JP5987497B2 - Heat transfer working medium containing fluorinated ether - Google Patents

Description

  The present invention relates to a heat transfer working medium containing fluorinated ether as a main component and a method of using the same.

  The Kyoto Protocol, which regulates greenhouse gas emissions such as carbon dioxide, methane, dinitrogen monoxide, and chlorofluorocarbon alternatives, has come into effect, and greenhouse gas emissions are currently restricted. For this reason, the development of waste heat power generation by utilizing unused energy to suppress greenhouse gases has become an important issue. Waste heat generated from various industries such as steel, petroleum, chemicals, cement, pulp and paper, ceramics, and biomass, or waste heat from gas turbines, engines and other prime movers, and low temperature waste gas and hot water waste heat are sufficient today It is hard to say that is being used.

  In general, an organic Rankine cycle (ORC) using an organic compound as a working medium is a closed Rankine cycle that does not discharge the working medium to the outside, and an evaporator that vaporizes the working medium, a generator, an expander, a condenser, and a recirculation Consists of a pump and the like. The Rankine cycle rotates through four processes of adiabatic compression, constant pressure heating (evaporation), adiabatic expansion, and constant pressure cooling (condensation) in the pump. In the constant pressure heating process, heat exchange with an external heat source is performed, the vaporized working medium is carried to the expander, adiabatically expanded, energy (work) is given to the outside, and taken out as electric energy or the like.

  Conventionally, water has been used as a working medium for Rankine cycle and has been put into practical use for a long time (for example, Patent Document 1). However, since water has a high freezing point of 0 ° C and a large specific volume of steam, when using a heat source with a relatively low operating temperature range (about 200 ° C or less), the equipment becomes large and the cycle efficiency is high. Has the disadvantage of lowering.

  Against this background, various studies have been made on organic Rankine cycle (ORC) using an organic compound having a boiling point lower than that of water as a working medium as a low-temperature exothermic technique. A technique using an organic fluorine compound has been proposed.

For example, Patent Document 2 discloses the use of fluorinated ketones such as CF ₃ CF ₂ (CO) CF (CF ₃ ) ₂ as a working medium. Patent Document 3 discloses 4-trifluoromethyl-1,1,1,3,5,5,5-heptafluoro-2-2 as a working medium of an organic Rankine cycle system that uses waste heat from a fuel cell. Organofluorine compounds containing pentene are disclosed.

In Patent Document 4, a working medium in which 1,1,2,2-tetrafluoro-2,2,2-trifluoroethyl ether is used as a main component and alcohol having 1 to 4 carbon atoms is mixed is used for Rankine cycle or the like. It is disclosed. Patent Document 5 discloses that HFCs such as C ₄ F ₉ C ₂ H ₅ are used as a heat medium for heat cycle such as Rankine cycle.

  Patent Document 6 discloses an organic Rankine cycle using fluoroolefins such as 1-chloro-3,3,3-trifluoropropene and monochlorononafluoropentene as a working medium.

  Compounds containing fluorine in the molecule have found widespread use as working media in many commercial and industrial applications besides ORC. The vapor compression cycle is one of the most commonly used methods for achieving cooling or heating in refrigeration equipment, air conditioning equipment, and hot water supply equipment.

  In general, a vapor compression cycle (also referred to as a vapor compression refrigeration cycle or a heat pump cycle) is a closed cycle in which a working medium is not discharged to the outside, and an evaporator that vaporizes the working medium, and a compressor and an evaporator that increase the pressure of steam. Consists of a condenser that condenses the working medium under conditions of higher temperature and higher pressure, a throttle expander (sometimes called an expansion valve), and the like. The vapor compression cycle rotates through four processes: constant pressure heating (evaporation), adiabatic compression adiabatic expansion in the compressor, constant pressure cooling (condensation), and adiabatic expansion by the throttle expander.

  As the working medium for the vapor compression cycle, chlorofluorocarbon (CFC) or hydrochlorofluorocarbon (HCFC), which is a working medium containing fluorine and chlorine, has been used in the past, but it is used in stages from the viewpoint of protecting the ozone layer. Is being abolished. At present, as an alternative working fluid, hydrofluorocarbon (HFC) containing no chlorine is mainly used.

  However, HFC is concerned that it has a large global warming potential (GWP) and contributes significantly to global warming. For this reason, hydrofluoroolefin (HFO), which is a fluorine-containing unsaturated compound, has been proposed as an alternative working fluid as a working fluid having a low global warming potential.

  For example, Patent Document 7 discloses that a composition containing 2,3,3,3-tetrafluoropropene (HFO) and a polyalkylene glycol (PAG) lubricant is used as a working medium for an automobile air conditioner. .

  Further, in Patent Document 8, a mixed composition of tetrafluoropropene such as 2,3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene and difluoromethane is used as a working fluid for a low-temperature refrigerator. It is disclosed to be used as In Patent Document 9 or 10, a composition containing trans-1,3,3,3-tetrafluoropropene is used as a working fluid for an air conditioning system as a first component of a ternary working fluid. Is disclosed.

  Further, in Patent Document 8, a mixed composition of tetrafluoropropene such as 2,3,3,3-tetrafluoropropene or 1,3,3,3-tetrafluoropropene and difluoromethane is used as a working fluid for a low-temperature refrigerator. It is disclosed to be used as In Patent Document 9 or 10, a composition containing trans-1,3,3,3-tetrafluoropropene is used as a working fluid for an air conditioning system as a first component of a ternary working fluid. Is disclosed.

  A boiling-cooling type heat exchanger that cools semiconductor elements, electronic devices, and the like by using latent heat of vaporization of a working medium enclosed in a heat exchanger such as a heat pipe is known.

  A heat pipe is a heat transfer element that transfers heat using one end of a pipe-shaped container as an evaporation section and the other end as a condensation section. In principle, when one end of the pipe is warmed, the working medium evaporates and absorbs heat. Next, the vaporized gas diffuses in the pipe and releases latent heat at the other end, which becomes a low temperature portion, to condense. The working medium (liquid) returns to one end which becomes the high temperature portion of the pipe again by gravity or capillary force, and heat is transported from the high temperature portion to the low temperature portion.

  Hydrocarbon working media that have a low environmental impact, such as a low global warming potential, are used for heat pipes without fear of ozone layer destruction. For example, Patent Document 11 discloses the use of hydrocarbons such as n-pentane as a working medium for an aluminum heat pipe.

  As other alternative working media, various studies have been made on using HFC or HFE (hydrofluoroether) -based compounds as working media for heat pipes. For example, Patent Document 12 includes 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (HFE- 347 pc-f), and the working ratio of HFC-134a and HFE-347pc-f in the working medium is HFE-347pc with respect to HFC-134a and 100 vol% at room temperature. A heat pipe in which -f is 0.5 to 1.5 vol% is disclosed.

  A boiling cooler is a pressure-resistant airtight container filled with a working medium inside, with one end of the container in contact with an object to be cooled such as a semiconductor and the other end as air or water. This is a heat exchanger that transfers heat using the part in contact with the fluid to be heated as a condensing part. In principle, when heat is applied to the evaporation part of the boiling cooler from a high-temperature heat source in contact with the boiling cooler, the working fluid inside the boiling cooler evaporates and absorbs heat. Next, the evaporated gas diffuses in the boiling cooler, releases the latent heat of condensation in the condensing part that dissipates heat to the heated fluid, and returns to the liquid. The working medium (liquid) returns to the evaporation part again by gravity or capillary force, and heat is transported from the high temperature part to the low temperature part.

  For example, Patent Document 13 discloses a boiling cooler for cooling a heating element such as a diode or a transistor with respect to a boiling cooler in which a fluorocarbon working medium is enclosed, although no specific working medium name is described. ing.

US Pat. No. 3,393,515 Special table 2007/52062 gazette Special table 2008/506919 International Publication No. 2007/105724 Pamphlet International Publication 2008/105410 Pamphlet US Patent No. 2010/0139274 A1 Special table 2007/553511 gazette JP 2010/47754 A JP2011 / 168781A JP 2011/256361 A JP 2001-55564 A JP 2010-65879 A JP 2003-197839 A

  In Patent Documents 1 to 6, for the purpose of heat recovery at a medium to low temperature of about 50 to 200 ° C., many organic Rankine cycle or heat pump cycle working media have been proposed so far. From the viewpoint of performance, such as load and thermal cycle characteristics (power generation cycle efficiency), it is not yet sufficient from the viewpoint of performance, and further improvement in performance is desired.

  Moreover, as a working medium for a heat cycle currently used for a working medium for an organic Rankine cycle, for example, 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3- Examples of the working medium include pentafluoropropane (HFC-245fa) and 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123). However, since these compounds have a very large global warming potential or have a large environmental load from the viewpoint of ozone layer destruction, there is a concern that they will be used permanently in the future.

  In Patent Documents 7 to 10, air conditioners using a vapor compression cycle using a low GWP working fluid have been proposed, both of which are working media suitable for air conditioning applications (cooling, heating), but for hot water supply or steam generation. There is no description of an application example to the heat pump cycle, and it is difficult to say that the working medium is suitable for these uses.

  Patent Document 11 proposes a heat pipe using a low GWP hydrocarbon as a working medium. However, the illustrated working medium n-pentane has a very low flash point of −49 ° C. and has a flammability. strong. Further, in Patent Document 12, a heat pipe using a mixed composition of HFC-134a and HFE-347pc-f as a working fluid has been proposed and is a non-flammable working medium. There are concerns about using it.

  In Patent Document 13, a boiling cooler using fluorocarbon as a working medium is proposed, but a specific example of the working medium is not given.

  An object of the present invention is to provide a novel heat transfer working medium that is nonflammable or slightly flammable, has a low environmental load, and has further improved heat cycle characteristics and heat transfer characteristics.

[Invention 1]
That is, the present invention is a heat transfer working medium containing a fluorinated ether having 2 to 6 carbon atoms.

