WO2016104287A1

WO2016104287A1 - Heat transfer medium containing 2-chloro-1,3,3,3-tetrafluoropropene

Info

Publication number: WO2016104287A1
Application number: PCT/JP2015/085224
Authority: WO
Inventors: 祥雄西口; 昌彦谷; 井村　英明; 覚岡本; 高田　直門; 金井　正富
Original assignee: セントラル硝子株式会社
Priority date: 2014-12-24
Filing date: 2015-12-16
Publication date: 2016-06-30
Also published as: JP6435854B2; JP2016121248A

Abstract

Provided are the following: a heat transfer medium which contributes very little to ozone layer destruction or global warming, is non-combustible and can be used safely; a coolant cycle system, heat pump system or organic Rankine cycle system having heat cycle characteristics that are equivalent to, or better than, existing coolants; and a heat transfer method or method for converting heat energy into mechanical energy in a system that includes this heat transfer medium. Provided is the heat transfer medium characterized by containing 50 mass % or more of 2-chloro-1,3,3,3-tetrafluoropropene. Provided is the coolant cycle system, the heat pump system, and the organic Rankine cycle system which exhibit excellent heat cycle characteristics as a result of the heat transfer medium being housed.

Description

Heat transfer medium containing 2-chloro-1,3,3,3-tetrafluoropropene

The present invention relates to a heat transfer medium containing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), a refrigeration cycle system including the heat transfer medium, a heat pump system, an organic Rankine cycle, and the heat transfer. The present invention relates to a heat transfer method and a method for converting thermal energy into mechanical energy in a system containing a medium.

Chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC) have been used as refrigerants used in refrigeration cycle systems such as refrigerators. CFC and HCFC are positioned as ozone depleting substances because they contain chlorine atoms in their molecules and have a long atmospheric lifetime. The use of these refrigerants has been phased out in accordance with the Montreal Protocol guidelines.

Hydrohydrocarbon (HFC) has been developed as an alternative to CFC and HCFC. HFC does not correspond to ozone depleting substances because it does not contain chlorine atoms in its molecule. HFC is used not only as a refrigerant for a refrigeration cycle system but also as a refrigerant for a high-temperature heat pump system and a working medium for an organic Rankine cycle.

However, HFC has a long atmospheric lifetime, a high global warming potential (GWP), and a large contribution to global warming. In order not only to prevent ozone layer destruction but also to prevent global warming, the development of new refrigerants that can replace existing HCFC refrigerants and HFC refrigerants has been strongly desired.

Hydrofluoroolefin (HFO), which is a fluorine-containing unsaturated compound, and hydrochlorofluoroolefin (HCFO), which also contains chlorine, are alternative refrigerants that contribute substantially to the destruction of the ozone layer and are extremely low in GWP. Proposed. As representative examples of recently developed HFO refrigerants, 2,3,3,3-tetrafluoropropene (HFO-1234yf) or trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)) is available. A typical example of the HCFO refrigerant is trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)).

In applications such as refrigeration cycle systems, high-temperature heat pump cycle systems, or organic Rankine cycle systems, it is highly desirable that the refrigerant and the lubricating oil be compatible. Mineral oils, alkylbenzene oils and poly-α-olefin (PAO) oils that have been used with CFC or HCFC refrigerants are not compatible with HFC refrigerants and HFO refrigerants.

As lubricating oils compatible with HFC refrigerant and HFO refrigerant, lubricating oils containing oxygen such as polyol ester oil (POE), polyvinyl ether oil (PVE), polyalkylene glycol oil (PAG) have been developed. In general, oxygen-containing lubricating oils have the advantage of being compatible with many refrigerants, but have the disadvantages of being expensive and hygroscopic compared to hydrocarbon-based lubricating oils that do not contain oxygen. For this reason, compounds that are compatible with hydrocarbon-based lubricating oils that do not contain oxygen, such as mineral oil, are extremely useful as refrigerants because of their economic advantages and the ability to prevent decomposition and corrosion due to moisture. It can be said that it has favorable properties.

Also, in applications such as a refrigeration cycle system, a high temperature heat pump system, or an organic Rankine cycle system, it is highly desirable that the refrigerant be nonflammable. On the other hand, 2,3,3,3-tetrafluoropropene (HFO-1234yf) or trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), which are typical HFO refrigerants, are all used. Slightly flammable.

Patent Document 1 proposes 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) as a new working medium for heat cycle. HCFO-1224yd described in Patent Document 1 has a cis isomer or a trans isomer which is a geometric isomer, but a specific thermophysical value of each geometric isomer is not disclosed. Patent Document 1 describes that the thermal cycle characteristics of HCFO-1224yd have a performance that can replace the existing HFC refrigerant, which is a very important property when used as a working medium for thermal cycle. There is no disclosure regarding compatibility with lubricating oil, presence or absence of combustibility, thermal stability, and corrosiveness to metals.

