WO2022191205A1 - 冷媒を含む組成物、その使用、並びにそれを有する冷凍機及びその冷凍機の運転方法 - Google Patents
冷媒を含む組成物、その使用、並びにそれを有する冷凍機及びその冷凍機の運転方法 Download PDFInfo
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- WO2022191205A1 WO2022191205A1 PCT/JP2022/010086 JP2022010086W WO2022191205A1 WO 2022191205 A1 WO2022191205 A1 WO 2022191205A1 JP 2022010086 W JP2022010086 W JP 2022010086W WO 2022191205 A1 WO2022191205 A1 WO 2022191205A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- point
- refrigerant
- hfo
- mass
- r1234ze
- Prior art date
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 172
- 239000000203 mixture Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims description 13
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical group F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 claims abstract description 4
- 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 claims abstract description 3
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010586 diagram Methods 0.000 claims description 36
- 239000010721 machine oil Substances 0.000 claims description 25
- 239000012530 fluid Substances 0.000 claims description 18
- -1 fluorocarbon compounds Chemical class 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 239000007850 fluorescent dye Substances 0.000 description 6
- 239000000700 radioactive tracer Substances 0.000 description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 3
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 3
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 3
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 3
- 229920001774 Perfluoroether Polymers 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FYIRUPZTYPILDH-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoropropane Chemical compound FC(F)C(F)C(F)(F)F FYIRUPZTYPILDH-UHFFFAOYSA-N 0.000 description 2
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- JRHMNRMPVRXNOS-UHFFFAOYSA-N trifluoro(methoxy)methane Chemical compound COC(F)(F)F JRHMNRMPVRXNOS-UHFFFAOYSA-N 0.000 description 2
- ORNGPPZBMMHKPM-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-2-(1,1,2,2,2-pentafluoroethoxy)ethane Chemical compound FC(F)(F)C(F)(F)OC(F)(F)C(F)(F)F ORNGPPZBMMHKPM-UHFFFAOYSA-N 0.000 description 1
- FDOPVENYMZRARC-UHFFFAOYSA-N 1,1,1,2,2-pentafluoropropane Chemical compound CC(F)(F)C(F)(F)F FDOPVENYMZRARC-UHFFFAOYSA-N 0.000 description 1
- OYAUGTZMGLUNPS-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-(1,1,1,2,3,3,3-heptafluoropropan-2-yloxy)propane Chemical compound FC(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)F OYAUGTZMGLUNPS-UHFFFAOYSA-N 0.000 description 1
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 1
- QZFIQARJCSJGEG-UHFFFAOYSA-N 1,1,1,2-tetrafluoro-2-(1,2,2,2-tetrafluoroethoxy)ethane Chemical compound FC(F)(F)C(F)OC(F)C(F)(F)F QZFIQARJCSJGEG-UHFFFAOYSA-N 0.000 description 1
- CXJWJJZGJZNBRK-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(1,1,1,3,3,3-hexafluoropropan-2-yloxy)propane Chemical compound FC(F)(F)C(C(F)(F)F)OC(C(F)(F)F)C(F)(F)F CXJWJJZGJZNBRK-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 1
- VWCLQNINSPFHFV-UHFFFAOYSA-N 10-oxapentacyclo[12.8.0.02,11.04,9.015,20]docosa-1(14),2(11),4,6,8,12,15,17,19,21-decaene Chemical compound C1=CC=C2C3=CC=C4OC5=CC=CC=C5CC4=C3C=CC2=C1 VWCLQNINSPFHFV-UHFFFAOYSA-N 0.000 description 1
- DPQNQLKPUVWGHE-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropan-1-amine Chemical compound NCC(F)(F)C(F)(F)F DPQNQLKPUVWGHE-UHFFFAOYSA-N 0.000 description 1
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical compound FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 description 1
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- WSNAAHWRJMRVCU-UHFFFAOYSA-N 2-tert-butyl-3,4-dimethylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C WSNAAHWRJMRVCU-UHFFFAOYSA-N 0.000 description 1
- PRDFNJUWGIQQBW-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-yne Chemical compound FC(F)(F)C#C PRDFNJUWGIQQBW-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- BOTGCZBEERTTDQ-UHFFFAOYSA-N 4-Methoxy-1-naphthol Chemical compound C1=CC=C2C(OC)=CC=C(O)C2=C1 BOTGCZBEERTTDQ-UHFFFAOYSA-N 0.000 description 1
- FKTCIVHJKSDNRI-UHFFFAOYSA-N 6-butyl-2,3-dimethylphenol Chemical group CCCCC1=CC=C(C)C(C)=C1O FKTCIVHJKSDNRI-UHFFFAOYSA-N 0.000 description 1
- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229960003505 mequinol Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 102220110933 rs151253274 Human genes 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
-
- 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 disclosure relates to a composition containing a refrigerant, its use, a refrigerator having the same, and a method of operating the refrigerator.
- Patent Document 1 As a working medium for heat cycle that can be substituted for R410A, a working medium for heat cycle containing trifluoroethylene (HFO-1123) and 1,2-difluoroethylene (HFO-1132) has been proposed (Patent Document 1). .
- the present disclosure aims to provide a novel low GWP mixed refrigerant.
- Section 1 A composition comprising a refrigerant, the refrigerant is trans-1,2-difluoroethylene (HFO-1132(E)), 1,3,3,3-tetrafluoropropene (R1234ze) and 2,3,3,3-tetrafluoro-1-propene A composition comprising (R1234yf). Section 2.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segment enclosed by the line segments AB, BF, FE and EA connecting the four points of Line segments AB, BF and EA are straight lines, and a point on line segment FE is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748), Item 1.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segments enclosed by the line segments CD, DF, FE and EC connecting the four points of Line segments DF and EC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment FE The upper point is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748), Item 1.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments AB, BH, HG and GA connecting the four points of Line segments AB, BH, and GA are straight lines,
- a point on the line segment HG is represented by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242)
- Item 1 The composition according to item 1.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments AB, BJ, JI and IA connecting the four points of Line segments AB, BJ, and IA are straight lines, and a point on line segment JI is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76), Item 1.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H'(31.3, 1.0, 67.7) and Point G'(44.1, 54.9, 1.0) is within or on the line segment enclosed by the line segments AB, BH', H'G' and G'A connecting the four points of Line segments AB, BH', and G'A are straight lines, and a point on line segment H'G' is (x, -0.08728x2+10.791x-251.26, 0.08728x2 -11.791x+351.26) represented, Item 1.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments CD, DH, HG and GC connecting the four points of Line segments DH and GC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment HG
- the point above is denoted by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242 ), Item 1.