[Invention 2]
Fluorinated ether
1,1,2,2-tetrafluoro-1-methoxyethane,
2-methoxy-1,1,1,3,3,3-hexafluoropropane,
1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether,
2,2,2-trifluoroethyl trifluoromethyl ether,
3H-hexafluoropropyl trifluoromethyl ether,
2,2,3,3,3-pentafluoropropyl trifluoromethyl ether,
Heptafluoro-1-methoxypropane,
1,2,2,2-tetrafluoroethyl methyl ether,
Heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether,
Difluoromethylpropyl-2,2,3,3,3-pentafluoropropyl ether,
1,1,2,3,3,3-hexafluoropropyldifluoromethyl ether,
Octafluoro-3-methoxypropene,
Trans-1-methoxy-3,3,3-trifluoropropene,
Cis-1-methoxy-3,3,3-trifluoropropene,
1,2-dichlorotrifluoroethyl trifluoromethyl ether,
2,2,3-trifluoro-4- (trifluoromethyl) -1,3-dioxole,
1,3,3,4,4-pentafluoro-2-methoxycyclobutene 1,1,3,3-tetrafluorodimethyl ether,
Pentafluoroethyl methyl ether,
1,2,2,2-tetrafluoroethyl difluoromethyl ether,
2,2-difluoroethyl trifluoromethyl ether,
Pentafluoroethyl-2,2,2-trifluoroethyl ether,
Difluoromethyl-2,2,2-trifluoroethyl ether,
Heptafluoroisopropyl methyl ether,
Pentafluoroethyl ethyl ether,
Ethyl trifluoromethyl ether,
2,2,2-trifluoroethyl methyl ether,
Bis (fluoromethyl) ether,
1,1-difluoroethyl methyl ether-2,2,2-trifluoroethyl ether,
2,2,3,3,3-pentafluoropropyl methyl ether,
t-butyl-1,1,2,2-tetrafluoroethyl ether,
2,2-difluoroethyl methyl ether,
n-butyl-1,1,2,2-tetrafluoroethyl ether,
Methyl hexafluoroisopropyl ether,
1,1,2,3,3,3-hexafluoropropyl methyl ether,
2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether,
1,1,1,2,3,3,3-heptafluoro-2- (fluoromethoxymethyl) -propane,
2-chloro-1,1,2-trifluoroethyl difluoromethyl ether,
1,2,2,2-tetrachloro-1-fluoroethyl methyl ether,
Pentafluoroethyl trifluorovinyl ether,
Heptafluoropropyl trifluorovinyl ether,
Ethyl trifluorovinyl ether,
2,2,3,3,3-pentafluoropropyl vinyl ether,
A heat transfer medium comprising at least one compound selected from the group consisting of 3,3,4,4-tetrafluoro-1,2-dimethoxycyclobutene.

[Invention 3]
Fluorinated ether
1,1,2,2-tetrafluoro-1-methoxyethane,
2-methoxy-1,1,1,3,3,3-hexafluoropropane,
1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether,
2,2,2-trifluoroethyl trifluoromethyl ether,
3H-hexafluoropropyl trifluoromethyl ether,
2,2,3,3,3-pentafluoropropyl trifluoromethyl ether,
Heptafluoro-1-methoxypropane,
1,2,2,2-tetrafluoroethyl methyl ether,
Heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether,
Difluoromethylpropyl-2,2,3,3,3-pentafluoropropyl ether,
1,1,2,3,3,3-hexafluoropropyldifluoromethyl ether,
Octafluoro-3-methoxypropene,
A heat transfer medium comprising at least one compound selected from the group consisting of trans-1-methoxy-3,3,3-trifluoropropene 2,2,3,3,3-pentafluoropropyl methyl ether.

[Invention 4]
Fluorinated ether
1,1,2,2-tetrafluoro-1-methoxyethane,
2-methoxy-1,1,1,3,3,3-hexafluoropropane,
1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether,
2,2,3,3,3-pentafluoropropyl trifluoromethyl ether,
Heptafluoro-1-methoxypropane at least one compound selected from the group consisting of trans-1-methoxy-3,3,3-trifluoropropene 2,2,3,3,3-pentafluoropropyl methyl ether Including heat transfer medium.

[Invention 5]
A heat transfer medium comprising at least 50% by mass or more of fluorinated ether.

[Invention 6]
further,
Trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)),
Cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)),
Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)), cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)),
2-Chloro-3,3,3-trifluoropropene (HCFO-1233xf)
A heat transfer medium comprising at least one compound selected from the group consisting of:

[Invention 7]
further,
Trans-1-bromo-3,3,3-trifluoropropene,
Cis-1-bromo-3,3,3-trifluoropropene,
2-bromo-3,3,3-trifluoropropene,
Trans-2-bromo-1,3,3,3-tetrafluoropropene,
Cis-2-bromo-1,3,3,3-tetrafluoropropene trans-1-chloro-pentafluoropropene,
Cis-1-chloro-pentafluoropropene,
Trans-1-chloro-1,3,3,3-tetrafluoropropene,
Cis-1-chloro-1,3,3,3-tetrafluoropropene,
Trans-1-chloro-2,3,3,3-tetrafluoropropene,
Cis-1-chloro-2,3,3,3-tetrafluoropropene,
Trans-2-chloro-1,3,3,3-tetrafluoropropene,
A heat transfer medium comprising at least one compound selected from the group consisting of cis-2-chloro-1,3,3,3-tetrafluoropropene.

[Invention 8]
further,
1-chloro-3,3,3-trifluoro-2-methylpropene,
1-chloro-3,3,3-trifluoro-2- (trifluoromethyl) propene,
Trans-2-chloro-1,1,1,3,3,3-hexafluoro-2-butene,
Cis-2-chloro-1,1,1,3,3,3-hexafluoro-2-butene,
Trans-2-chloro-heptafluoro-2-butene,
Cis-2-chloro-heptafluoro-2-butene,
Trans-1-chloro-2-fluoroethylene,
Cis-1-chloro-2-fluoroethylene,
1,1-dichloro-2,2-difluoroethylene,
1,2-dichloro-1,2-difluoroethylene,
1,2-dichloro-1-fluoroethylene,
1,1-dichloro-2-fluoroethylene,
Trans-1-chloro-2-fluoropropene,
3-chloro-2-fluoropropene,
2-chloro-3,3,3-trifluoropropene,
2-chloro-3-fluoropropene,
Trans-1,2-dichloro-3,3,3-trifluoropropene,
Cis-1,2-dichloro-3,3,3-trifluoropropene,
Trans-1,2-dichloro-tetrafluoropropene,
Cis-1,2-dichloro-tetrafluoropropene,
1,1-dichloro-tetrafluoropropene,
Trans-1-chloro-pentafluoropropene,
Cis-1-chloro-pentafluoropropene,
2-chloro-pentafluoropropene,
3-chloro-pentafluoropropene,
Trans-1,3-dichloro-3,3-difluoropropene,
Cis-1,3-dichloro-3,3-difluoropropene,
A heat transfer medium comprising at least one compound selected from the group consisting of:

[Invention 9]
further,
1,1-difluoro-2-vinylcyclopropane,
Perfluorocyclohexene,
A heat transfer medium comprising at least one compound selected from the group consisting of:

[Invention 10]
further,
3,3,3-trifluoropropyne,
1-chloro-3,3,3-trifluoropropyne,
1-bromo-3,3,3-trifluoropropyne,
1,1,1-trifluoro-2-butyne,
3,3,4,4,5,5,5-heptafluoropentyne,
3,4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butyne,
A heat transfer medium comprising at least one compound selected from the group consisting of:

[Invention 11]
further,
Difluoromethane (HFC-32),
1,1,1,2,2-pentafluoroethane (HFC-125),
1,1,1,2-tetrafluoroethane (HFC-134a),
1,1-difluoroethane (HFC-152a),
1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea),
1,1,1,3,3,3-hexafluoropropane (HFC-236fa),
1,1,1,3,3-pentafluoropropane (HFC-245fa),
1,1,1,2,3-pentafluoropropane (HFC-245eb),
1,1,2,2,3-pentafluoropropane (HFC-245ca),
1,1,1,3,3-pentafluorobutane (HFC-365mfc),
1,1,1,3,3,3-hexafluoroisobutane (HFC-356 mmz),
1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-43-10-mee)
A heat transfer medium comprising at least one compound selected from the group consisting of:

[Invention 12]
Furthermore, the heat transfer medium which contains 5-50 mass% of C3-C8 saturated hydrocarbons in a heat transfer medium.

[Invention 13]
The saturated hydrocarbon is selected from the group consisting of butane, isobutane, neopentane, n-pentane, i-pentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, and cyclooctane. A heat transfer medium which is at least one compound.

[Invention 14]
Furthermore, the heat transfer medium which contains 5 mass%-50 mass% of C1-C4 alcohol in a working medium.

[Invention 15]
Furthermore, the heat transfer medium containing 10 mass% or less of water.

[Invention 16]
The heat transfer medium according to any one of claims 1 to 15, further comprising 10% by mass or less of carbon dioxide.

[Invention 17]
A heat transfer medium comprising 50% by mass to 99% by mass of 1,1,2,2-tetrafluoro-1-methoxyethane and 1% by mass to 50% by mass of HFO-1234ze (Z).

[Invention 18]
A heat transfer medium comprising 50% by mass to 99% by mass of 2-methoxy-1,1,1,3,3,3-hexafluoropropane and 1% by mass to 50% by mass of HFO-1234ze (Z).

[Invention 19]
A heat transfer medium comprising 50% by mass to 99% by mass of octafluoro-3-methoxypropene and 1% by mass to 50% by mass of HFO-1234ze (Z).

[Invention 20]
A heat transfer medium comprising 50% by mass to 99% by mass of 3H-hexafluoropropyl trifluoromethyl ether and 1% by mass to 50% by mass of HCFO-1233zd (E).

[Invention 21]
A heat transfer medium comprising 50% by mass to 99% by mass of heptafluoro-1-methoxypropane and 1% by mass to 50% by mass of HCFO-1233zd (Z).

[Invention 22]
A heat transfer medium comprising 50% by mass to 99% by mass of 1,2,2,2-tetrafluoroethyl methyl ether and 1% by mass to 50% by mass of HCFO-1233zd (Z).

[Invention 23]
A heat transfer medium comprising 50% by mass to 99% by mass of heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether and 1% by mass to 50% by mass of HCFO-1233zd (Z).

[Invention 24]
A heat transfer medium further comprising a lubricant.

[Invention 25]
The lubricant is a mineral oil (paraffinic oil or naphthenic oil) or a synthetic oil alkylbenzene (AB), poly (alpha-olefin), ester, polyol ester (POE), polyalkylene glycol (PAG), A heat transfer medium selected from polyvinyl ethers (PVE) and combinations thereof.