Based on the above background, it is nonflammable, contributes very little to the destruction of the ozone layer and global warming, and is compatible with both oxygen-containing lubricants and hydrocarbon lubricants that do not contain oxygen. However, there is a need for a refrigerant that has good thermal stability, does not corrode metals, and has excellent thermal cycle characteristics that can replace existing refrigerants.

International Publication No. 2012/157773

The present invention relates to a heat transfer medium that has a very small contribution to ozone layer destruction and global warming, is nonflammable and can be used safely, a refrigeration cycle system having a heat cycle characteristic equal to or higher than that of an existing refrigerant, a heat pump system, and an organic It is an object of the present invention to provide a Rankine cycle system, a heat transfer method in a system including the heat transfer medium, and a method for converting thermal energy into mechanical energy.

The present inventors have intensively studied to solve the above problems. The present inventors focused on unsaturated halogenated hydrocarbons, and in particular, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) has a double bond in the molecule, so It has been found that the lifetime is shortened and the contribution to ozone layer destruction and global warming is extremely small. In addition, with the knowledge that 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is nonflammable and has excellent heat transfer characteristics when used as a heat transfer medium. The present invention has been completed.

2-Chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) has geometric isomers of cis form (HCFO-1224xe (Z)) and trans form (HCFO-1224xe (E)). Each of the isomers has an extremely small ozone depletion coefficient and a global warming coefficient, is nonflammable and has excellent heat transfer characteristics, and is suitable as a heat transfer medium. According to one embodiment of the present invention, as 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), cis isomer (HCFO-1224xe (Z)) or trans isomer (HCFO-1224xe (E) )) May be used. Also, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is used as a mixture of cis isomer (HCFO-1224xe (Z)) and trans isomer (HCFO-1224xe (E)). Also good.

According to one embodiment of the present invention, there is provided a heat conducting medium containing 50% by mass or more of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe).

According to an embodiment of the present invention, the heat transfer medium may include 50% by mass or more of cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)).

According to one embodiment of the present invention, the heat transfer medium is a mixture of cis- and trans-isomers of 2-chloro-1,3,3,3-tetrafluoropropene and the 2-chloro-1,3,3 In the mass ratio of the cis isomer to the trans isomer of 3,3-tetrafluoropropene, the mass ratio of the cis isomer is 50% by mass to 99.9% by mass, and the mass ratio of the trans isomer is 0.1% by mass to 50% by mass. % Or less.

According to an embodiment of the present invention, the heat transfer medium may include lubricating oil.

According to an embodiment of the present invention, the lubricating oil may be a mineral oil containing paraffinic oil or naphthenic oil, or alkylbenzenes (AB), poly-α-olefin (PAO), esters, polyols that are synthetic oils. It may be selected from esters (POE), polyalkylene glycols (PAG), polyvinyl ethers (PVE) and combinations thereof.

According to an embodiment of the present invention, the heat transfer medium may further include a stabilizer.

In the heat transfer medium, the stabilizer is a nitro compound, an epoxy compound, a phenol, an imidazole, an amine, a diene compound, a phosphate ester, an aromatic unsaturated hydrocarbon, an isoprene, a propadiene, It may be selected from terpenes and the like and combinations thereof.

According to one embodiment of the present invention, a refrigeration cycle system using any one of the heat transfer media described above is provided.

According to an embodiment of the present invention, there is provided a heat pump cycle system using any one of the heat transfer media described above.

According to one embodiment of the present invention, an organic Rankine cycle system using any one of the heat transfer media described above is provided.

According to an embodiment of the present invention, the method includes vaporizing the heat transfer medium according to any one of the above, compressing the heat transfer medium, condensing the heat transfer medium, and squeezing and expanding the heat transfer medium. A heat transfer method using a refrigeration cycle system or a heat pump system containing the heat transfer medium is provided.

According to an embodiment of the present invention, the heat transfer medium according to any one of the above is vaporized, the heat transfer medium is expanded, the heat transfer medium is condensed, and the heat transfer medium is pressurized and transferred by a pump. A method of converting thermal energy into mechanical energy using an organic Rankine cycle system containing the heat transfer medium.

According to one embodiment of the present invention, the heat transfer according to any one of the above, to a refrigeration cycle system or a high-temperature heat pump cycle system using a heat transfer medium containing 2,2-dichloro-1,1,1-trifluoroethane. A method for replacing a heat transfer medium in a refrigeration cycle system or a high temperature heat pump cycle system is provided.