- composition according to item 1. Item 8. In the refrigerant, the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments CD, DJ, JI and IC connecting the four points of Line segments DJ and IC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment JI The point above is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76), Item 1.
- composition according to item 1. Item 9.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7)
- the line segment DH' is a straight line
- a point on line segment PD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54)
- a point on line segment H'P is represented by (x, -0.08728x 2 +10.791x-251.26, 0.08728x 2 -11.791x+351.26), Item 1.
- composition according to item 1 Item 10.
- Item 10. The composition according to any one of Items 1 to 9, further comprising refrigerating machine oil.
- Item 11. The composition according to any one of Items 1 to 10, which is used as a substitute refrigerant for R404A.
- Item 12. A refrigerator comprising the composition according to any one of Items 1 to 10 as a working fluid.
- Item 13. A method for operating a refrigerator, A method comprising circulating the composition according to any one of Items 1 to 10 as a working fluid in a refrigerator.
- Item 14. Use of the composition according to any one of items 1 to 10 as a substitute refrigerant for R410A.
- the refrigerant of the present disclosure has a low GWP.
- FIG. 1 is a three-component composition diagram in which the sum of HFO-1132(E), R1234ze and R1234y is 100% by mass, and points A to F are indicated.
- the term "refrigerant” includes at least a compound with a refrigerant number (ASHRAE number) starting with R, which indicates the type of refrigerant, defined by ISO817 (International Organization for Standardization), and furthermore, the refrigerant number is Even if they are not attached yet, those having properties as refrigerants equivalent to those are included.
- Refrigerants are roughly classified into “fluorocarbon compounds” and “non-fluorocarbon compounds” in terms of compound structure.
- “Fluorocarbon compounds” include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs).
- composition containing a refrigerant includes (1) refrigerant itself (including a mixture of refrigerants) and (2) other components, which are mixed with at least refrigerating machine oil. and (3) a working fluid for a refrigerator containing a refrigerator oil.
- the composition of (2) is referred to as a "refrigerant composition” to distinguish it from the refrigerant itself (including mixtures of refrigerants).
- the working fluid for a refrigerator (3) is described as a "refrigerating machine oil-containing working fluid” to distinguish it from the "refrigerant composition”.
- the second refrigerant can be used only by changing a small number of parts (at least one of refrigerating machine oil, gaskets, packing, expansion valves, dryers and other parts) and adjusting the equipment as necessary. means that it can operate under optimum conditions. In other words, this type refers to operating the same equipment by "alternating" the refrigerant.
- equipment designed to operate with a second refrigerant may be used with a second refrigerant installed for the same use as the existing use of the first refrigerant.
- alternate This typology refers to providing the same application by "replacement" of the refrigerant.
- a refrigerator refers to a general device that removes heat from an object or space to make it lower in temperature than the surrounding outside air and maintain this low temperature.
- a refrigerator is a conversion device that converts energy by obtaining energy from the outside and performing work in order to move heat from a low temperature area to a high temperature area.
- the refrigerant is "WCF slightly flammable” means that the most flammable composition (Worst case of formulation for flammability; WCF) according to the US ANSI/ASHRAE34-2013 standard has a burning velocity of 10 cm / s or less.
- the refrigerant is ASHRAE slightly flammable (WCF & WCFF slightly flammable) means that the WCF has a burning rate of 10 cm / s or less, and WCF is used for storage, transportation,
- the most flammable fraction composition (Worst case of fractionation for flammability; WCFF) specified by performing a leakage test during use has a burning speed of 10 cm/s or less, and meets the American ANSI/ASHRAE34-2013 standard for flammability. It means that the division is judged as "2L class".
- Refrigerants of the present disclosure include HFO-1132(E), R1234ze and R1234yf.
- the refrigerant of the present disclosure is a low GWP mixed refrigerant.
- the refrigerant of the present disclosure preferably satisfies the following requirements. At this time, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 70% or more based on R404A. ⁇ Requirements> In the refrigerant, the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segment enclosed by the line segments AB, BF, FE and EA connecting the four points of Line segments AB, BF and EA are straight lines, and a point on line segment FE is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).
- the refrigerant of the present disclosure preferably satisfies the following requirements. At this time, the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable), and the refrigerating capacity ratio based on R404A is 70% or more.
- ASHRAE slightly flammable WCF & WCFF slightly flammable
- the refrigerating capacity ratio based on R404A is 70% or more.
- the refrigerant the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segments enclosed by the line segments CD, DF, FE and EC connecting the four points of Line segments DF and EC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment FE The top point is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).
- the refrigerant of the present disclosure preferably satisfies the following requirements. At this time, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 100% or more based on R134a. ⁇ Requirements> In the refrigerant, the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments AB, BH, HG and GA connecting the four points of Line segments AB, BH, and GA are straight lines,
- a point on line segment HG is represented by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242).
- the refrigerant of the present disclosure preferably satisfies the following requirements. At this time, the refrigerant of the present disclosure becomes WCF slightly flammable and has a boiling point of ⁇ 40° C. or less. ⁇ Requirements> In the refrigerant, the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments AB, BJ, JI and IA connecting the four points of Line segments AB, BJ, and IA are straight lines, and a point on line segment JI is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).
- the refrigerant of the present disclosure preferably satisfies the following requirements.
- the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a refrigerating capacity ratio of 150% or more based on R134a.
- ASHRAE slightly flammable WCF & WCFF slightly flammable
- the refrigerant has a refrigerating capacity ratio of 150% or more based on R134a.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H'(31.3, 1.0, 67.7) and Point G'(44.1, 54.9, 1.0) is within or on the line segment enclosed by the line segments AB, BH', H'G' and G'A connecting the four points of Line segments AB, BH', and G'A are straight lines, and a point on line segment H'G' is (x, -0.08728x2+10.791x-251.26, 0.08728x2 -11.791x+351.26) represented.