[Invention 26]
A heat transfer medium further comprising a stabilizer.

[Invention 27]
A heat transfer medium wherein the stabilizer is selected from nitro compounds, epoxy compounds, phenols, imidazoles, amines, diene compounds, phosphates and the like and combinations thereof.

[Invention 28]
A heat transfer medium further comprising a flame retardant.

[Invention 29]
A heat transfer medium wherein the flame retardant is selected from phosphates, halogenated aromatics, fluorinated iodocarbons, fluorinated bromocarbons and the like and combinations thereof.

[Invention 30]
A heat transfer device containing the heat transfer medium described above.

[Invention 31]
Use of a heat transfer medium in a heat transfer device.

[Invention 32]
A heat transfer device configured to generate power from heat using a Rankine cycle or a variation thereof.

[Invention 33]
A heat transfer device that utilizes industrial waste heat when generating power using the Rankine cycle or variations thereof.

[Invention 34]
A heat transfer device that is a cooling device.

[Invention 35]
A heat transfer device selected from the group consisting of a commercial air conditioning system, a commercial refrigerator system, and a commercial freezer system.

[Invention 36]
A heat transfer device that is a boiling cooling system.

[Invention 37]
A heat transfer device which is a power control unit cooling system or CPU cooling system for automobiles.

[Invention 38]
A heat transfer device that is a heating device.

[Invention 39]
A heat transfer device that generates water of 60 ° C. or higher using a heat pump cycle or a modified method thereof.

[Invention 40]
A heat transfer device that generates water vapor at 100 ° C. or higher using a heat pump cycle or a modified method thereof.

[Invention 41]
An absorption heat pump system containing the heat transfer medium described above.

[Invention 42]
An absorption heat pump system, wherein the absorbent is a compound comprising at least one selected from the group consisting of ethers, esters, polyols, amides, amines, imides, ketones, aldehydes, and nitriles.

[Invention 43]
Absorbents are dimethyllaurylamine, N-methyldicyclohexylamine, quinoline, monoethanolamine, monoisopropanolamine, dimethylformamide, dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, tetrahydro Furfuryl alcohol, diethylene glycol, ethyl acetoacetate, diethyl oxalate, dimethyl malonate, cyclohexanone, isophorone, acetonyl acetone, triethyl phosphate, tributyl phosphate, boric acid triglycol ether ester, n-heptaldehyde, 1,3-dimethyl Selected from the group consisting of -2-imidazolidone and 1,3-dipropyl-2-imidazolidone Without even a compound consisting of one, the absorption heat pump system.

  According to the heat transfer medium of the present invention, it is possible to provide a working medium that is nonflammable or slightly flammable, has a small influence on the environment, and is excellent in heat transfer characteristics. Preferred working media of the present invention do not contribute substantially to global warming compared to many currently used hydrofluoroalkanes.

It is the schematic of the organic Rankine cycle which can apply the working medium which concerns on this invention. It is the cycle diagram which described the state change of the working medium in a Rankine cycle on the pressure-specific enthalpy diagram (Ph diagram). It is the schematic of the heat pump cycle which can apply the working medium which concerns on this invention. It is the cycle diagram which described the state change of the working medium in a vapor compression cycle on a pressure-specific enthalpy diagram (Ph diagram). It is a Ts diagram in Example 1 of the present invention. It is a Ph diagram in Example 1 of the present invention. It is a Ts diagram in Example 2 of the present invention. It is a Ph diagram in Example 2 of the present invention. It is a Ts diagram in Example 3 of the present invention. It is a Ph diagram in Example 3 of the present invention. It is a Ts diagram in Example 4 of the present invention. It is a Ph diagram in Example 4 of the present invention. It is a Ts diagram in Example 5 of this invention. It is a Ph diagram in Example 5 of the present invention. It is a Ts diagram in comparative example 1 of the present invention. It is a Ph diagram in comparative example 1 of the present invention. It is a Ts diagram in comparative example 2 of the present invention. It is a Ph diagram in comparative example 2 of the present invention. It is a Ph diagram in Example 6 of the present invention. It is a Ph diagram in Example 7 of the present invention. It is a Ph diagram in Example 8 of the present invention. It is a Ph diagram in Example 9 of the present invention. It is a Ph diagram in Example 10 of the present invention. It is a Ph diagram in comparative example 3 of the present invention. It is a Ph diagram in comparative example 4 of the present invention. It is the schematic of the experimental apparatus used for Examples 9, 10 and Comparative Example 5.

  The “heat transfer medium” in the present invention contains a specific fluorinated ether, and includes not only the fluorinated ether alone but also additives such as a lubricant, a stabilizer, a flame retardant and the like which are added as necessary. It also means including. In the present specification, the “heat transfer medium” may be appropriately referred to as a heat cycle working medium or simply a working medium.

  The heat transfer medium of the present invention is characterized by containing at least one or more of specific fluorinated ethers. Specifically, 1,1,2,2-tetrafluoro-1-methoxyethane, 2-methoxy-1,1,1,3,3,3-hexafluoropropane, 1,1,2,2-tetrafluoro Ethyl-2,2,2-trifluoroethyl ether, 2,2,2-trifluoroethyl trifluoromethyl ether, 3H-hexafluoropropyl trifluoromethyl ether, 2,2,3,3,3-pentafluoropropyl Trifluoromethyl ether, heptafluoro-1-methoxypropane, 1,2,2,2-tetrafluoroethyl methyl ether, heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether, difluoromethylpropyl-2, 2,3,3,3-pentafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl Difluoromethyl ether, octafluoro-3-methoxypropene, trans-1-methoxy-3,3,3-trifluoropropene, cis-1-methoxy-3,3,3-trifluoropropene, 1,2-dichlorotripene Fluoroethyl trifluoromethyl ether, 2,2,3-trifluoro-4- (trifluoromethyl) -1,3-dioxole, 1,3,3,4,4-pentafluoro-2-methoxycyclobutene 1, 1,3,3-tetrafluorodimethyl ether, pentafluoroethyl methyl ether, 1,2,2,2-tetrafluoroethyl difluoromethyl ether, 2,2-difluoroethyl trifluoromethyl ether, pentafluoroethyl-2,2, 2-trifluoroethyl ether, difluoromethyl-2,2,2-to Trifluoroethyl ether, heptafluoroisopropyl methyl ether, pentafluoroethyl ethyl ether, ethyl trifluoromethyl ether, 2,2,2-trifluoroethyl methyl ether, bis (fluoromethyl) ether, 1,1-difluoroethyl methyl ether -2,2,2-trifluoroethyl ether, 2,2,3,3,3-pentafluoropropyl methyl ether, t-butyl-1,1,2,2-tetrafluoroethyl ether, 2,2-difluoro Ethyl methyl ether, n-butyl-1,1,2,2-tetrafluoroethyl ether, methyl hexafluoroisopropyl ether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 2,2,2 -Trifluoroethyl-1,1,2,2-tetraf Oloethyl ether, 1,1,1,2,3,3,3-heptafluoro-2- (fluoromethoxymethyl) -propane, 2-chloro-1,1,2-trifluoroethyl difluoromethyl ether, 1, 2,2,2-tetrachloro-1-fluoroethyl methyl ether, pentafluoroethyl trifluorovinyl ether, heptafluoropropyl trifluorovinyl ether, ethyl trifluorovinyl ether, 2,2,3,3,3-pentafluoropropyl vinyl ether, 3,3,4,4-tetrafluoro-1,2-dimethoxycyclobutene can be mentioned. These compounds can be used alone or as a mixture of two or more.

Suitable fluorinated ethers include 1,1,2,2-tetrafluoro-1-methoxyethane (CF ₂ HCF ₂ OCH ₃ : boiling point 37 ° C.), 2-methoxy-1,1,1,3,3, 3-hexafluoropropane ((CF ₃ ) ₂ CHOCH ₃ : boiling point 50 ° C.), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF ₂ HCF ₂ OCH ₂ CF ₃ : Boiling point 56 ° C.) 2,2,2-trifluoroethyl trifluoromethyl ether (CF ₃ CH ₂ OCF ₃ : boiling point 5.6 ° C.), 3H-hexafluoropropyl trifluoromethyl ether (CHF ₂ CF ₂ CF ₂ OCF _3: boiling point 23-24 ° C.), 2,2,3,3,3-pentafluoro-propyl trifluoromethyl ether _{(CF 3 CF 2 CH 2 OCF} 3: boiling point 6.2 ° C.), heptafluoro-1-methoxy propane _{(CF 3 CF 2 CF 2 OCH} 3: boiling point 34.2 ° C.), 1,2,2,2-tetrafluoroethyl methyl ether _{(CF 3} CHFOCH 3: boiling point 38-39 ° C.), heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether (CF ₃ CF ₂ CF ₂ OCFCCF ₃ : boiling point 40-42 ° C.), difluoromethylpropyl-2,2,3,3 , 3-pentafluoropropyl ether (CF ₃ CF ₂ CH ₂ OCHF ₂ : boiling point 46 ° C.), 1,1,2,3,3,3-hexafluoropropyl difluoromethyl ether (CF ₃ CHFCF ₂ OCHF ₂ : boiling point 47 ° C.), 1,2-dichloro-trifluoroethyl trifluoromethyl ether _(CF 2 ClCFClOCF ₃ Boiling point 40-41 ° C.), octafluoro-3-methoxy propene _{(CF 2 = CFCF 2 OCF 3} : boiling point 9 to 10 ° C.), trans-1-methoxy-3,3,3-trifluoropropene (trans-CF ₃ CH = CHOCH ₃ : boiling point 61-63 ° C.), cis-1-methoxy-3,3,3-trifluoropropene (cis-CF ₃ CH═CHOCH ₃ : boiling point 102-104 ° C.), 2,2,3- Trifluoro-4- (trifluoromethyl) -1,3-dioxole (C ₄ HF ₆ O ₂ : boiling point 14-15 ° C.), 1,3,3,4,4-pentafluoro-2-methoxycyclobutene ( C ₅ H ₃ F ₅ O: boiling point 35 to 37 ° C.). These compounds can be used alone or as a mixture of two or more.