According to one embodiment of the present invention, an organic Rankine cycle system using a heat transfer medium containing 2,2-dichloro-1,1,1-trifluoroethane is supplied with any of the foregoing heat transfer media A method for replacing a heat transfer medium in an organic Rankine cycle system is provided.

According to the heat transfer medium of the present invention, the heat transfer has small environmental impact, is nonflammable, has good thermal stability, does not corrode against metals, and has excellent heat transfer characteristics. A medium can be provided. Moreover, the refrigeration cycle system, heat pump system, and organic Rankine cycle system excellent in heat transfer characteristics can be provided by using the heat transfer medium of the present invention.

It is the schematic of the refrigerating cycle system or high temperature heat pump system which can apply the heat transfer medium which concerns on this invention. 1 is a schematic view of an organic Rankine cycle system to which a heat transfer medium according to the present invention can be applied. 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 Ph diagram in Example 10 of this invention. It is Ph diagram in the comparative example 2 of this invention. It is a Ph diagram in Example 11 of the present invention. It is a Ph diagram in Example 12 of the present invention. It is a Ph diagram in Example 13 of the present invention. It is Ph diagram in the comparative example 3 of this invention. It is a Ph diagram in Example 14 of the present invention. It is a Ph diagram in Example 15 of the present invention. It is a Ph diagram in Example 16 of the present invention. It is Ph diagram in the comparative example 4 of this invention. It is a Ts diagram in Example 17 of this invention. It is a Ts diagram in Example 18 of this invention. It is a Ts diagram in Example 19 of this invention. It is a Ts diagram in comparative example 5 of the present invention. It is a Ts diagram in Example 20 of this invention. It is a Ts diagram in Example 21 of this invention. It is a Ts diagram in Example 22 of this invention. It is a Ts diagram in comparative example 6 of the present invention. FIG. 3 is a diagram for explaining a process for producing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) from fluorine-containing olefins.

Before describing the details of the present invention described below, terms used in the following description will be described.

In this specification, “heat transfer medium” refers to a medium that exchanges heat with a medium to be cooled or a medium to be heated in a heat exchanger of a refrigeration cycle system, a high-temperature heat pump cycle system, or an organic Rankine cycle system. The heat transfer medium may be a single compound or a mixture. The heat transfer medium may be represented by other terms commonly understood by those skilled in the art to which the present invention belongs, for example, refrigerant, refrigerant composition, heat transfer composition, working fluid, working fluid composition, working Sometimes expressed as a medium.

In this specification, “non-combustible” means that the judgment is made according to the American version of the American Society for Testing and Materials (ASTM) standard E-681 and the 2010 version of the American Society of Heating, Air Conditioning and Air Conditioning Engineers (ASHRAE) standard 34-2010. Refers to the nature of a compound or composition that is determined to be non-flammable. In general, in many heat transfer applications, such as refrigeration cycle systems, it is preferable to use a non-flammable heat transfer medium.

In this specification, “compatibility” indicates the properties of a refrigerant and a lubricating oil that are determined to be compatible when determined in accordance with the 2009 edition of Japanese Industrial Standards JIS K2211 Annex D. In general, for many heat transfer applications such as refrigeration cycle systems, it is preferred that the refrigerant and the lubricating oil be compatible. Moreover, in this specification, lubricating oil may be represented as refrigeration oil.

In this specification, the “refrigeration cycle system” is a vapor compression type refrigeration cycle system including at least an evaporator, a compressor, a condenser, and an expansion valve as element devices, and is mainly intended for cooling. Refers to the system. The expansion valve is a device for expanding and contracting the heat transfer medium, and may be a capillary tube. The refrigeration cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery device, a non-condensable gas separator, and the like in addition to the element devices. The refrigeration cycle system may be used as a refrigerator, an air conditioning system, or a cooling device.

In this specification, the “high temperature heat pump cycle system” is a vapor compression heat pump cycle system including at least an evaporator, a compressor, a condenser, and an expansion valve as element devices, and is mainly intended for heating. Refers to a system that The expansion valve is a device for constricting and expanding the heat transfer medium, and may be a capillary tube. The high-temperature heat pump cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery device, a non-condensable gas separator, and the like in addition to the element devices. The high temperature heat pump cycle system may be used as a hot water supply system, a steam generation system, or a heating device. The high-temperature heat pump cycle system may use solar heat energy, factory waste heat, or the like as a heat source.