- the refrigerant of the present disclosure preferably satisfies the following requirements.
- the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a refrigerating capacity ratio of 100% or more based on R134a.
- ASHRAE slightly flammable WCF & WCFF slightly flammable
- the refrigerant has a refrigerating capacity ratio of 100% or more based on R134a.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments CD, DH, HG and GC connecting the four points of Line segments DH and GC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment HG The top point is denoted by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242 ).
- the refrigerant of the present disclosure preferably satisfies the following requirements.
- the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a boiling point of -40°C or less.
- ASHRAE slightly flammable WCF & WCFF slightly flammable
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments CD, DJ, JI and IC connecting the four points of Line segments DJ and IC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment JI The top point is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).
- the refrigerant of the present disclosure preferably satisfies the following requirements.
- the refrigerant of the present disclosure becomes ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a refrigerating capacity ratio of 150% or more based on R134a.
- ASHRAE slightly flammable WCF & WCFF slightly flammable
- the refrigerant has a refrigerating capacity ratio of 150% or more based on R134a.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7)
- the line segment DH' is a straight line
- a point on line segment PD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54)
- a point on line segment H'P is represented by (x, -0.08728x 2 +10.791x-251.26, 0.08728x 2 -11.791x+351.26).
- the refrigerant of the present disclosure may contain additional refrigerants in addition to HFO-1132(E), R1234ze and R1234yf within a range that does not impair the above characteristics and effects.
- the refrigerant of the present disclosure preferably contains 99.5% by mass or more, and preferably 99.75% by mass or more, of the total of HFO-1132(E), R1234ze and R1234yf relative to the total refrigerant. More preferably, it contains 99.9% by mass or more, even more preferably 99.999% by mass or more, and most preferably 99.9999% by mass or more.
- the refrigerants of the present disclosure may consist essentially of HFO-1132(E), R1234ze and R1234yf, in which case the refrigerants of the present disclosure comprise HFO-1132(E), R1234ze and R1234y, and It may consist only of unavoidable impurities.
- Refrigerants of the present disclosure may consist solely of HFO-1132(E), R1234ze and R1234yf.
- the additional refrigerant is not particularly limited and can be selected from a wide range.
- the mixed refrigerant may contain one kind alone or two or more kinds as an additional refrigerant.
- Additional refrigerants include acetylene, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124 , CFC-1113, HFC-152a, HFC-161 and 3,3,3-trifluoropropyne.
- the total amount of the additional refrigerant is preferably 0.5% by mass or less, more preferably 0.25% by mass or less, further preferably 0.1% by mass or less, and 0.01% by mass with respect to the total refrigerant. Most preferably:
- Refrigerant compositions of the present disclosure comprise at least the refrigerant of the present disclosure and can be used for the same applications as the refrigerant of the present disclosure.
- the refrigerant composition of the present disclosure can be used to obtain a working fluid for refrigerators by further mixing with at least refrigerator oil.
- the refrigerant composition of the present disclosure further contains at least one other component in addition to the refrigerant of the present disclosure.
- the refrigerant composition of the present disclosure may optionally contain at least one of the following other components. As described above, when the refrigerant composition of the present disclosure is used as a working fluid in refrigerators, it is usually mixed with at least refrigerator oil.
- the refrigerant compositions of the present disclosure are preferably substantially free of refrigerating machine oil.
- the content of refrigerating machine oil is preferably 1% by mass or less, more preferably 0.1% by mass or less, relative to the entire refrigerant composition.
- the refrigerant compositions of the present disclosure may contain trace amounts of water.
- the water content in the refrigerant composition is preferably 0.1% by mass or less with respect to the entire refrigerant. Since the refrigerant composition contains a trace amount of water, the intramolecular double bond of the unsaturated fluorocarbon compound that may be contained in the refrigerant is stabilized, and oxidation of the unsaturated fluorocarbon compound is less likely to occur. , the stability of the refrigerant composition is improved.
- Tracers are added to the refrigerant compositions of the present disclosure in detectable concentrations so that any dilution, fouling, or other modification of the refrigerant compositions of the present disclosure can be traced.
- the refrigerant composition of the present disclosure may contain a single tracer, or may contain two or more tracers.
- the tracer is not particularly limited and can be appropriately selected from commonly used tracers.
- Tracers include, for example, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, Aldehyde, ketone, nitrous oxide (N 2 O) and the like.
- Hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons and fluoroethers are particularly preferred as tracers.
- FC- 14 tetrafluoromethane, CF4
- HCC-40 chloromethane, CH3Cl
- HFC-23 trifluoromethane , CHF3
- HFC-41 fluoromethane, CH3Cl
- HFC - 125 penentafluoroethane, CF3CHF2
- HFC-134a (1,1,1,2 - tetrafluoroethane, CF3CH2F
- HFC-134 1,1,2,2 - tetrafluoroethane, CHF2CHF2
- HFC-143a 1,1,1 - trifluoroethane, CF3CH3
- HFC-143 (1,1,2 - trifluoroethane, CHF2CH2F
- HFC-152a 1,1 - difluoroethane, CHF2CH3
- HFC-152a (1,1 - difluoroethane, CHF2CH3 ) HFC-152 (1
- the refrigerant composition of the present disclosure may contain a total of about 10 parts per million (ppm) or more by weight of the tracer relative to the total refrigerant composition.
- Refrigerant compositions of the present disclosure may also contain less than about 1000 ppm total tracer, based on the total refrigerant composition.
- Refrigerant compositions of the present disclosure may preferably contain about 30 ppm or more, more preferably about 50 ppm or more of total tracer, based on the total refrigerant composition.
- Refrigerant compositions of the present disclosure may contain total tracers, preferably less than or equal to about 500 ppm, and less than or equal to about 300 ppm, based on the total refrigerant composition.
- the refrigerant composition of the present disclosure may contain one type of ultraviolet fluorescent dye alone, or may contain two or more types thereof.
- the ultraviolet fluorescent dye is not particularly limited, and can be appropriately selected from commonly used ultraviolet fluorescent dyes.
- ultraviolet fluorescent dyes examples include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof. Either or both of naphthalimide and coumarin are particularly preferred as UV fluorescent dyes.