  These compounds are non-flammable or slightly flammable, have high reactivity with hydroxyl radicals, and have a short atmospheric lifetime. Therefore, the impact on global warming is extremely small, so the burden on the environment is small. In addition, any of the working media of the present invention has a higher critical temperature than HFC-134a and is advantageous as a heat transfer fluid. In addition, it is desirable that these compounds are contained in the working medium (100% by mass) at least 50% by mass or more, preferably 75% by mass or more, more preferably 90% by mass or more. If it is less than 50% by mass, the effects of the working medium of the present invention (stability of the working medium, thermal cycle performance, etc.) are hardly obtained, which is not preferable.

  In addition to the fluorinated ethers described above, the heat transfer medium of the present invention includes other fluorinated ethers, fluorinated alkenes, fluorinated alkynes, hydrofluorocarbons (HFCs), alcohols, saturated hydrocarbons, and the like. An additive compound may be contained. Hereinafter, other additive compounds will be described in detail. The amount of these compounds added is desirably 50% by mass or less, preferably 25% by mass or less, and more preferably 10% by mass or less so as not to impair the effect of the working medium of the present invention.

<Other additive compounds: fluorinated alkene, fluorinated alkyne>
Moreover, the following fluorinated alkene or fluorinated alkyne can be added to the working medium for heat cycle of the present invention. Specifically, trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)), trans -1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)), cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)), 2-chloro -3,3,3-trifluoropropene (HCFO-1233xf), trans-1-bromo-3,3,3-trifluoropropene, cis-1-bromo-3,3,3-trifluoropropene, 2- Bromo-3,3,3-trifluoropropene, trans-2-bromo-1,3,3,3-tetrafluoropropene, cis-2-bromo-1,3,3,3-teto Fluoropropene, trans-1-chloro-pentafluoropropene, cis-1-chloro-pentafluoropropene, trans-1-chloro-1,3,3,3-tetrafluoropropene, cis-1-chloro-1,3 , 3,3-tetrafluoropropene, trans-1-chloro-2,3,3,3-tetrafluoropropene, cis-1-chloro-2,3,3,3-tetrafluoropropene, trans-2-chloro -1,3,3,3-tetrafluoropropene, cis-2-chloro-1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoro-2-methylpropene, 1 -Chloro-3,3,3-trifluoro-2- (trifluoromethyl) propene, trans-2-chloro-1,1,1,3,3,3-hexafluoro-2-butene, cis 2-chloro-1,1,1,3,3,3-hexafluoro-2-butene, trans-2-chloro-heptafluoro-2-butene, cis-2-chloro-heptafluoro-2-butene, trans -1-chloro-2-fluoroethylene, cis-1-chloro-2-fluoroethylene, 1,1-dichloro-2,2-difluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 1,2 -Dichloro-1-fluoroethylene, 1,1-dichloro-2-fluoroethylene, trans-1-chloro-2-fluoropropene, 3-chloro-2-fluoropropene, 2-chloro-3,3,3-tri Fluoropropene, 2-chloro-3-fluoropropene, trans-1,2-dichloro-3,3,3-trifluoropropene, cis-1,2-dichloro-3,3,3-trifluoropropene , Trans-1,2-dichloro-tetrafluoropropene, cis-1,2-dichloro-tetrafluoropropene, 1,1-dichloro-tetrafluoropropene, trans-1-chloro-pentafluoropropene, cis-1-chloro Pentafluoropropene, 2-chloro-pentafluoropropene, 3-chloro-pentafluoropropene, trans-1,3-dichloro-3,3-difluoropropene, cis-1,3-dichloro-3,3-difluoropropene 1,1-difluoro-2-vinylcyclopropane, perfluorocyclohexene, 3,3,3-trifluoropropyne, 1-chloro-3,3,3-trifluoropropyne, 1-bromo-3,3,3 -Trifluoropropyne, 1,1,1-trifluoro-2-butyne, 3,3,4,4,5,5,5-heptafluorope Chin, 3,4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butyne, particularly preferably, trans-1,3,3,3-tetrafluoropropene _(trans-CF 3 CH = CHF : Boiling point -19 ° C), cis-1,3,3,3-tetrafluoropropene (cis-CF ₃ CH = CHF: boiling point 9 ° C), trans-1-chloro-3,3,3-trifluoropropene ( trans-CF ₃ CH═CHCl: boiling point 19 ° C.), cis-1-chloro-3,3,3-trifluoropropene (cis-CF ₃ CH═CHCl: boiling point 39 ° C.), 2-chloro-3,3, 3-trifluoropropene (CF ₃ CCl═CH ₂ : boiling point 15 ° C.), trans-1,1,1,4,4,4-hexafluoro-2-butene (trans-CF ₃ CH═CHCF ₃ : boiling point 9) ℃) Cis-1,1,1,4,4,4-hexafluoro-2-butene _{(cis-CF 3 CH = CHCF} 3: boiling point 33 ° C.), trans -1,1,1,3- tetrafluoro-2- Butene (trans-CF ₃ CH = CFCH ₃ : boiling point 17 ° C.), cis-1,1,1,3-tetrafluoro-2-butene (cis-CF ₃ CH═CFCH ₃ : boiling point 49 ° C.), 1,1 , 2,3,3,4,4-heptafluoro-1-butene (CHF ₂ CF ₂ CF═CF ₂ : boiling point 21 ° C.), 3- (trifluoromethyl) -3,4,4,4-tetrafluoro -1-butene ((CF ₃ ) ₂
CFCH═CH ₂ : boiling point 23 ° C.), 2,4,4,4-tetrafluoro-1-butene (CF ₃ CH ₂ CF═CH ₂ : boiling point 30 ° C.), 3,3,3-trifluoro-2- (Trifluoromethyl) -1-propene ((CF ₃ ) ₂ CH═CH ₂ : boiling point 14 ° C.), trans-1,2-dichloro-3,3,3-trifluoropropene (trans-CF ₃ CCl═CHCl : Boiling point 60 ° C.), cis-1,2-dichloro-3,3,3-trifluoropropene (cis-CF ₃ CCl═CHCl: boiling point 53 ° C.), 1-chloro-pentafluoropropene (CF ₃ CF═CFCl) : Boiling point 8 ° C.), 2-chloro-3,3,3-trifluoropropene (CF ₃ CCl═CH ₂ : boiling point 15 ° C.), cis-1-chloro-2-fluoroethylene (CHF═CHCl: boiling point) 15 ° C.), 1,1-dichloro-2,2-difluoroethylene (CCl ₂ ═CF ₂ : boiling point 19 ° C.), 1-chloro-1,3,3,3-tetrafluoropropene (CF ₃ CH═CFCl: Boiling point 19-20 ° C.), 1,2-dichloro-1,2-difluoroethylene (CFCl═CFCl: boiling point 21-22 ° C.), 2-chloroheptafluoro-2-butene (CF ₃ CCl═CFCF ₃ : boiling point 32) ° C), cis-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (cis-CF ₃ CCl═CHCF ₃ : boiling point 34.5-35.5 ° C.), 1, 1-dichloro-2-fluoroethylene (CCl ₂ ═CHF: boiling point 37.3 ° C.), trans-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (trans-CF ₃₎ CCl = CHCF : Boiling point 41 to 42 ° C.), 1-chloro-3,3,3-trifluoro-2- (trifluoromethyl) propene _{((CF 3) 2 C =} CHCl: boiling point 43-54 ° C.), 1-chloro - 3,3,3-trifluoro-2-methylpropene (CF ₃ C (CH ₃ ) = CHCl: boiling point 46 ° C.) 1,1,2,3,3-pentafluoropropene, 1,1,1-tri Fluoro-2-butene, 2- (trifluoromethyl) propene, trans-1,1,1,3-tetrafluoro-2-butene, 2,4,4,4-tetrafluoro-1-butene, 3,3 , 4,4,4-pentafluoro-1-butene, trans-1,1,1,4,4,4-hexafluoro-2-butene, cis-1,1,1,4,4,4-hexa Fluoro-2-butene, 1,1,1,2,4,4,4-heptafluoro-2-butene, 1,1,2,3,3,4,4-heptaful Oro-1-butene, octafluoro-2-butene, trans-2H, 3H-octafluoro-2-pentene, cis-2H, 3H-octafluoro-2-pentene, 1,1,4,4,4-penta Fluoro-2- (trifluoromethyl) -1-butene, 3,3,4,4,5,5,5-heptafluoro-1-pentene, 3- (trifluoromethyl) -3,4,4,4 -Tetrafluoro-1-butene, 2H-nonafluoro-2-pentene, decafluoro-3-methyl-1-butene, 1H, 1H, 2H-nonafluoro-1-hexene, perfluoro-4-methyl-2-hexene, 1-chloro-3,3,3-trifluoro-2-methylpropene, 1-chloro-3,3,3-trifluoro-2- (trifluoromethyl) propene, trans-2-chloro-1,1, 1,3,3,3-hexafluo -2-butene, cis-2-chloro-1,1,1,3,3,3-hexafluoro-2-butene, trans-2-chloro-heptafluoro-2-butene, cis-2-chloro-hepta Fluoro-2-butene, trans-1-chloro-2-fluoroethylene, cis-1-chloro-2-fluoroethylene, 1,1-dichloro-2,2-difluoroethylene, 1,2-dichloro-1,2 -Difluoroethylene, 1,2-dichloro-1-fluoroethylene, 1,1-dichloro-2-fluoroethylene, trans-1-chloro-2-fluoropropene, 3-chloro-2-fluoropropene, 2-chloro- 3,3,3-trifluoropropene, 2-chloro-3-fluoropropene, trans-1,2-dichloro-3,3,3-trifluoropropene, cis-1,2-dichloro-3,3,3 Trifluoropropene, trans-1,2-dichloro-tetrafluoropropene, cis-1,2-dichloro-tetrafluoropropene, 1,1-dichloro-tetrafluoropropene, trans-1-chloro-pentafluoropropene, cis- 1-chloro-pentafluoropropene, 2-chloro-pentafluoropropene, 3-chloro-pentafluoropropene, trans-1,3-dichloro-3,3-difluoropropene, cis-1,3-dichloro-3,3 -Difluoropropene, 1,1-difluoro-2-vinylcyclopropane, perfluorocyclohexene can be mentioned. These compounds can be used alone or as a mixture of two or more.