In this specification, the “organic Rankine cycle system” is a Rankine cycle system including at least an evaporator, an expander, a condenser, and a booster pump as component devices, and mainly converts thermal energy into electric energy. Refers to the target system. The organic Rankine cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery device, a non-condensable gas separator and the like in addition to the element devices. The organic Rankine cycle system may be used as a power generation device that recovers medium and low temperature heat. The organic Rankine cycle system may use solar heat energy, factory waste heat, or the like as a heat source.

Hereinafter, a refrigeration cycle system, a high-temperature heat pump system, and a heat transfer method according to the present invention will be described with reference to the drawings. However, the refrigeration cycle system, the high-temperature heat pump system, and the heat transfer method of the present invention are not construed as being limited to the description of the embodiments and examples shown below. Note that in the drawings referred to in the embodiments and examples of the present invention, the same portions or portions having similar functions are denoted by the same reference numerals, and repeated description thereof is omitted.

The heat transfer medium according to the present invention contains 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) in an amount of 50% by mass or more, more preferably 85% by mass or more. The 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) or trans It may be -2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)), or may be a mixture of the cis isomer and the trans isomer.

The heat transfer method according to the present invention uses the 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) as a heat transfer medium. The heat transfer method according to the present invention includes cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)), trans-2-chloro-1,3,3,3. -Tetrafluoropropene (HCFO-1224xe (E)) or a mixture of the cis and trans isomers is used as the heat transfer medium. The present inventors have found that any of the heat transfer media according to the present invention is nonflammable, has a small environmental load, and has excellent heat cycle characteristics and heat transfer characteristics.

2-Chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) will be described below.

<HCFO-1224xe>
2-Chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) contains a carbon-carbon double bond in the molecule and has a high reactivity with a hydroxyl radical. (GWP) is extremely small and the environmental load is small. In addition, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is nonflammable in both cis form (HCFO-1224xe (Z)) and trans form (HCFO-1224xe (E)). A mixture of a cis form (HCFO-1224xe (Z)) and a trans form (HCFO-1224xe (E)) of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) -1224xe (Z)) is 0.1 to 99.9% by mass, and the trans-isomer (HCFO-1224xe (E)) is 0.1 to 99.9% by mass. It is nonflammable with the composition.

2-Chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) can be produced from fluorine-containing olefins produced industrially. For example, as shown in FIG. 23, commercially available 1,3,3,3-tetrafluoropropene (HFO-1234ze) (hereinafter, the trans form of 1,3,3,3-tetrafluoropropene is converted to HFO-1234ze. (E) The cis isomer is HFO-1234ze (Z), and if the mixture or geometric isomer is not distinguished, it is also called HFO-1234ze). Since the geometrical isomer of HFO-1234ze as a starting material is not limited, HFO-1234ze (E), HFO-1234ze (Z), or a mixture thereof can be used. When HFO-1234ze and chlorine are reacted under light irradiation, 2,3-dichloro-1,1,1,3-tetrafluoropropane (hereinafter also referred to as HCFC-234da) is produced. Next, HCFO-1224xe is produced by bringing HCFC-234da into contact with a basic aqueous solution such as an aqueous potassium hydroxide solution. When this is precision distilled in a high-column distillation column, HCFO-1224xe (Z) and HCFO-1224xe (E) can be isolated. When a phase transfer catalyst is used when contacting HCFC-234da with a basic aqueous solution, it is possible to suppress by-production of 1,2-dichloro-3,3,3-trifluoropropene (HCFC-1223xd). preferable.

2,3-dichloro-1,1,1,3-tetrafluoropropane (HCFC-234da) has erythro and threo diastereomeric isomers, which can be separated by distillation. When erythro HCFC-234da is brought into contact with a basic aqueous solution such as an aqueous potassium hydroxide solution, HCFO-1224xe (Z) is produced as a main component. On the other hand, when the threo form of HCFC-234da is brought into contact with a basic aqueous solution such as an aqueous potassium hydroxide solution, HCFO-1224xe (E) is produced as the main component. Here, it is not easy to perform precision distillation of HCFO-1224xe (E) and HCFO-1224xe (Z). Therefore, when isolating HCFO-1224xe (E) and HCFO-1224 (Z), the HCFC-234da diasteromer isomer is isolated once in advance, and the erythro and threo forms of HCFC-234da are used as starting materials. Thus, high-purity HCFO-1224xe (E) and HCFO-1224 (Z) can be produced. Therefore, as described above, dehydrochlorination after once distilling the erythro and threo forms of HCFC-234da to obtain high purity HCFO-1224xe (E) and / or HCFO-1224xe (Z) It is mentioned as one of the preferable aspects.