- the refrigerant composition of the present disclosure may contain one stabilizer alone, or may contain two or more stabilizers.
- the stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.
- stabilizers include nitro compounds, ethers and amines.
- Nitro compounds include, for example, aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.
- Ethers include, for example, 1,4-dioxane.
- amines examples include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.
- the stabilizer content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the entire refrigerant.
- the stabilizer content is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the entire refrigerant.
- the refrigerant composition of the present disclosure may contain a single polymerization inhibitor, or may contain two or more polymerization inhibitors.
- the polymerization inhibitor is not particularly limited, and can be appropriately selected from commonly used polymerization inhibitors.
- polymerization inhibitors examples include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.
- the content of the polymerization inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the entire refrigerant.
- the content of the polymerization inhibitor is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the entire refrigerant.
- the refrigerating machine oil-containing working fluid of the present disclosure contains at least the refrigerant or refrigerant composition of the present disclosure and refrigerating machine oil, and is used as a working fluid in a refrigerating machine.
- the refrigerating machine oil-containing working fluid of the present disclosure is obtained by mixing refrigerating machine oil used in a compressor of a refrigerator with a refrigerant or a refrigerant composition.
- the working fluid containing refrigerating machine oil generally contains 10% by mass or more of refrigerating machine oil.
- the working fluid containing refrigerating machine oil generally contains 50% by mass or less of refrigerating machine oil.
- composition of the present disclosure may contain one type of refrigerating machine oil alone, or may contain two or more types of refrigerating machine oil.
- the refrigerating machine oil is not particularly limited, and can be appropriately selected from commonly used refrigerating machine oils. In this case, if necessary, it is possible to appropriately select a refrigerating machine oil that is more excellent in terms of the miscibility with the mixture and the effect of improving the stability of the mixture.
- the base oil of the refrigerator oil for example, at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE) and polyvinyl ether (PVE) is preferable.
- PAG polyalkylene glycol
- POE polyol ester
- PVE polyvinyl ether
- the refrigerating machine oil may contain additives in addition to the base oil.
- the additive may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents and antifoaming agents. .
- a refrigerating machine oil with a kinematic viscosity of 5 cSt or more at 40°C is preferable in terms of lubrication.
- the refrigerating machine oil having a kinematic viscosity of 400 cSt or less at 40° C. is preferable.
- the refrigerating machine oil-containing working fluid of the present disclosure may further contain at least one additive, if necessary.
- additives include the following compatibilizers.
- the working fluid containing refrigerator oil of the present disclosure may contain one type of compatibilizer alone or may contain two or more types of compatibilizer.
- the compatibilizer is not particularly limited and can be appropriately selected from commonly used compatibilizers.
- Compatibilizers include, for example, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.
- Polyoxyalkylene glycol ether is particularly preferred as the compatibilizer.
- the refrigerator operation method of the present disclosure is a method of operating the refrigerator using the refrigerant of the present disclosure.
- the method of operating the refrigerator of the present disclosure includes a step of circulating the refrigerant of the present disclosure in the refrigerator.
- a mixed refrigerant was prepared by mixing HFO-1132(E), R1234ze and R1234yf in mass % shown in Table 1 based on the sum of these.
- a GWP of 1 was assumed for HFO-1132(E).
- the refrigerating capacity of R410A and the above mixed refrigerant was obtained by conducting theoretical calculations of the refrigerating cycle of the mixed refrigerant under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0). .
- COP (refrigeration capacity or heating capacity) / power consumption
- the burning rate test was performed using the device shown in Fig. 1 as follows. First, the mixed refrigerant used was made 99.5% pure or better and degassed by repeated freezing, pumping and thawing cycles until no trace of air was visible on the vacuum gauge. Burning rates were measured by the closed method. The initial temperature was ambient temperature. Ignition was achieved by creating an electrical spark between the electrodes in the center of the sample cell. The discharge duration was 1.0-9.9ms and the ignition energy was typically about 0.1-1.0J. Flame propagation was visualized by the Schlieren method. A cylindrical container (inner diameter: 155 mm, length: 198 mm) with two light-transmitting acrylic windows was used as the sample cell, and a xenon lamp was used as the light source. Schlieren images of flames were recorded with a high-speed digital video camera at a framing speed of 600 fps and saved on a PC.
- the burning velocity (Su (cm/s)) is expressed by the volume of unburned gas consumed per unit time by a flame front of unit area, and is calculated by the following formula.
- Su Sb* ⁇ u/ ⁇ b Sb; Flame propagation velocity (cm/s) ⁇ u; adiabatic flame temperature (unburned) ⁇ b;Adiabatic flame temperature (burned)
- Sb was obtained from the Schlieren video image
- ⁇ u was the measured temperature
- ⁇ b was calculated from the combustion heat and constant pressure specific heat of the combustion gas.
- the refrigerant of the present disclosure when the refrigerant of the present disclosure satisfies the following requirements, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 70% or more based on R404A.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segment enclosed by the line segments AB, BF, FE and EA connecting the four points of Line segments AB, BF and EA are straight lines, and a point on line segment FE is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).
- the refrigerant of the present disclosure satisfies the following requirements, it is found that the refrigerant of the present disclosure becomes WCFF slightly flammable and has a refrigerating capacity ratio of 70% or more based on R404A.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) is within or on the line segments enclosed by the line segments CD, DF, FE and EC connecting the four points of Line segments DF and EC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment FE The top point is represented by (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).
- the refrigerant of the present disclosure when the refrigerant of the present disclosure satisfies the following requirements, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 100% or more based on R134a.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments AB, BH, HG and GA connecting the four points of Line segments AB, BH, and GA are straight lines,
- a point on line segment HG is represented by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242).
- the refrigerant of the present disclosure when the refrigerant of the present disclosure satisfies the following requirements, the refrigerant of the present disclosure becomes slightly flammable with WCF and has a boiling point of ⁇ 40° C. or lower.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments AB, BJ, JI and IA connecting the four points of Line segments AB, BJ, and IA are straight lines, and a point on line segment JI is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).