<Other additive compounds: Hydrofluorocarbons>
As other halocarbons, methylene chloride containing halogen atoms, trichloroethylene, tetrachloroethylene, and hydrofluorocarbons include difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC- 125), fluoroethane (HFC-161), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1 -Trifluoroethane (HFC-143a), difluoroethane (HFC-152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,2,3- Pentafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,2,2,3-penta Fluoropropane (HFC-245ca), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,3,3,3-hexafluoroisobutane (HFC-356 mmz), 1, Examples thereof include 1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-43-10-mee).

<Alcohol>
Other compounds include methanol having 1 to 4 carbon atoms, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, 2,2,2-trifluoroethanol, pentafluoropropanol, tetrafluoro. Alcohols such as propanol and 1,1,1,3,3,3-hexafluoro-2-propanol can be included.

<Saturated hydrocarbon>
Other compounds include propane, n-butane, i-butane, neopentane, n-pentane, i-pentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, and n-heptane having 3 to 8 carbon atoms. , Cycloheptane, n-octane, cyclooctane and other saturated hydrocarbons can be mixed. Among these, neopentane, n-pentane, i-pentane, cyclopentane, methylcyclopentane, n-hexane and cyclohexane are particularly preferable. Since these saturated hydrocarbons have a low global warming potential, the global warming potential can be further reduced by adding them to the specific fluorinated olefin according to the present invention. In addition, since these saturated hydrocarbons are inexpensive and easily available, it is possible to reduce the cost of the working medium for heat cycle of the present invention.

<Other additive compounds>
In addition, other compounds may include water, carbon dioxide, ammonia, and dimethyl ether (DME).

<Lubricant>
In addition, when the heat transfer working medium of the present invention is used as a Rankine cycle working medium, the lubricating oil used in the expander sliding portion of the turbine or the like is mineral oil (paraffinic oil or naphthenic oil) or synthetic oil alkylbenzene. (AB), poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols (PAG) or polyvinyl ethers (PVE) can be used.

  In addition, when the heat transfer working medium of the present invention is used as a working medium for a heat pump cycle, the lubricant used in the compressor sliding portion 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.

  Examples of alcohols used as starting materials for polyol esters include neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, and di- (penta). And esters of hindered alcohols such as erythritol and tri- (pentaerythritol).

  Examples of the carboxylic acid used as a raw material for the 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 C1-C18 methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, linear or Examples include compounds obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide, etc. to a branched aliphatic alcohol such as hexanol.

  Examples of polyvinyl ethers include polymethyl vinyl ether, polyethyl vinyl ether, poly n-propyl vinyl ether, polyisopropyl vinyl ether and the like.

<Stabilizer>
In addition, the heat transfer working medium of the present invention can use a stabilizer in order to improve thermal stability, oxidation resistance and the like. Examples of the stabilizer include nitro compounds, epoxy compounds, phenols, imidazoles, amines and the like.

  Examples of the nitro compound include known compounds, and examples thereof include aliphatic and / or aromatic derivatives. Examples of the aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. As 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.

  Examples of the phenols include phenols containing various substituents such as alkyl groups, alkenyl groups, alkoxy groups, carboxyl groups, carbonyl groups, and halogens in addition to the hydroxyl groups. For example, 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, p-t-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol , Eugenol, isoeugenol, butylhydroxyanisole, monovalent phenols such as phenol and xylenol, or divalent tert-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone, etc. Examples of phenol and the like.

  Examples of imidazoles include 1-methylimidazole, 1-n-butylimidazole, 1-methylimidazole, 1-methylimidazole, 1-n-butylimidazole having 1 to 18 carbon atoms, a linear or branched alkyl group, a cycloalkyl group, or an aryl group as the N-position substituent. Phenylimidazole, 1-benzylimidazole, 1- (β-oxyethyl) imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1,2- Examples include dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, 1-ethyl-2-methylimidazole, and the like. These compounds may be used alone or in combination.

  Examples of amines include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, α-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, tetraethyl Npentamin, benzylamine, dibenzylamine, diphenylamine, diethylhydroxylamine and the like. These may be used alone or in combination of two or more.

  Moreover, the stabilizer used for this invention may contain hydrocarbons, such as (alpha) -methylstyrene, p-isopropenyl toluene, isoprenes, propadiene, terpenes other than the said compound.

  The stabilizer may be added in advance to one or both of the working medium and the lubricant, or may be added alone in the condenser. At this time, although the usage-amount of a stabilizer is not specifically limited, 0.001-10 mass parts is preferable with respect to a main working medium (100 mass parts), 0.01-5 mass parts is more preferable, 0 0.02 to 2 parts by mass is more preferable. If the added amount of the stabilizer exceeds the upper limit value or less than the lower limit value, the stability of the working medium, the thermal cycle performance, etc. cannot be obtained sufficiently.

<Flame Retardant>
Further, the heat transfer working medium of the present invention can use a flame retardant to improve the combustibility. Examples of the flame retardant include phosphates, halogenated aromatic compounds, fluorinated iodocarbons, fluorinated bromocarbons, and the like.

  The heat transfer working medium of the present invention is nonflammable, has a low environmental load, and has excellent thermal cycle characteristics. Therefore, organic Rankine cycle working media used in power generation systems, vapor compression refrigeration cycle (heat pump) system working media, absorption heat pumps, heat pipes, etc., cooling systems or heat pump system cycle cleaning washing It can be used as an agent, a metal cleaning agent, a flux cleaning agent, a diluting solvent, a foaming agent, an aerosol and the like.

  The heat transfer working medium of the present invention can be applied not only to 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 there.

  Hereinafter, the Rankine cycle system using the heat transfer working medium of the present invention will be described in detail.

<Rankin cycle system>
Rankine cycle system is an evaporator that heats the working medium with geothermal energy, solar heat, medium to low temperature (about 30-300 ° C) waste heat, etc. In this system, the generator is driven by the work generated by the adiabatic expansion and the work generated by the adiabatic expansion is performed.

  FIG. 1 is a schematic view showing an example of an organic Rankine cycle system to which the working medium of the present invention can be applied. The configuration and operation (repetitive cycle) of Rankine cycle system 100 in FIG. 1 will be described below.

  The Rankine cycle system 100 of the present invention includes an evaporator 10 (boiler) that takes in heat and a condenser 11 (condenser) that distributes heat. The Rankine cycle system 100 further includes a power generation turbine 12 driven by a driving fluid that circulates through the system, and a pump 13 that increases the pressure of the liquid exiting the condenser 11 and consumes power. The generator 14 that generates electric power is driven by the power generation turbine 12.

  When the Rankine cycle is repeated using the working medium of the present invention, it can be taken out as electrical energy or the like through the following (a) to (e).

(A) In the heat exchanger (evaporator 10), the liquid working medium exchanges heat with waste heat and vaporizes.

(B) Remove the vaporized working medium from the heat exchanger.

(C) The vaporized working medium is passed through an expander (power generation turbine 12) and converted into mechanical (electrical) energy.

(D) The working medium discharged from the expander is passed through the condenser, and the gaseous working medium is condensed and liquefied.

(E) The liquefied working medium is recirculated to step (a) by a pump.

  The Rankine cycle is a cycle composed of an adiabatic change and an isobaric change. If the state change of the working medium is described on a pressure-specific enthalpy diagram (Ph diagram), it can be expressed as shown in FIG.

  The curve in FIG. 2 is a saturation curve. In FIG. 2, the transition from 1 to 2 is a process in which adiabatic expansion is performed by an expander such as a turbine, and work is generated by steam of a high-temperature and high-pressure working medium. That is, power is generated during the transition from 1 to 2. The transition from 2 to 3 is a process in which isobaric cooling is performed by a condenser, the working medium vapor (cycle point 2) in a low temperature and constant pressure state is condensed, and the working medium is liquefied. The transition from 3 to 4 is a process in which adiabatic compression is performed by a pump and the working medium is set to a high-pressure working medium (cycle point 4). The transition from 4 to 1 is a process in which isobaric heating is performed by an evaporator to convert a high-pressure working medium (cycle point 4) into a high-temperature and high-pressure working medium vapor (cycle point 1).

<Vapor compression cycle system>
In the vapor compression cycle system, the heat of an object to be cooled, such as air, water or brine, is transferred to the working medium as latent heat of vaporization of the working medium, and the generated refrigerant vapor is transferred to the air at a predetermined temperature in the compressor. If it is cooled with water, it is compressed by adding compression work to a pressure that easily condenses, exhausts the condensation heat with a condenser and liquefies, and the condensed working medium liquid is squeezed and expanded to low pressure and low temperature with an expansion valve, It is a system that sends it to the evaporator and evaporates it. In the evaporator, when the working medium receives the heat energy of the object to be cooled, the system cools the object to be cooled and lowers the temperature to a lower temperature, and can be applied to a known system. This is a system that heats the load fluid by applying thermal energy of the working medium to the load fluid in the condenser, and raises the temperature to a higher temperature, and can be applied to a known system.

  In the evaporator or condenser of the vapor compression cycle system, examples of the fluid to be cooled or the fluid to be heated that exchanges heat with the working medium include air, water, brine, and silicone oil. These are preferably selected and used according to the cycle operating temperature conditions.

  FIG. 3 is a schematic view showing an example of a vapor compression cycle system to which the working medium of the present invention can be applied. The configuration and operation (repetitive cycle) of the vapor compression cycle system 200 of FIG. 3 will be described below.

  The vapor compression cycle system 200 of the present invention includes an evaporator 10 that takes in heat and a condenser 12 that supplies heat. Further, the vapor compression cycle system 200 increases the pressure of the working medium vapor that has exited the evaporator 10 and consumes power, and the expansion valve 13 that squeezes and expands the working medium supercooled liquid that has exited the condenser 12. Have

  When the vapor compression cycle system is repeated using the working medium of the present invention, energy equal to or higher than the input power can be extracted as thermal energy in the condenser through the following (a) to (e).

(A) The working medium in a liquid state in the heat exchanger (evaporator 10) exchanges heat with the fluid to be cooled (air, water, etc.) and vaporizes.

(B) Remove the vaporized working medium from the heat exchanger.

(C) Pass the vaporized working medium through the compressor 11 and supply high-pressure superheated steam.

(D) The working medium discharged from the compressor is passed through the condenser, and the gaseous working medium exchanges heat with the fluid to be heated (air, water, etc.), and condenses and liquefies.

(E) The liquefied working medium is squeezed and expanded by an expansion valve, supplied with low-pressure wet steam, and recirculated to step (a).