Alternatively, when 2-chloro-1,1,1,3,3-pentafluoropropane (hereinafter also referred to as HCFC-235da) is contacted with a basic aqueous solution such as an aqueous potassium hydroxide solution, HCFO-1224xe (Z ) Can be obtained. HCFC-235da can be obtained as a by-product during the production of HCFO-1233zd.

In one embodiment of the present invention, the heat transfer medium may have a mass ratio of cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) of 50% by mass or more. It is preferably 85% by mass or more. By having such a composition, the heat transfer medium of the present invention can make the contribution to ozone layer destruction and global warming extremely small.

In one embodiment of the present invention, the heat transfer medium contains 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), preferably 50% by mass or more, particularly preferably 85% by mass or more. The 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is a mixture of a cis form (HCFO-1224xe (Z)) and a trans form (HCFO-1224xe (E)). And the mass ratio of the cis isomer to the trans isomer is 50 mass% to 99.9 mass% in the cis isomer (HCFO-1224xe (Z)), and the trans isomer (HCFO-1224xe (E) )) In a mass ratio of 0.1% by mass to 50% by mass. By having such a composition, the heat transfer medium of the present invention can make the contribution to ozone layer destruction and global warming extremely small.

In one embodiment of the present invention, the water content of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) contained in the heat transfer medium of the present invention is not particularly limited. The total amount is preferably 50 ppm or less, more preferably 20 ppm or less, and most preferably 10 ppm or less. Low water content from the viewpoint of the effects on thermal stability, chemical stability and electrical insulation of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and lubricating oil preferable.

As described above, since 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is nonflammable, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO— When the heat transfer medium of the present invention including 1224xe) is used in a refrigeration cycle system, a heat pump system, an organic Rankine cycle system, etc., it is not necessary to use a flammable inhibitor. Further, according to one embodiment of the present invention, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is a refrigeration cycle system, a heat pump system, an organic Rankine that uses a combustible heat transfer medium. You may add to a cycle system etc. as a combustible inhibitor.

<Lubricating oil>
When the heat transfer medium of the present invention is used in a refrigeration cycle system or a high-temperature heat pump cycle system, the lubricating oil used in the compressor sliding portion is mineral oil (paraffinic oil or naphthenic oil) or synthetic oil. Alkylbenzenes (AB), poly-α-olefins (PAO), esters, polyol esters (POE), polyalkylene glycols (PAG) or polyvinyl ethers (PVE) may be used. These lubricating oils may be used alone or in combination of two or more. As will be described later, the heat transfer medium of the present invention is completely compatible with these lubricating oils over a wide temperature range, and also has good compatibility with lubricating oils containing no oxygen atoms (mineral oil, alkylbenzenes, etc.). Have Therefore, these lubricating oils can be effectively used as a heat transfer medium in a refrigeration cycle system or a high temperature heat pump cycle system that uses the sliding part of the compressor.

In addition, when the heat transfer medium of the present invention is used as a working medium for an organic Rankine cycle system, the lubricating oil used in the expander sliding portion is a mineral oil (paraffinic oil or naphthenic oil) or an alkylbenzene that is a synthetic oil. (AB), poly-α-olefin (PAO), esters, polyol esters (POE), polyalkylene glycols (PAG) or polyvinyl ethers (PVE) may be used. These lubricating oils may be used alone or in combination of two or more. As will be described later, the heat transfer medium of the present invention is completely compatible with these lubricating oils over a wide temperature range, and also has good compatibility with lubricating oils containing no oxygen atoms (mineral oil, alkylbenzenes, etc.). Have Therefore, these lubricating oils can be effectively used as a working medium in an organic Rankine cycle system using the expander sliding portion.

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, di- (penta Erythritol), tri- (pentaerythritol) and other hindered alcohols, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3- Propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3 -Propanediol, 2,2-die 1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, glycerin, polyglycerin, 1 , 3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose and the like.

Examples of carboxylic acids used as starting materials for polyol esters include butanoic acid, 2-methylpropanoic acid, pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, Methylpentanoic acid, 4-methylpentanoic acid, 2,2-dimethylbutanoic acid, 2,3-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, hexanoic acid, 2-methylhexanoic acid, 3-methylbutanoic acid, 4- Methylbutanoic acid, 5-methylbutanoic acid, 2,2-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 3,4-dimethylpentanoic acid, 4, 4-dimethylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 1,1,2-trimethylbutanoic acid, 1,2,2-trimethyl Rubutanoic acid, 1-ethyl-1-methylbutanoic acid, 1-ethyl-2-methylbutanoic acid, octanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 3,5-dimethylhexanoic acid, 2,4-dimethylhexane Acid, 3,4-dimethylhexanoic acid, 4,5-dimethylhexanoic acid, 2,2-dimethylhexanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2-propylpentanoic acid, nonanoic acid, 2,2-dimethylheptanoic acid, 2-methyloctanoic acid, 2-ethylheptanoic acid, 3-methyloctanoic acid, 3,5,5-trimethylhexanoic acid 2-ethyl-2,3,3-trimethylbutyric acid, 2,2,4,4-tetramethylpentanoic acid, 2,2,3,3-tetramethylpentanoic acid, , 2,3,4-tetramethylpentanoic acid, 2,2-diisopropylpropanoic acid, acetic acid, propionic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecane Examples include acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, and oleic acid.