- the refrigerant of the present disclosure when the refrigerant of the present disclosure satisfies the following requirements, the refrigerant of the present disclosure becomes WCF slightly flammable and has a refrigerating capacity ratio of 150% or more based on R134a.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H'(31.3, 1.0, 67.7) and Point G'(44.1, 54.9, 1.0) is within or on the line segment enclosed by the line segments AB, BH', H'G' and G'A connecting the four points of Line segments AB, BH', and G'A are straight lines, and a point on line segment H'G' is (x, -0.08728x2+10.791x-251.26, 0.08728x2 -11.791x+351.26) represented.
- the refrigerant of the present disclosure satisfies the following requirements, it is found that the refrigerant of the present disclosure becomes WCFF slightly flammable and has a refrigerating capacity ratio of 100% or more based on R134a.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), point H(2.1, 1.0, 96.9) and point G(14.4, 84.6, 1.0) is within or on the line segments enclosed by the line segments CD, DH, HG and GC connecting the four points of Line segments DH and GC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment HG The top point is denoted by (x, -0.1974x 2 +10.054x-19.242 , 0.1974x 2 -11.054x+119.242 ).
- the refrigerant of the present disclosure satisfies the following requirements, it is found that the refrigerant of the present disclosure becomes WCFF slightly flammable and has a boiling point of ⁇ 40° C. or lower.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are Point C(38.7, 60.3, 1.0), point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I(22.6, 76.4, 1.0) is within or on the line segment enclosed by the line segments CD, DJ, JI and IC connecting the four points of Line segments DJ and IC are straight lines, and a point on line segment CD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and line segment JI The top point is represented by (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).
- the refrigerant of the present disclosure satisfies the following requirements, it is found that the refrigerant of the present disclosure becomes WCFF slightly flammable and has a refrigerating capacity ratio of 150% or more based on R134a.
- the sum of HFO-1132(E), R1234ze and R1234y is 100, where x, y and z are the mass % based on the sum of HFO-1132(E), R1234ze and R1234yf.
- the coordinates (x, y, z) are point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7)
- the line segment DH' is a straight line
- a point on line segment PD is represented by (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 +-0.8166x-35.54)
- a point on line segment H'P is represented by (x, -0.08728 x 2 +10.791x-251.26, 0.08728x 2 -11.791x+351.26).
- the approximation formula that indicates the coordinates of the points on each line segment was obtained by obtaining the approximation formula for the curve that connects the three points using the least-squares method.
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Abstract
Description
冷媒を含む組成物であって、
前記冷媒が、トランス-1,2-ジフルオロエチレン(HFO-1132(E))、1,3,3,3-テトラフルオロプロペン(R1234ze)及び2,3,3,3-テトラフルオロ-1-プロペン(R1234yf)を含む、組成物。
項2.
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点F(17.0, 1.0, 82.0)及び
点E(34.1, 64.9, 1.0)
の4点をそれぞれ結ぶ線分AB、BF、FE及びEAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BF及びEAは直線であり、かつ
線分FE上の点は、(x, -0.0556x2+6.5772x-94.748, 0.0556x2-7.5772x+194.748)で表わされる、
項1に記載の組成物。
項3.
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点F(17.0, 1.0, 82.0)及び
点E(34.1, 64.9, 1.0)
の4点をそれぞれ結ぶ線分CD、DF、FE及びECで囲まれる図形の範囲内又は前記線分上にあり、
線分DF及びECは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分FE上の点は、(x, -0.0556x2+6.5772x-94.748, 0.0556x2-7.5772x+194.748)で表わされる、
項1に記載の組成物。
項4.
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点H(2.1, 1.0, 96.9)及び
点G(14.4, 84.6, 1.0)
の4点をそれぞれ結ぶ線分AB、BH、HG及びGAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BH、及びGAは直線であり、
線分HG上の点は、(x, -0.1974x2+10.054x-19.242 , 0.1974x2-11.054x+119.242)で表わされる、
項1に記載の組成物。
項5.
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点J(12.3, 1.0, 86.7)及び
点I(22.6, 76.4, 1.0)
の4点をそれぞれ結ぶ線分AB、BJ、JI及びIAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BJ、及びIAは直線であり、かつ
線分JI上の点は、(x, -0.1609x2+12.934x-133.76, 0.1609x2-13.934x+233.76)で表わされる、
項1に記載の組成物。
項6.
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点H’(31.3, 1.0, 67.7)及び
点G’(44.1, 54.9, 1.0)
の4点をそれぞれ結ぶ線分AB、BH’、H’G’及びG’Aで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BH’、及びG’Aは直線であり、かつ
線分H’G’上の点は、(x, -0.08728x2+10.791x-251.26, 0.08728x2-11.791x+351.26)で表わされる、
項1に記載の組成物。
項7.
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点H(2.1, 1.0, 96.9)及び
点G(14.4, 84.6, 1.0)
の4点をそれぞれ結ぶ線分CD、DH、HG及びGCで囲まれる図形の範囲内又は前記線分上にあり、
線分DH及びGCは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分HG上の点は、(x, -0.1974x2+10.054x-19.242 , 0.1974x2-11.054x+119.242 )で表わされる、
項1に記載の組成物。
項8.
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点J(12.3, 1.0, 86.7)及び
点I(22.6, 76.4, 1.0)
の4点をそれぞれ結ぶ線分CD、DJ、JI及びICで囲まれる図形の範囲内又は前記線分上にあり、
線分DJ及びICは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分JI上の点は、(x, -0.1609x2+12.934x-133.76, 0.1609x2-13.934x+233.76)で表わされる、
項1に記載の組成物。
項9.
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点P(41.95, 47.8, 10.25)、
点D(52.4, 1.0, 46.6)及び
点H’(31.3, 1.0, 67.7)
の3点をそれぞれ結ぶ線分PD、DH’及びH’Pで囲まれる図形の範囲内又は前記直線上にあり、
線分DH’は直線であり、
線分PD上の点は(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分H’P上の点は(x, -0.08728x2+10.791x-251.26, 0.08728x2-11.791x+351.26)で表わされる、
項1に記載の組成物。
項10.
さらに、冷凍機油を含有する、項1~9のいずれか一項に記載の組成物。
項11.
R404Aの代替冷媒として用いられる、項1~10のいずれか一項に記載の組成物。
項12.