  The vapor compression cycle system is a cycle composed of an adiabatic change and an isobaric change, and a state change of a working medium can be expressed as shown in FIG. 4 when described on a pressure-specific enthalpy diagram (Ph diagram). .

  The curve in FIG. 4 is a saturation curve. In FIG. 4, the transition from 1 to 2 is a process in which adiabatic compression is performed by a compressor to generate high-temperature and high-pressure working medium superheated steam. The transition from 2 to 3 is a process in which isobaric cooling is performed by the condenser, the working medium vapor (cycle point 2) in a high temperature and constant pressure state is condensed, and the working medium is liquefied. That is, heat energy is taken out to the superheated medium during the transition from 2 to 3. The transition from 3 to 4 is a process in which expansion expansion is performed by an expansion valve, and the working medium is changed to low-pressure wet steam (cycle point 4). The transition from 4 to 1 is a process in which isobaric heating is performed by an evaporator, and a low-pressure working medium (cycle point 4) is converted into a high-temperature and low-pressure working medium superheated steam (cycle point 1).

<Heat pipe>
A heat pipe is a heat transfer element that transfers heat using one end of a pipe-shaped container as an evaporation section and the other end as a condensation section. In principle, when one end of the pipe is warmed, the working medium evaporates and absorbs heat. Next, the vaporized gas diffuses in the pipe and releases latent heat at the other end, which becomes a low temperature portion, to condense. The working medium (liquid) returns to one end which becomes the high temperature portion of the pipe again by gravity or capillary force, and heat is transported from the high temperature portion to the low temperature portion. The working medium of the present invention can also be applied to a latent heat transport system such as a two-phase closed thermosyphon device having the same principle as a heat pipe. The driving force for circulating the working fluid in the heat pipe is not limited to gravity or capillary force, and mechanical work such as a pump may be used.

<Boiling cooler>
A boiling cooler is a pressure-resistant airtight container filled with a working medium inside, with one end of the container in contact with an object to be cooled such as a semiconductor and the other end as air or water. This is a heat exchanger that transfers heat using the part in contact with the fluid to be heated as a condensing part. In principle, when heat is applied to the evaporation part of the boiling cooler from a high-temperature heat source in contact with the boiling cooler, the working fluid inside the boiling cooler evaporates and absorbs heat. Next, the evaporated gas diffuses in the boiling cooler, releases the latent heat of condensation in the condensing part that dissipates heat to the heated fluid, and returns to the liquid. The working medium (liquid) returns to the evaporation part again by gravity or capillary force, and heat is transported from the high temperature part to the low temperature part. The driving force for circulating the working fluid in the boiling cooler is not limited to gravity or capillary force, and mechanical work such as a pump may be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the Example which concerns.

[Example 1]
<2-methoxy-1,1,1,3,3,3-hexafluoropropane: HFE-356 mmz>
In the organic Rankine cycle system 100 of FIG. 1, Rankine cycle performance (power generation cycle efficiency) when the 2-methoxy-1,1,1,3,3,3-hexafluoropropane of the present invention was applied was evaluated. 5 and 6 show a Ts diagram and a Ph diagram in Example 1. FIG. In FIG. 6, cycle points 1, 2, 3, and 4 indicate Rankine cycle calculation condition 1.

  Moreover, about evaluation, as shown in Table 1-Table 3, on Rankine cycle calculation conditions, the cycle structure apparatus efficiency was set to the expansion turbine 0.8, the circulation pump 0.6, and the generator 0.95. As evaluation conditions, condition 1: effective power generation amount 10 kW, evaporation temperature 77 ° C. (assuming heat source water 88 ° C.), condensing temperature 42 ° C. (assuming cooling water 32 ° C.), and condition 2: effective power generation amount 10 kW, Two conditions were used: an evaporation temperature of 140 ° C. (assuming heat source water or waste gas of 150 ° C.) and a condensation temperature of 42 ° C. (assuming cooling water of 32 ° C.). The physical property values of the working medium were obtained by using REFPROP ver.8.0 of National Institute of Standards and Technology (NIST) or by the physical property estimation method.

Below, it shows about Table 1-Table 3 which shows Rankine cycle calculation conditions.

  The following items were assumed in deriving the basic formula for calculating Rankine cycle performance (power generation cycle efficiency).

(A) The ideal expansion process of Rankine cycle is isentropic expansion, and expansion turbine insulation efficiency η _T is introduced in consideration of actual machine loss.

(B) The generator loss due to the expansion turbine is considered by the generator efficiency η _G.

(C) The circulation pump power is driven by power generation electricity, and pump efficiency η _P including motor efficiency is introduced.

      The pump is a can type and the loss is included in the cycle as heat.

(D) Ignored because the circulation pump power of bearing lubricant is very small.

(E) Ignore heat loss and pressure loss of piping.

(F) The working medium at the evaporator outlet is saturated steam.

(G) The working medium at the outlet of the condenser is a saturated liquid.

Hereinafter, the basic formula for calculating Rankine cycle performance (power generation cycle efficiency) will be described in detail. The basic formula is Ebara Times No. 211 (2006-4), p. The calculation formula of “Development of waste heat power generation equipment (examination of working medium and expansion turbine)” on page 11 was used. In FIG. 2, cycle point 1-2 is composed of an expansion turbine, cycle point 2-3 is composed of a condenser, cycle point 3-4 is composed of a circulation pump, and cycle point 4-1 is composed of a steam generator. In addition, the dotted line (cycle point 1-2 _Tth ) in a figure shows isentropic expansion.

In FIG. 2, the theoretically generated power L _Tth of the expansion turbine with the working medium circulation amount G and the generated power L _T considering the expansion turbine efficiency are

  It can be expressed.

The power generation amount E _G uses the generator efficiency,

  It becomes.

The circulation pump pumps the working medium liquid at the outlet of the condenser from the condenser pressure P _C to the high-pressure steam generator pressure P _E , and the required power E _P considering the theoretical required power L _pth and pump efficiency. Is

The effective power generation amount E _cycle is given by the following equation.

The heat input Q _E to the steam generator is

The efficiency of the power generation cycle is

It becomes.

  In addition, in said (1)-(8), various symbols mean the following.

G: Working medium circulation rate
L _th : Theoretical power of expansion turbine
Lt: Generated power
E _G : Power generation amount
E _P : Power required for circulation pump
Pc: Condenser pressure
P _E : Steam generator pressure
L _pth : Theoretical required power
_Ev : Required power
E _cycle : Effective power generation
Q _E : Heat input η _cycle : Power generation cycle efficiency ρ: Working medium density h: Specific enthalpy
_1,2,3,4 : Cycle point

[Example 2]
<1,1,2,2-tetrafluoro-1-methoxyethane: HFE-254pc>
The same conditions as in Example 1 except that 1,1,2,3-tetrafluoro-1-methoxyethane was used instead of 1,1,1,3,3,3-hexafluoro-2-methoxypropane. Then, Rankine cycle performance (power generation cycle efficiency) was evaluated. 7 and 8, a Ts diagram and a Ph diagram in Example 2 are shown. In FIG. 8, cycle points 1, 2, 3, and 4 indicate Rankine cycle calculation condition 1. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate Rankine cycle calculation condition 2.

[Example 3]
<Trans-1-methoxy-3,3,3-trifluoropropene: HFE-1363mzz (E)>
The same conditions as in Example 1 except that trans-1-methoxy-3,3,3-trifluoropropene was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. Then, Rankine cycle performance (power generation cycle efficiency) was evaluated. 9 and 10 show a Ts diagram and a Ph diagram in Example 3. FIG. In FIG. 10, cycle points 1, 2, 3, and 4 indicate Rankine cycle calculation condition 1. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate Rankine cycle calculation condition 2.

[Example 4]
<Heptafluoro-1-methoxypropane: HFE-347mcc>
Rankine cycle performance (power generation) under the same conditions as in Example 1 except that heptafluoro-1-methoxypropane was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. Cycle efficiency). 11 and 12 show a Ts diagram and a Ph diagram in Example 4. FIG. In FIG. 12, cycle points 1, 2, 3, and 4 indicate Rankine cycle calculation condition 1. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate Rankine cycle calculation condition 2.

[Example 5]
<2,2,3,3,3-pentafluoropropyl trifluoromethyl ether: HFE-338mcf>
Example 1 was used except that 2,2,3,3,3-pentafluoropropyl trifluoromethyl ether was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. The Rankine cycle performance (power generation cycle efficiency) was evaluated under the same conditions. 13 and 14 show a Ts diagram and a Ph diagram in Example 5. FIG. In FIG. 12, cycle points 1, 2, 3, and 4 indicate Rankine cycle calculation condition 1. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate Rankine cycle calculation condition 2.

[Comparative Example 1]
<1,1,1,2-tetrafluoroethane: HFC-134a>
Rankine was used under the same conditions as in Example 1 except that 1,1,1,2-tetrafluoroethane was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. The cycle performance (power generation cycle efficiency) was evaluated. 13 and 14 show a Ts diagram and a Ph diagram in Comparative Example 1. FIG. In FIG. 15, cycle points 1, 2, 3, and 4 indicate Rankine cycle calculation condition 1.

[Comparative Example 2]
<1,1,1,3,3-pentafluoropropane: HFC-245fa>
Under the same conditions as in Example 2 except that 1,1,1,3,3-pentafluoropropane was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. The Rankine cycle performance (power generation cycle efficiency) was evaluated. 15 and 16 show a Ts diagram and a Ph diagram in Comparative Example 2. FIG. In the figure, cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate Rankine cycle calculation condition 2.

Tables 4 and 5 show the comparison of the calculation results of Rankine cycle performance (power generation cycle efficiency) of Example 1 and Comparative Examples 1 and 2 for Conditions 1 and 2, respectively.

  From the cycle efficiencies of Examples 1 to 5 and Comparative Example 1 in Table 4, the working medium of the present invention has a larger cycle efficiency than the currently used HFC-134a, and is superior as a working medium for Rankine cycle. is there. The cycle efficiency increases as the temperature difference between the evaporation and condensation conditions increases.

  From the cycle efficiencies of Examples 1 to 4 and Comparative Example 2 in Table 5, the working medium of the present invention has a larger cycle efficiency than the currently used HFC-245fa, and is superior as a Rankine cycle working medium. is there. The cycle efficiency increases as the temperature difference between the evaporation and condensation conditions increases.