Polyalkylene glycol is methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, linear or branched hexanol, etc. Examples thereof include compounds obtained by addition polymerization of an aliphatic alcohol having 1 to 18 carbon atoms with ethylene oxide, propylene oxide, butylene oxide, or the like.

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

In one embodiment of the present invention, the acid value of the lubricating oil contained in the heat transfer medium of the present invention is not particularly limited. However, in order to prevent corrosion of metals used in refrigeration cycle systems and the like, In order to prevent decomposition, it is preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH / g or less. In addition, in this specification, an acid value means the acid value measured based on Japanese Industrial Standard JISK2501.

In one embodiment of the present invention, the ash content of the lubricating oil contained in the heat transfer medium of the present invention is not particularly limited, but in order to increase the thermal stability and chemical stability of the lubricating oil and suppress the generation of sludge, etc. Preferably it is 100 ppm or less, More preferably, it is good also as 50 ppm or less. In addition, in this specification, an ash content means the value of the ash content measured based on Japanese Industrial Standard JISK2272.

In one embodiment of the present invention, the kinematic viscosity of the lubricating oil contained in the heat transfer medium of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 3 to 1000 mm ² / s, more preferably 4 to 500 mm. ² / s, most preferably 5 to 400 mm ² / s. The kinematic viscosity at 100 ° C. is preferably 1 to 100 mm ² / s.

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

Examples of the nitro compound include known compounds, but 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.

The phenols include phenols containing various substituents such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group, and a halogen in addition to the hydroxyl group. For example, 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol Monovalent phenol such as eugenol, isoeugenol, butylhydroxyanisole, phenol, xylenol or divalent such as t-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone Examples of phenol and the like.

Examples of the imidazoles include 1-methylimidazole, 1-n-butylimidazole having a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or an aryl group as the N-position substituent. 1-phenylimidazole, 1-benzylimidazole, 1- (β-oxyethyl) imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1, Examples include 2-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 benzylamine, 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, dibenzylamine, tribenzylamine, 2-ethylhexylamine, aniline N, N-dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetrae Renpentamin, benzylamine, dibenzylamine, diphenylamine, diethylhydroxylamine and the like. These may be used alone or in combination of two or more.

Examples of the hydrocarbons include aromatic unsaturated hydrocarbons such as α-methylstyrene and p-isopropenyltoluene, isoprenes, propadiene and terpenes. These may be used alone or in combination of two or more.

The stabilizer may be added in advance to one or both of the refrigerant and the lubricating oil, or may be added alone in the condenser. At this time, although the usage-amount of a stabilizer is not specifically limited, 0.001 mass% or more and 10 mass% or less are preferable with respect to a main refrigerant | coolant (100 mass%), 0.01 mass% or more and 5 mass% or less are preferable. More preferably, it is 0.02 mass% or more and 2 mass% or less. If the added amount of the stabilizer exceeds 10% by mass or less than 0.001% by mass with respect to the main refrigerant (100% by mass), sufficient stability and thermal cycle performance of the refrigerant cannot be obtained.

<Drying agent>
According to one embodiment of the present invention, the heat transfer medium of the present invention may be used in a refrigeration cycle system, a heat pump system, an organic Rankine cycle system, etc. with a desiccant useful for water removal. The desiccant may be selected from activated alumina, silica gel, molecular sieves typified by zeolite, and combinations thereof.

As the desiccant used for the purpose of removing moisture contained in the heat transfer medium, molecular sieve is preferable. The type of molecular sieve is not particularly limited, but zeolite is particularly preferred from the viewpoints of chemical reactivity with the heat transfer medium, hygroscopic ability as a desiccant, and breaking strength. Representative zeolites include Zeorum A-3 and Zeorum A-4 (manufactured by Tosoh Corporation), but are not limited to these zeolites. The pore diameter of zeolite is not particularly limited, but 3A or 4A is particularly preferable in order to selectively remove only moisture in the thermal cycle system without adsorbing the heat transfer medium. By using the zeolite having the pore diameter, adsorption of the heat transfer medium to the zeolite is difficult to occur, and corrosion of materials constituting the thermal cycle system and generation of insoluble products can be suppressed.