項1~10のいずれか一項に記載の組成物を作動流体として含む、冷凍機。
項13.
冷凍機の運転方法であって、
項1~10のいずれか一項に記載の組成物を作動流体として冷凍機において循環させる工程を含む、方法。
項14.
R410Aの代替冷媒としての、項1~10のいずれ一項に記載の組成物の使用。
<用語の定義>
本明細書において用語「冷媒」には、ISO817(国際標準化機構)で定められた、冷媒の種類を表すRで始まる冷媒番号(ASHRAE番号)が付された化合物が少なくとも含まれ、さらに冷媒番号が未だ付されていないとしても、それらと同等の冷媒としての特性を有するものが含まれる。冷媒は、化合物の構造の面で、「フルオロカーボン系化合物」と「非フルオロカーボン系化合物」とに大別される。「フルオロカーボン系化合物」には、クロロフルオロカーボン(CFC)、ハイドロクロロフルオロカーボン(HCFC)及びハイドロフルオロカーボン(HFC)が含まれる。
本開示の冷媒は、HFO-1132(E)、R1234ze及びR1234yfを含む。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点F(17.0, 1.0, 82.0)及び
点E(34.1, 64.9, 1.0)
の4点をそれぞれ結ぶ線分AB、BF、FE及びEAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BF及びEAは直線であり、かつ
線分FE上の点は、(x, -0.0556x2+6.5772x-94.748, 0.0556x2-7.5772x+194.748)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点F(17.0, 1.0, 82.0)及び
点E(34.1, 64.9, 1.0)
の4点をそれぞれ結ぶ線分CD、DF、FE及びECで囲まれる図形の範囲内又は前記線分上にあり、
線分DF及びECは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分FE上の点は、(x, -0.0556x2+6.5772x-94.748, 0.0556x2-7.5772x+194.748)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点H(2.1, 1.0, 96.9)及び
点G(14.4, 84.6, 1.0)
の4点をそれぞれ結ぶ線分AB、BH、HG及びGAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BH、及びGAは直線であり、
線分HG上の点は、(x, -0.1974x2+10.054x-19.242 , 0.1974x2-11.054x+119.242)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点J(12.3, 1.0, 86.7)及び
点I(22.6, 76.4, 1.0)
の4点をそれぞれ結ぶ線分AB、BJ、JI及びIAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BJ、及びIAは直線であり、かつ
線分JI上の点は、(x, -0.1609x2+12.934x-133.76, 0.1609x2-13.934x+233.76)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点H’(31.3, 1.0, 67.7)及び
点G’(44.1, 54.9, 1.0)
の4点をそれぞれ結ぶ線分AB、BH’、H’G’及びG’Aで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BH’、及びG’Aは直線であり、かつ
線分H’G’上の点は、(x, -0.08728x2+10.791x-251.26, 0.08728x2-11.791x+351.26)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点H(2.1, 1.0, 96.9)及び
点G(14.4, 84.6, 1.0)
の4点をそれぞれ結ぶ線分CD、DH、HG及びGCで囲まれる図形の範囲内又は前記線分上にあり、
線分DH及びGCは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分HG上の点は、(x, -0.1974x2+10.054x-19.242 , 0.1974x2-11.054x+119.242 )で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点J(12.3, 1.0, 86.7)及び
点I(22.6, 76.4, 1.0)
の4点をそれぞれ結ぶ線分CD、DJ、JI及びICで囲まれる図形の範囲内又は前記線分上にあり、
線分DJ及びICは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分JI上の点は、(x, -0.1609x2+12.934x-133.76, 0.1609x2-13.934x+233.76)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点P(41.95, 47.8, 10.25)、
点D(52.4, 1.0, 46.6)及び
点H’(31.3, 1.0, 67.7)
の3点をそれぞれ結ぶ線分PD、DH’及びH’Pで囲まれる図形の範囲内又は前記直線上にあり、
線分DH’は直線であり、
線分PD上の点は(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分H’P上の点は(x, -0.08728x2+10.791x-251.26, 0.08728x2-11.791x+351.26)で表わされる。
本開示の冷媒組成物は、本開示の冷媒を少なくとも含み、本開示の冷媒と同じ用途のために使用することができる。また、本開示の冷媒組成物は、さらに少なくとも冷凍機油と混合することにより冷凍機用作動流体を得るために用いることができる。
本開示の冷媒組成物は、本開示の冷媒に加え、さらに少なくとも一種のその他の成分を含有する。本開示の冷媒組成物は、必要に応じて、以下のその他の成分のうち少なくとも一種を含有していてもよい。上述の通り、本開示の冷媒組成物を、冷凍機における作動流体として使用するに際しては、通常、少なくとも冷凍機油と混合して用いられる。したがって、本開示の冷媒組成物は、好ましくは冷凍機油を実質的に含まない。具体的には、本開示の冷媒組成物は、冷媒組成物全体に対する冷凍機油の含有量が好ましくは1質量%以下であり、より好ましくは0.1質量%以下である。
本開示の冷媒組成物は微量の水を含んでもよい。冷媒組成物における含水割合は、冷媒全体に対して、0.1質量%以下とすることが好ましい。冷媒組成物が微量の水分を含むことにより、冷媒中に含まれ得る不飽和のフルオロカーボン系化合物の分子内二重結合が安定化され、また、不飽和のフルオロカーボン系化合物の酸化も起こりにくくなるため、冷媒組成物の安定性が向上する。
トレーサーは、本開示の冷媒組成物が希釈、汚染、その他何らかの変更があった場合、その変更を追跡できるように検出可能な濃度で本開示の冷媒組成物に添加される。
FC-14(テトラフルオロメタン、CF4)
HCC-40(クロロメタン、CH3Cl)
HFC-23(トリフルオロメタン、CHF3)
HFC-41(フルオロメタン、CH3Cl)
HFC-125(ペンタフルオロエタン、CF3CHF2)
HFC-134a(1,1,1,2-テトラフルオロエタン、CF3CH2F)
HFC-134(1,1,2,2-テトラフルオロエタン、CHF2CHF2)
HFC-143a(1,1,1-トリフルオロエタン、CF3CH3)
HFC-143(1,1,2-トリフルオロエタン、CHF2CH2F)
HFC-152a(1,1-ジフルオロエタン、CHF2CH3)
HFC-152(1,2-ジフルオロエタン、CH2FCH2F)