  From the results of Tables 4 and 5, when using a relatively low temperature heat source of 100 ° C. or lower, or when using a heat source of about 135 ° C., trans-1-methoxy-3,3,3-trifluoropropene is It is especially effective. The condensation temperature was set to 32 ° C., which is slightly higher than the cooling water temperature normally used in factories and the like, and the evaporation temperature was set at 88 ° C. and 135 ° C. assuming medium and low temperature exhaust heat.

  In addition, the working medium of the present invention can be used in currently used 1,1,1,2-tetrafluoroethane (HFC-134a) or 1,1,1,3,3-pentafluoropropane (HFC-245fa). In comparison, all have critical temperatures equal to or higher, and have good thermophysical properties as shown in the Ts diagrams (FIGS. 5, 7, 9 and 11). If an isentropic change is assumed, the amount of heat received during one cycle is the area surrounded by the cycle in the Ts diagram, and therefore, a higher critical temperature is advantageous.

  Further, in the Rankine cycle of Condition 1, 1,1,1,2-tetrafluoropropane (HFC-134a) currently used has a wetness because a part of the vapor is condensed at the outlet of the expander. On the other hand, all of the working medium of the present invention is superheated steam at the outlet of the expander. Considering the corrosion of the expander material and the like, the working medium at the outlet of the expander is preferably superheated steam. Therefore, the working medium of the present invention is advantageous also in this respect.

  Since the working medium of the present invention is nonflammable, has a small environmental load, and has excellent thermal cycle characteristics, it can be suitably used in a power generation system such as an organic Rankine cycle system. Therefore, it is possible to greatly contribute to the reduction of power consumption by excellent power generation efficiency. In addition, by selecting a more appropriate working medium from the working medium of the present invention according to the available high-temperature heat source temperature, it can be used for utilization of factory waste heat, etc. from low to mid-low temperatures that have not been fully utilized so far. You can see that

[Example 6]
<2-methoxy-1,1,1,3,3,3-hexafluoropropane: HFE-356 mmz>
The coefficient of performance (COP) is a generally accepted measure of working medium performance and represents the relative thermodynamic efficiency of the working medium in a particular heating or cooling cycle, including evaporation or condensation of the working medium. Especially useful. The ratio of the amount of heat that the working medium receives from the medium to be cooled in the evaporator to the amount of work applied by the compressor when compressing the steam is represented by COP _R. On the other hand, it represents the ratio working medium in the condenser for the amount of work added by the compressor in compressing the vapor of the heat releasing to the heated medium at COP _H.

  The volume capacity of the working medium represents the amount of cooling or heating provided by the working medium per unit suction volume of the compressor. That is, for a specific compressor, the larger the volume capacity of the working medium, the larger the amount of heat that the working medium can absorb or dissipate.

  In the performance evaluation of the heat pump cycle using 2-methoxy-1,1,1,3,3,3-hexafluoropropane as a working medium, the coefficient of performance was calculated under the conditions shown in Tables 6 to 8. The evaluation conditions are as follows: condition 3: evaporation temperature 25 ° C., condensation temperature 85 ° C. condition 4: evaporation temperature 70 ° C., condensation temperature 130 ° C., and condition 5: evaporation temperature 2 ° C., condensation temperature 40 ° C. did. The physical property values of the working medium were obtained by using REFPROP ver.8.0 of National Institute of Standards and Technology (NIST) or by the physical property estimation method.

Below, it shows about Table 6-Table 7 which shows heat pump cycle calculation conditions.

  Heat pump cycle condition 3 assumes hot water generation by heat exchange with heat source water in a condenser.

  The heat pump cycle condition 4 assumes steam generation by heat exchange with the heat source water in the condenser.

  Heat pump cycle condition 5 assumes cold water generation by heat exchange with heat source water in the evaporator.

  In calculating the heat pump cycle performance (COP), the following items were assumed.

(A) The compression process of the compressor is assumed to be isentropic compression.

(B) The throttle expansion process in the expansion valve is an isoenthalpy expansion.

(C) Ignores heat loss and pressure loss in piping and heat exchangers.

(D) The compressor efficiency η _{C is set} to 0.7.

Hereinafter, the formula for calculating the heat pump cycle performance (COP) will be described in detail. The amount of heat input Q _E to the evaporator is

, And the heat dissipation amount Q _C in the condenser,

It becomes.

However, when the working medium enthalpy at the compressor outlet after isentropic compression is represented by h _2th , the working medium enthalpy h _{2 at} the compressor outlet when considering the compressor efficiency is

It becomes.

The work W applied by the compressor when compressing the working medium vapor is

It becomes.

Heat pump cycle cooling performance (COP _R ) and heat pump cycle heating performance (COP _H )

It becomes.

  In addition, in said (9)-(14), various symbols mean the following.

G: Working medium circulation rate W: Compression work
Q _E : Heat input
Q _C : Heat dissipation COP _R : Performance coefficient (cooling)
COP _H : Performance coefficient (heating)
h: Specific enthalpy
_1,2,3,4 : Cycle point
_2th : Cycle points after isentropic compression In FIG. 19, the _Ph diagram in Example 6 is shown. In FIG. 19, cycle points 1, 2, 3, and 4 indicate heat pump cycle calculation condition 3. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate heat pump cycle calculation conditions 4, and cycle points 1 ″, 2 ′ ′, 3 ′ ′, 4 ′ ′ indicate heat pump cycle calculation conditions 5.

[Example 7]
<1,1,2,2-tetrafluoro-1-methoxyethane: HFE-254pc>
The same as Example 6 except that cis-1,1,1,3-tetrafluoro-2-butene was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. The heat pump cycle performance (COP) was evaluated under the conditions. In addition, in FIG. 20, the Ph diagram in Example 7 is shown. In FIG. 20, cycle points 1, 2, 3, and 4 indicate heat pump cycle calculation condition 3. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate heat pump cycle calculation conditions 4, and cycle points 1 ″, 2 ′ ′, 3 ′ ′, 4 ′ ′ indicate heat pump cycle calculation conditions 5.

[Example 8]
<Trans-1-methoxy-3,3,3-trifluoropropene: HFE-1363mzz (E)>
The same conditions as in Example 6 were used except that 2,4,4,4-tetrafluoro-1-butene was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. The heat pump cycle performance (COP) was evaluated. In addition, in FIG. 21, the Ph diagram in Example 8 is shown. In FIG. 21, cycle points 1, 2, 3, and 4 indicate heat pump cycle calculation condition 3. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate heat pump cycle calculation conditions 4, and cycle points 1 ″, 2 ′ ′, 3 ′ ′, 4 ′ ′ indicate heat pump cycle calculation conditions 5.

[Example 9]
<Heptafluoro-1-methoxypropane: HFE-347mcc>
Implemented except that trans-1,1,1,3,3,3-hexafluoro-2-butene was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane Under the same conditions as in Example 6, the heat pump cycle performance (COP) was evaluated. In addition, in FIG. 22, the Ph diagram in Example 9 is shown. In FIG. 22, cycle points 1, 2, 3, and 4 indicate heat pump cycle calculation condition 3. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate heat pump cycle calculation conditions 4, and cycle points 1 ″, 2 ′ ′, 3 ′ ′, 4 ′ ′ indicate heat pump cycle calculation conditions 5.

[Example 10]
<2,2,3,3,3-pentafluoropropyl trifluoromethyl ether: HFE-338mcf>
Implemented except that trans-1,1,1,3,3,3-hexafluoro-2-butene was used instead of 2-methoxy-1,1,1,3,3,3-hexafluoropropane Under the same conditions as in Example 6, the heat pump cycle performance (COP) was evaluated. In addition, in FIG. 20, the Ph diagram in Example 10 is shown. In FIG. 23, cycle points 1, 2, 3, and 4 indicate heat pump cycle calculation condition 3. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate heat pump cycle calculation conditions 4, and cycle points 1 ″, 2 ′ ′, 3 ′ ′, 4 ′ ′ indicate heat pump cycle calculation conditions 5.

[Comparative Example 3]
<1,1,1,2-tetrafluoroethane: HFC-134a>
The heat pump cycle performance (COP) was evaluated under the same conditions as in Example 5 except that 1,1,1,2-tetrafluoroethane was used instead of the working medium of the present invention. In addition, in FIG. 24, the Ph diagram in the comparative example 3 is shown. In FIG. 24, cycle points 1, 2, 3, and 4 indicate heat pump cycle calculation condition 3. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate heat pump cycle calculation conditions 4, and cycle points 1 ″, 2 ′ ′, 3 ′ ′, 4 ′ ′ indicate heat pump cycle calculation conditions 5.

[Comparative Example 4]
<1,1,1,3,3-pentafluoropropane: HFC-245fa>
The vapor compression cycle performance (COP) was evaluated under the same conditions as in Example 3 except that 1,1,1,3,3-pentafluoropropane was used instead of the working medium of the present invention. In addition, in FIG. 22, the Ts diagram and the Ph diagram in the comparative example 4 are shown. In FIG. 25, cycle points 1, 2, 3, and 4 indicate heat pump cycle calculation condition 3. Cycle points 1 ′, 2 ′, 3 ′, 4 ′ indicate heat pump cycle calculation conditions 4, and cycle points 1 ″, 2 ′ ′, 3 ′ ′, 4 ′ ′ indicate heat pump cycle calculation conditions 5.

Tables 9, 10 and 11 show the comparison results of the heat pump cycle performance (COP) of Examples 6 to 10 and Comparative Example 3 or 4 for Conditions 3, 4 and 5, respectively.

  From the relative COPs of Examples 6 to 10 and Comparative Examples 3 or 4 in Tables 9 to 11, the working medium of the present invention has a coefficient of performance larger than that of currently used HFC-134a or HFC-245fa, It is advantageous as a working medium for a vapor compression cycle.

  From the compressor outlet temperatures of Examples 6 to 10 and Comparative Examples 3 or 4 in Tables 9 to 11, the working medium of the present invention has a compressor outlet temperature higher than that of currently used HFC-134a or HFC-245fa. This is also advantageous from the viewpoint of maintainability of the heat pump cycle device.

  In addition, the working medium of the present invention has a critical temperature equal to or higher than that of the currently used HFC-134a or HFC-245fa, and has a Ts diagram (FIGS. 5, 7, 9, and 11). , FIG. 13) has good thermophysical properties.