The size of the zeolitic desiccant is not particularly limited, but is preferably 0.5 mm or more and 5 mm or less in order to prevent clogging in the heat cycle system and not to reduce the drying ability. The shape of the zeolitic desiccant is not particularly limited, but is preferably spherical or cylindrical.

The heat transfer medium of the present invention is nonflammable, has a low environmental load, and has excellent thermal cycle characteristics. Therefore, heat medium for high-temperature heat pumps used for generating pressurized hot water or superheated steam, etc., working medium for organic Rankine cycle used for power generation systems, refrigerant for vapor compression refrigeration cycle system, absorption heat pump, heat pipe Etc., or cleaning agents for cycle cleaning of cooling systems or heat pump systems, metal cleaning agents, flux cleaning agents, diluting solvents, foaming agents, aerosols and the like.

It should be noted that the heat transfer medium and heat transfer method of the present invention can be applied not only to a package-type small apparatus but also to a factory-scale large-scale system.

Hereinafter, the refrigeration cycle system using the heat transfer composition of the present invention will be described in detail.

<Refrigeration cycle system>
In the refrigeration cycle system, the heat of the object to be cooled, such as air, water or brine, is transferred by the evaporator as the latent heat of vaporization of the refrigerant, and the generated refrigerant vapor is compressed by adding work to the compressor and condensed. This is a system in which the heat of condensation is discharged and liquefied by an evaporator, and the condensed refrigerant is expanded and expanded to a low pressure and low temperature by an expansion valve, and sent to an evaporator to evaporate. In the evaporator, the refrigerant receives the thermal energy of the object to be cooled, thereby cooling the object to be cooled and lowering the temperature to a lower temperature. Also, in the condenser, the heat energy of the refrigerant is given to the load fluid. Thus, the load fluid is heated to raise the temperature to a higher temperature, and can be applied to a known system.

In the evaporator or condenser of the refrigeration cycle system, examples of the fluid to be cooled or the fluid to be heated that exchange heat with the refrigerant (heat transfer medium) include air, water, brine, and silicone oil. These are preferably selected and used according to the cycle operating temperature conditions.

FIG. 1 is a schematic diagram showing an example of a refrigeration cycle system to which the heat transfer medium of the present invention can be applied. The configuration and operation (repetitive cycle) of the refrigeration cycle system 100 of FIG. 1 will be described below.

The refrigeration cycle system 100 according to the present invention includes an evaporator 11 that takes in heat and a condenser 13 that supplies heat. Furthermore, the refrigeration cycle system 100 increases the pressure of the refrigerant (heat transfer medium of the present invention) that has exited the evaporator 11 and squeezes the compressor 12 that consumes power, and the refrigerant supercooled liquid that has exited the condenser 13. And an expansion valve 14 for expansion.

When the heat cycle of the refrigeration cycle system is repeated using the heat transfer medium of the present invention, energy equal to or greater than the input power is extracted from the medium to be cooled as heat energy in the evaporator 11 through the following steps (a) to (d). That is, it can be cooled.
(A) In the heat exchanger (evaporator 11), the liquid refrigerant is heat-exchanged with the fluid to be cooled (air, water, etc.) and vaporized.
(B) The vaporized refrigerant is taken out from the heat exchanger, the vaporized refrigerant is passed through the compressor 12, and high-pressure superheated steam is supplied.
(C) The refrigerant discharged from the compressor 12 is passed through the condenser 13 to exchange heat between the gaseous refrigerant and the fluid to be heated (air, water, etc.) to be liquefied.
(D) The liquefied refrigerant is throttled and expanded by the expansion valve 14, supplied with low-pressure wet steam, and recirculated to step (a).

As described above, the refrigeration cycle system containing the heat transfer medium of the present invention as a refrigerant has at least one evaporator 11, a compressor 12, a condenser 13, and an expansion valve 14, and these It has piping for transporting refrigerant between elements. The refrigeration cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery device, and a non-condensable gas separator in addition to the element devices.

The type of the compressor is not particularly limited, but may be a single-stage or multistage centrifugal compressor or a positive displacement compressor. As the positive displacement compressor, a rotary piston compressor, a rotary vane compressor, a scroll compressor, a screw compressor, a piston / crank compressor, or a piston / swash plate compressor may be used.

In one embodiment of the present invention, the refrigeration cycle system containing the heat transfer medium of the present invention is a compressor selected from the group consisting of a single stage centrifugal compressor, a multistage centrifugal compressor, and a screw compressor. You may have. In order to maximize the heat transfer characteristics of the present invention, it is particularly preferable to use a single-stage or multi-stage centrifugal compressor.

