱伝達用組成物の代わりに、1,1,1,3,3-ペンタフルオロプロパンおよび1,1,1,3,3-ペンタフルオロブタン混合熱伝達用組成物を用いた高温ヒートポンプサイクルの性能評価において、表3に示す条件で成績係数を算出した。なお、図16において、比較例3(1,1,1,3,3-ペンタフルオロプロパン:1,1,1,3,3-ペンタフルオロブタンの質量比が95:5)におけるPh線図を示す。
SUS316製オートクレーブに作動媒体30gを充填し、150℃に加熱して、5週間保持した。ガスクロマトグラフィーを用いて、作動媒体の分解生成物および作動媒体の異性体生成物の有無について、評価を行った。得られた結果を表19に示す。
シス-1,3,3,3-テトラフルオロプロペン(HFO-1234ze(Z))を用いて熱安定性試験を行った。JIS-K-2211「冷凍機油」のシールドチューブテストに準拠して、熱伝達用組成物1.0gと金属片(鉄、銅、アルミニウムの各試験片)をガラス試験管に封入し、所定温度に加熱して2週間保持した。なお、加熱温度を175、200または250℃とした。2週間後の熱伝達用組成物の外観、純度、酸分(F-イオン)を測定し、熱安定性の評価を行った。得られた結果を表20に示す。
1,1,1,3,3-ペンタフルオロプロパン(HFC-245fa)を用いて熱安定性試験を行った。JIS-K-2211「冷凍機油」のシールドチューブテストに準拠して、熱伝達用組成物1.0gと金属片(鉄、銅、アルミニウムの各試験片)をガラス試験管に封入し、所定温度に加熱して2週間保持した。なお、加熱温度を175、200または250℃とした。2週間後の熱伝達用組成物の外観、純度、酸分(F-イオン)を測定し、熱安定性の評価を行った。得られた結果を表21に示す。
JIS-K-2211「冷凍機油」の熱伝達用組成物と冷凍機油の相溶性試験に準拠して、熱伝達用組成物1.7gと冷凍機油0.3gを厚肉ガラス試験管中に加え、液体窒素で冷却し、熱伝達用組成物および冷凍機油の混合物を固化した。熱伝達用組成物および冷凍機油の混合物が固化した後、試験管の上部と真空ポンプを接続して、残存する空気を除去し、試験管の上部をガスバーナーで溶封した。溶封した厚肉ガラス試験管を-20℃まで冷却した恒温槽に入れ、恒温槽の温度とガラス試験管内の組成物が等しい温度となるまで静置した。その後、目視により、熱伝達用組成物と冷凍機油との相溶性について、評価を行った。恒温槽の温度を-20~+80℃まで変化させて、相溶性を評価した。得られた結果を表22~26に示す。表22~26において、均一に相溶したときは○、二層分離または組成物に濁りを生じたときは×で評価した。
鉱物油(MO):スニソ4GS(日本サン石油製)
ポリオールエステル油(POE):SUNICE T68(日本サン石油製)
アルキルベンゼン油(AB):アトモス68N(JX日鉱日石エネルギー製)
ポリアルキレングリコール油(PAG):SUNICE P56(日本サン石油製)
ポリビニルエーテル油(PVE):ダフニーハーメチックオイルFVC68D(出光興産製)
Claims (14)
- 熱伝達組成物を気化させる工程と、前記熱伝達組成物を圧縮する工程と、熱伝達組成物の凝縮する工程と、前記熱伝達組成物を減圧する工程とを順次行う、前記熱伝達組成物を収容した高温ヒートポンプシステムを用いた、熱伝達方法であって、
前記熱伝達組成物は、シス-1,3,3,3-テトラフルオロプロペンの質量比率が95.0質量%以上99.9質量%以下であり、トランス-1,3,3,3-テトラフルオロプロペンまたは2,3,3,3-テトラフルオロプロペンの質量比率が0.1質量%以上5.0質量%以下であり、且つ、凝縮温度が70℃以上であることを特徴とする熱伝達方法。 - 熱伝達組成物を気化させる工程と、前記熱伝達組成物を圧縮する工程と、熱伝達組成物の凝縮する工程と、前記熱伝達組成物を減圧する工程とを順次行う、前記熱伝達組成物を収容した高温ヒートポンプシステムを用いた、熱伝達方法であって、
前記熱伝達組成物は、シス-1,3,3,3-テトラフルオロプロペンの質量比率が80.0質量%以上99.9質量%以下であり、トランス-1-クロロ-3,3,3-トリフルオロプロペンまたは1,1,1,3,3-ペンタフルオロプロパンの質量比率が0.1質量%以上20.0質量%以下であり、且つ、凝縮温度が70℃以上であることを特徴とする熱伝達方法。 - 前記熱伝達組成物のシス-1,3,3,3-テトラフルオロプロペンの質量比率が90.0質量%以上99.9質量%以下であり、1,1,1,3,3-ペンタフルオロプロパンの質量比率0.1質量%以上10.0質量%以下であることを特徴とする請求項2に記載の熱伝達方法。
- 前記熱伝達組成物のシス-1,3,3,3-テトラフルオロプロペンの質量比率が90.0質量%以上99.9質量%以下であり、トランス-1-クロロ-3,3,3-トリフルオロプロペンの質量比率0.1質量%以上10.0質量%以下であることを特徴とする請求項2に記載の熱伝達方法。
- 前記熱伝達組成物が潤滑剤を含むことを特徴とする請求項1に記載の熱伝達方法。
- 前記潤滑剤が、鉱物油(パラフィン系油またはナフテン系油)または合成オイルのアルキルベンゼン類(AB)、ポリ(アルファ-オレフィン)、エステル類、ポリオールエステル類(POE)、ポリアルキレングリコール類(PAG)、ポリビニルエーテル類(PVE)およびそれらの組合せから選択されることを特徴とする請求項5に記載の熱伝達方法。
- 前記熱伝達組成物が安定化剤をさらに含むことを特徴とする請求項1に記載の熱伝達方法。
- 前記安定化剤が、ニトロ化合物、エポキシ化合物、フェノール類、イミダゾール類、アミン類、ジエン系化合物類、ホスフェート類、芳香族不飽和炭化水素類、イソプレン類、プロパジエン類、テルペン類等およびそれらの組合せから選択されることを特徴とする請求項7に記載の熱伝達方法。
- 前記熱伝達組成物が難燃剤をさらに含むことを特徴とする請求項1に記載の熱伝達方法。
- 前記難燃剤が、ホスフェート類、ハロゲン化芳香族化合物、フッ素化ヨードカーボン、フッ素化ブロモカーボン等およびそれらの組合せから選択されることを特徴とする請求項9に記載の熱伝達方法。
- 60℃以上の温水、加圧熱水または過熱蒸気を生成することを特徴とする請求項1に記載の熱伝達方法。
- 80℃以上の温水、加圧熱水または過熱蒸気を生成することを特徴とする請求項1に記載の熱伝達方法。
- 110℃以上の加圧熱水または過熱蒸気を生成することを特徴とする請求項1に記載の熱伝達方法。
- 請求項1に記載の熱伝達方法を用いる高温ヒートポンプ装置。
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