HFC-161(フルオロエタン、CH3CH2F)
HFC-245fa(1,1,1,3,3-ペンタフルオロプロパン、CF3CH2CHF2)HFC-236fa(1,1,1,3,3,3-ヘキサフルオロプロパン、CF3CH2CF3)HFC-236ea(1,1,1,2,3,3-ヘキサフルオロプロパン、CF3CHFCHF2)HFC-227ea(1,1,1,2,3,3,3-ヘプタフルオロプロパン、CF3CHFCF3)HCFC-22(クロロジフルオロメタン、CHClF2)
HCFC-31(クロロフルオロメタン、CH2ClF)
CFC-1113(クロロトリフルオロエチレン、CF2=CClF)
HFE-125(トリフルオロメチル-ジフルオロメチルエーテル、CF3OCHF2)HFE-134a(トリフルオロメチル-フルオロメチルエーテル、CF3OCH2F)HFE-143a(トリフルオロメチル-メチルエーテル、CF3OCH3)
HFE-227ea(トリフルオロメチル-テトラフルオロエチルエーテル、CF3OCHFCF3)HFE-236fa(トリフルオロメチル-トリフルオロエチルエーテル、CF3OCH2CF3)
本開示の冷媒組成物は、紫外線蛍光染料として、一種を単独で含有してもよいし、二種以上を含有してもよい。
本開示の冷媒組成物は、安定剤として、一種を単独で含有してもよいし、二種以上を含有してもよい。
本開示の冷媒組成物は、重合禁止剤として、一種を単独で含有してもよいし、二種以上を含有してもよい。
本開示の冷凍機油含有作動流体は、本開示の冷媒又は冷媒組成物と、冷凍機油とを少なくとも含み、冷凍機における作動流体として用いられる。具体的には、本開示の冷凍機油含有作動流体は、冷凍機の圧縮機において使用される冷凍機油と、冷媒又は冷媒組成物とが互いに混じり合うことにより得られる。冷凍機油含有作動流体には冷凍機油は一般に10質量%以上含まれる。冷凍機油含有作動流体には冷凍機油は一般に50質量%以下含まれる。
本開示の組成物は、冷凍機油として、一種を単独で含有してもよいし、二種以上を含有してもよい。
本開示の冷凍機油含有作動流体は、相溶化剤として、一種を単独で含有してもよいし、二種以上を含有してもよい。
本開示の冷凍機の運転方法は、本開示の冷媒を用いて冷凍機を運転する方法である。
R410A(R32=50%/R125=50%)及び上記混合冷媒のGWPは、IPCC(Intergovernmental Panel on Climate Change)第4次報告書の値に基づいて評価した。HFO-1132(E)のGWPは1と想定した。R410A及び上記混合冷媒の冷凍能力は、National Institute of Science and Technology(NIST)Reference Fluid Thermodynamic and Transport Properties Database(Refprop 9.0)を使い、下記条件で混合冷媒の冷凍サイクル理論計算を実施することにより求めた。
蒸発温度:-50℃(表1)及び(表5)、-10℃(表2)及び(表6)
凝縮温度:45℃
過熱度:5K
過冷却度:5K
圧縮機効率:70%
これらの値を、各混合冷媒についてのGWPと合わせて表1に示す。なお、比COP及び比冷凍能力については、R410A又はR134aに対する割合を示す。
COP =(冷凍能力又は暖房能力)/消費電力量
Su=Sb*ρu/ρb
Sb;火炎伝搬速度(cm/s)
ρu;断熱火炎温度(未燃)
ρb;断熱火炎温度(既燃)
ここで、Sbはシュリーレンビデオ画像から求め、ρuは測定温度、ρbは燃焼ガスの燃焼熱及び定圧比熱から算出した。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点F(17.0, 1.0, 82.0)及び
点E(34.1, 64.9, 1.0)
の4点をそれぞれ結ぶ線分AB、BF、FE及びEAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BF及びEAは直線であり、かつ
線分FE上の点は、(x, -0.0556x2+6.5772x-94.748, 0.0556x2-7.5772x+194.748)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点F(17.0, 1.0, 82.0)及び
点E(34.1, 64.9, 1.0)
の4点をそれぞれ結ぶ線分CD、DF、FE及びECで囲まれる図形の範囲内又は前記線分上にあり、
線分DF及びECは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分FE上の点は、(x, -0.0556x2+6.5772x-94.748, 0.0556x2-7.5772x+194.748)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点H(2.1, 1.0, 96.9)及び
点G(14.4, 84.6, 1.0)
の4点をそれぞれ結ぶ線分AB、BH、HG及びGAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BH、及びGAは直線であり、
線分HG上の点は、(x, -0.1974x2+10.054x-19.242 , 0.1974x2-11.054x+119.242)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点J(12.3, 1.0, 86.7)及び
点I(22.6, 76.4, 1.0)
の4点をそれぞれ結ぶ線分AB、BJ、JI及びIAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BJ、及びIAは直線であり、かつ
線分JI上の点は、(x, -0.1609x2+12.934x-133.76, 0.1609x2-13.934x+233.76)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点H’(31.3, 1.0, 67.7)及び
点G’(44.1, 54.9, 1.0)
の4点をそれぞれ結ぶ線分AB、BH’、H’G’及びG’Aで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BH’、及びG’Aは直線であり、かつ
線分H’G’上の点は、(x, -0.08728x2+10.791x-251.26, 0.08728x2-11.791x+351.26)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点H(2.1, 1.0, 96.9)及び
点G(14.4, 84.6, 1.0)
の4点をそれぞれ結ぶ線分CD、DH、HG及びGCで囲まれる図形の範囲内又は前記線分上にあり、
線分DH及びGCは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分HG上の点は、(x, -0.1974x2+10.054x-19.242 , 0.1974x2-11.054x+119.242 )で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点J(12.3, 1.0, 86.7)及び
点I(22.6, 76.4, 1.0)
の4点をそれぞれ結ぶ線分CD、DJ、JI及びICで囲まれる図形の範囲内又は前記線分上にあり、
線分DJ及びICは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分JI上の点は、(x, -0.1609x2+12.934x-133.76, 0.1609x2-13.934x+233.76)で表わされる。
<要件>
前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点P(41.95, 47.8, 10.25)、
点D(52.4, 1.0, 46.6)及び
点H’(31.3, 1.0, 67.7)