  Since the working medium of the present invention is nonflammable, has a low environmental load, and has excellent thermal cycle characteristics, it can be suitably used in a heating or cooling system such as a heat pump cycle system. Therefore, it is possible to greatly contribute to the reduction of power consumption by an excellent coefficient of performance. Moreover, it turns out that it can utilize as high-grade warm water or water vapor | steam by heating the warm water of the mid-low temperature range which has not been fully utilized until now by the heat pump cycle using the working medium of this invention.

[Example 11]
2-Methoxy-1,1,1,3,3,3-hexafluoropropane in a container of a boiling cooler formed by a pipe-shaped SUS316 container having an outer diameter of 16 mm, a wall thickness of 1.0 mm, and a length of 800 mm Was sealed as a working medium.

  As shown in FIG. 26, a sheathed heater 19 is wound around a substantially half portion on one end side of the boiling cooler 300 and covered with a heat insulating material 23 to equalize the temperature, thereby forming an evaporation portion 27. In addition, a water cooling jacket 21 was attached to a substantially half portion on the other end side of the boiling cooler 300 so as to be spaced apart from each other in the length direction of the sheathed heater 19 and the boiling cooler 300 to form a condensing unit 28. The part between the evaporation part 27 and the condensation part 28 in the boiling cooler 300 is a heat insulation part.

  The evaporator 27 and the condenser 28 were provided with an evaporator thermometer 20 and a condenser thermometer 22, respectively, and the temperature was measured. In order to measure the pressure in the boiling cooler 300, the pressure gauge 26 was installed. In addition, the amount of heat input to the evaporation unit 27 was controlled by a slider.

  As shown in FIG. 26, the evaporating unit 27 is at the lower side, the condensing unit 28 is at the upper side, the boiling cooler 300 is installed vertically, and the evaporating unit 27 of the boiling cooler 300 is heated by the sheath heater, Cooling water (inlet temperature = 25 ° C., supply rate = 8.5 g / sec) was supplied and circulated to cool the condensing unit 40. Various changes were made to the input heat quantity (W) by the sheathed heater, and the relationship between the input heat quantity (W) and the hydraulic fluid thermal resistance (° C./W) in the boiling cooler 300 was determined. When the input heat quantity is in the range of 0 W to 300 W, the temperature of the corresponding working medium is approximately 20 to 70 ° C.

  Thermal resistance (° C./W) is defined as the temperature difference between two points divided by the amount of heat transfer. Since thermal resistance is an index that represents the difficulty of transferring heat between two points, when comparing the thermal resistance values of boiling coolers enclosing a certain working medium, the smaller the thermal resistance value, the better the cooling performance. From this point of view, it can be said that the performance is superior.

The thermal resistance _{RT of the} entire boiling cooler can be represented by the sum of the evaporation section thermal resistance R _E , the working medium thermal resistance R _WF , and the condensing section thermal resistance _RC . Various changes were made to the input heat quantity (W) by the sheathed heater, and the relationship between the input heat quantity (W) and the operating pressure in the boiling cooler was determined. Table 12 shows the relative thermal resistance value when the input heat quantity is 300 W, the working medium temperature and the working pressure in the evaporation section.

Evaporation portion thermal resistance R _E is an evaporation outer wall temperature was determined by dividing the input heat of the sheathed heater the difference between the working medium inside temperature in the evaporator section center. The working medium thermal resistance R _WF was obtained by dividing the difference between the working medium internal temperature at the center of the evaporator and the working medium internal temperature at the center of the condensing part by the input heat amount of the sheathed heater. Further, the condensation heat resistance _RC was obtained by dividing the difference between the working medium internal temperature at the center of the condensing part and the temperature of water at the center of the condensing part jacket by the input heat amount of the sheathed heater.

  Various input heat amounts (W) by the sheathed heater were changed, and the relationship between the input heat amount (W) and the operating pressure in the boiling cooler was determined. The results are shown in the figure.

[Example 12]
The conditions were the same as in Example 11 except that the working medium was 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.

[Comparative Example 5]
The conditions were the same as in Example 11 except that the working medium was 1,1,1,2-tetrafluoroethane.

From the results shown in Table 12, the working medium of the present invention has a thermal resistance value _RT as a boiling cooler system that is reduced by about 10 to 20% compared to 1,1,1,2-tetrafluoroethane. It can be seen that heat transfer is efficiently performed as a working medium of the boiling cooler.

  The results shown in Table 12 indicate that the working medium of the present invention has a working pressure that is reduced by about 90% compared to 1,1,1,2-tetrafluoroethane, and can be cooled at a lower working pressure. ing. Since the pressure resistance performance of the material constituting the boiling cooler needs to be equal to or higher than the working pressure of the working medium, cooling at a lower pressure can be said to be a preferable result from the viewpoint of economics of manufacturing the apparatus.

[Example 13]
A thermal stability test was conducted using 2-methoxy-1,1,1,3,3,3-hexafluoropropane. In accordance with the shield tube test of JIS-K-2211 “Refrigerator Oil”, the working medium 1. 0 g and metal pieces (iron, copper, and aluminum wires) were sealed in a glass test tube, heated to 175 ° C., and held for 2 weeks. The appearance, purity, and acid content (F ^- ion) of the working medium after 2 weeks were measured, and thermal stability was evaluated. The obtained results are shown in Table 13.

[Example 14]
The conditions were the same as in Example 11 except that the working medium was 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether.

    None of the working media showed any pyrolysis products. As is clear from the results shown in Table 13, it can be seen that the working medium of the present invention is excellent in thermal stability and excellent in compatibility with iron, copper and aluminum.

[Example 15]
0.5 g of working medium and 0.5 g of lubricating oil were sealed in a glass test tube. The glass test tube was cooled to 0 ° C., and the compatibility between the working medium and the lubricating oil was evaluated visually. The obtained results are shown in Table 14. In Table 14, when the solution was uniformly mixed, the evaluation was ○, and when the two layers were separated, the evaluation was ×.

  For the compatibility test, the following four types of working media were used.

1,1,2,2-tetrafluoro-1-methoxyethane (HFE-254pc),
2-methoxy-1,1,1,3,3,3-hexafluoropropane (HFE-356 mmz), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (HFE- 347 pc-f),
Trans-1-methoxy-3,3,3-trifluoropropene (HFE-1363mzz (E))
The following four types of lubricants were used for the compatibility test.

Mineral oil (MO1): Turbine oil (manufactured by JX Nippon Oil & Energy)
Mineral oil (MO2): Suniso 4GS (manufactured by Nippon San Oil)
Alkylbenzene oil (AB): Atmos 68N (manufactured by JX Nippon Oil & Energy)
Polyalkylene glycol oil (PAG): SUNICE P56 (Nihon Sun Oil Co., Ltd.)
Polyvinyl ether oil (PVE): Daphne Hermetic Oil FVC68D (manufactured by Idemitsu Kosan)
Polyol ester oil (POE): Ze-GLES RB68 (manufactured by JX Nippon Mining & Energy)

  All working media had good compatibility with the synthetic oils PAG, PVE and POE. From the results in Table 14, it can be seen that the working medium of the present invention can be applied with an existing lubricant developed for hydrofluorocarbons.

Claims (16)

In a heat transfer device, a method of using a heat transfer medium comprising only 2-methoxy-1,1,1,3,3,3-hexafluoropropane or trans-1-methoxy-3,3,3-trifluoropropene There,
The heat transfer device is a heat transfer device that generates water of 60 ° C. or higher or water vapor of 100 ° C. or higher using a heat pump cycle.
How to use heat transfer media. The method of claim 1, wherein the heat transfer medium consists solely of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. The method of claim 1 wherein the heat transfer medium consists solely of trans-1-methoxy-3,3,3-trifluoropropene. The heat transfer medium further comprises mineral oil (paraffinic or naphthenic oil) or synthetic oil alkylbenzenes (AB), poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols ( 4. A method according to any one of claims 1 to 3 comprising a lubricant selected from PAG), polyvinyl ethers (PVE) and combinations thereof. 4. The heat transfer medium according to claim 1, wherein the heat transfer medium further comprises a lubricant selected from polyol esters (POE), polyalkylene glycols (PAG) and polyvinyl ethers (PVE). 5. Method. The method according to any one of claims 1 to 5, wherein the heat pump cycle is operated at a condensation temperature of 85 to 130 ° C. A heat transfer medium consisting only of 2-methoxy-1,1,1,3,3,3-hexafluoropropane or trans-1-methoxy-3,3,3-trifluoropropene,
A heat transfer device that generates water of 60 ° C. or higher or water vapor of 100 ° C. or higher using a heat pump cycle. The heat transfer device according to claim 6, wherein the heat transfer medium is composed only of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. The heat transfer device according to claim 6, wherein the heat transfer medium is composed solely of trans-1-methoxy-3,3,3-trifluoropropene. The heat transfer medium further comprises mineral oil (paraffinic or naphthenic oil) or synthetic oil alkylbenzenes (AB), poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols ( A heat transfer device according to any of claims 6 to 8, comprising a lubricant selected from PAG), polyvinyl ethers (PVE) and combinations thereof. 9. The heat transfer medium according to any one of claims 6 to 8, wherein the heat transfer medium further comprises a lubricant selected from polyol esters (POE), polyalkylene glycols (PAG) and polyvinyl ethers (PVE). Heat transfer device. The heat transfer device according to any one of claims 6 to 10, wherein the heat pump cycle is operated at a condensation temperature of 85 to 130 ° C. A heat transfer medium for hot water supply of 60 ° C. or higher or water vapor generation of 100 ° C. or higher by a heat pump system, which is composed only of 2-methoxy-1,1,1,3,3,3-hexafluoropropane. A heat transfer medium for hot water supply of 60 ° C. or higher or water vapor generation of 100 ° C. or higher by a heat pump system, consisting of trans-1-methoxy-3,3,3-trifluoropropene alone. Further, alkylbenzenes (AB), poly (alpha-olefin), esters, polyol esters (POE), polyalkylene glycols (PAG), polyvinyl ethers of mineral oil (paraffinic oil or naphthenic oil) or synthetic oil 15. A heat transfer medium according to claim 13 or claim 14 comprising a lubricant selected from the class (PVE) and combinations thereof. The heat transfer medium according to claim 13 or 14, further comprising a lubricant selected from polyol esters (POE), polyalkylene glycols (PAG) and polyvinyl ethers (PVE).

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