の3点をそれぞれ結ぶ線分PD、DH’及びH’Pで囲まれる図形の範囲内又は前記直線上にあり、
線分DH’は直線であり、
線分PD上の点は(x, -0.0455x2-0.1834x+135.54, 0.0455x2+-0.8166x-35.54)で表わされ、かつ
線分H’P上の点は(x, -0.08728x2+10.791x-251.26, 0.08728x2-11.791x+351.26)で表わされる。
Claims (14)
- 冷媒を含む組成物であって、
前記冷媒が、トランス-1,2-ジフルオロエチレン(HFO-1132(E))、1,3,3,3-テトラフルオロプロペン(R1234ze)及び2,3,3,3-テトラフルオロ-1-プロペン(R1234yf)を含む、組成物。 - 前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点F(17.0, 1.0, 82.0)及び
点E(34.1, 64.9, 1.0)
の4点をそれぞれ結ぶ線分AB、BF、FE及びEAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BF及びEAは直線であり、かつ
線分FE上の点は、(x, -0.0556x2+6.5772x-94.748, 0.0556x2-7.5772x+194.748)で表わされる、
請求項1に記載の組成物。 - 前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点F(17.0, 1.0, 82.0)及び
点E(34.1, 64.9, 1.0)
の4点をそれぞれ結ぶ線分CD、DF、FE及びECで囲まれる図形の範囲内又は前記線分上にあり、
線分DF及びECは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分FE上の点は、(x, -0.0556x2+6.5772x-94.748, 0.0556x2-7.5772x+194.748)で表わされる、
請求項1に記載の組成物。 - 前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点H(2.1, 1.0, 96.9)及び
点G(14.4, 84.6, 1.0)
の4点をそれぞれ結ぶ線分AB、BH、HG及びGAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BH、及びGAは直線であり、
線分HG上の点は、(x, -0.1974x2+10.054x-19.242 , 0.1974x2-11.054x+119.242)で表わされる、
請求項1に記載の組成物。 - 前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点J(12.3, 1.0, 86.7)及び
点I(22.6, 76.4, 1.0)
の4点をそれぞれ結ぶ線分AB、BJ、JI及びIAで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BJ、及びIAは直線であり、かつ
線分JI上の点は、(x, -0.1609x2+12.934x-133.76, 0.1609x2-13.934x+233.76)で表わされる、
請求項1に記載の組成物。 - 前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点A(72.0, 27.0, 1.0)、
点B(72.0, 1.0, 27.0)、
点H’(31.3, 1.0, 67.7)及び
点G’(44.1, 54.9, 1.0)
の4点をそれぞれ結ぶ線分AB、BH’、H’G’及びG’Aで囲まれる図形の範囲内又は前記線分上にあり、
線分AB、BH’、及びG’Aは直線であり、かつ
線分H’G’上の点は、(x, -0.08728x2+10.791x-251.26, 0.08728x2-11.791x+351.26)で表わされる、
請求項1に記載の組成物。 - 前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点H(2.1, 1.0, 96.9)及び
点G(14.4, 84.6, 1.0)
の4点をそれぞれ結ぶ線分CD、DH、HG及びGCで囲まれる図形の範囲内又は前記線分上にあり、
線分DH及びGCは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分HG上の点は、(x, -0.1974x2+10.054x-19.242 , 0.1974x2-11.054x+119.242 )で表わされる、
請求項1に記載の組成物。 - 前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点C(38.7, 60.3, 1.0)、
点D(52.4, 1.0, 46.6)、
点J(12.3, 1.0, 86.7)及び
点I(22.6, 76.4, 1.0)
の4点をそれぞれ結ぶ線分CD、DJ、JI及びICで囲まれる図形の範囲内又は前記線分上にあり、
線分DJ及びICは直線であり、かつ
線分CD上の点は、(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分JI上の点は、(x, -0.1609x2+12.934x-133.76, 0.1609x2-13.934x+233.76)で表わされる、
請求項1に記載の組成物。 - 前記冷媒において、HFO-1132(E)、R1234ze及びR1234yfの、これらの総和を基準とする質量%をそれぞれx、y及びzとするとき、HFO-1132(E)、R1234ze及びR1234yの総和が100質量%となる3成分組成図において、座標(x,y,z)が、
点P(41.95, 47.8, 10.25)、
点D(52.4, 1.0, 46.6)及び
点H’(31.3, 1.0, 67.7)
の3点をそれぞれ結ぶ線分PD、DH’及びH’Pで囲まれる図形の範囲内又は前記直線上にあり、
線分DH’は直線であり、
線分PD上の点は(x, -0.0455x2-0.1834x+135.54, 0.0455x2-0.8166x-35.54)で表わされ、かつ
線分H’P上の点は(x, -0.08728x2+10.791x-251.26, 0.08728x2-11.791x+351.26)で表わされる、
請求項1に記載の組成物。 - さらに、冷凍機油を含有する、請求項1~9のいずれか一項に記載の組成物。
- R404Aの代替冷媒として用いられる、請求項1~10のいずれか一項に記載の組成物。
- 請求項1~10のいずれか一項に記載の組成物を作動流体として含む、冷凍機。
- 冷凍機の運転方法であって、
請求項1~10のいずれか一項に記載の組成物を作動流体として冷凍機において循環させる工程を含む、方法。 - R410Aの代替冷媒としての、請求項1~10のいずれ一項に記載の組成物の使用。
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MCLINDEN MARK O.; KAZAKOV ANDREI F.; STEVEN BROWN J.; DOMANSKI PIOTR A.: "A thermodynamic analysis of refrigerants: Possibilities and tradeoffs for Low-GWP refrigerants", INTERNATIONAL JOURNAL OF REFRIGERATION, ELSEVIER, AMSTERDAM, NL, vol. 38, 26 October 2013 (2013-10-26), AMSTERDAM, NL , pages 80 - 92, XP028612602, ISSN: 0140-7007, DOI: 10.1016/j.ijrefrig.2013.09.032 * |
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