If non-condensable gas is mixed in the refrigeration cycle system, it will have the adverse effect of poor heat transfer and increased operating pressure in the condenser and evaporator, so measures must be taken to prevent the non-condensable gas from mixing in the system. There is. The heat transfer medium containing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) has a lower vapor pressure than existing refrigerants, and depending on the operating conditions, the heat cycle system may be negative. Pressure operation may occur. Oxygen contained in the air that may be mixed during the negative pressure operation reacts with the heat transfer medium and the lubricating oil, so it is preferable to remove the oxygen outside the heat cycle system using a non-condensable gas separator or the like.

冷 By using the heat transfer medium of the present invention in a refrigeration cycle system, cold water of 10 ° C or lower can be generated, preferably 7 ° C or lower, more preferably 5 ° C or lower.

In addition, the heat transfer medium of the present invention has a large global warming potential (GWP) containing 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) and an ozone depletion potential (ODP). It can be applied to refrigeration cycle systems that use or are designed to use non-negligible heat transfer media (environmental load heat transfer media). In the refrigeration cycle system, the environmental load type heat transfer medium including HCFC-123 is replaced with the heat transfer medium of the present invention, so that the GWP is reduced, the influence on the ozone layer is extremely reduced, and the load on the environment is reduced. Can be reduced.

One aspect of the method for replacing the environmental load type heat transfer medium accommodated in the refrigeration cycle system with the heat transfer medium of the present invention is to collect all the environmental load type heat transfer medium accommodated, and then It is a method of filling the heat transfer medium of the invention. A method for replacing the heat transfer medium is not particularly limited, but it is preferable to perform the method when the operation of the refrigeration cycle system is stopped. In order to recover the environmental load type heat transfer medium, it is desirable to use a recovery device used when recovering the fluorocarbon refrigerant in order to reduce the load on the environment. The method for filling the heat transfer medium of the present invention is not particularly limited, but the heat transfer medium may be filled using a pressure difference between the heat transfer medium and the refrigeration cycle system, or may be filled using mechanical power such as a pump. Good.

Hereinafter, a high-temperature heat pump cycle system using the heat transfer medium of the present invention will be described. The high-temperature heat pump cycle system is a vapor compression thermal cycle system similar to the refrigeration cycle system shown in FIG. 1, and is a system for heating by heat exchange in a condenser.

The condensation temperature of the heat transfer medium of the present invention in the high temperature heat pump cycle system is 60 ° C. or higher and 170 ° C. or lower, preferably 80 ° C. or higher and 150 ° C. or lower.

The condensation pressure of the heat transfer medium of the present invention in the high-temperature heat pump cycle system according to the present invention is determined by the composition of the heat transfer medium and the condensation temperature. That is, the condensation pressure is equal to the saturated vapor pressure of the heat transfer composition at the condensation temperature. Generally, if the condensation pressure exceeds 5.0 MPa, high pressure resistance is required for the compressor, the condenser and the piping parts, and these devices are expensive, which is not preferable. When the heat transfer medium according to the present invention is used, the condensation pressure can be made lower than 5.0 MPa, and known compressors, condensers, evaporators, expansion valves, and piping parts can be used. The high-temperature heat pump cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery device, and a non-condensable gas separator in addition to the element devices.

If non-condensable gas is mixed in the high-temperature heat pump cycle system, the heat transfer failure in the condenser or evaporator and the operating pressure increase will be adversely affected. It is necessary to take. For this reason, oxygen contained in the air that may be mixed when the system is under negative pressure operation depending on the operating conditions is converted into a heat cycle using a non-condensable gas separator or the like, as in the refrigeration cycle system described above. It is preferable to remove it outside the system.

When the high-temperature heat pump cycle system is repeated using the heat transfer medium of the present invention, energy higher than the input power can be taken out as heat energy in the condenser through the following steps (a) to (d). .
(A) The working medium in a liquid state is heat-exchanged with a fluid to be cooled (air, water, etc.) in a heat exchanger (evaporator) and vaporized.
(B) The vaporized refrigerant is taken out from the heat exchanger, the vaporized working medium is passed through a compressor, and high-pressure superheated steam is supplied.
(C) The working medium discharged from the compressor is passed through a condenser, and the gaseous working medium is heat-exchanged with a fluid to be heated (air, water, etc.) to be liquefied.
(D) The liquefied refrigerant is squeezed and expanded by an expansion valve, supplied with low-pressure wet steam, and recirculated to step (a).

By using the heat transfer medium of the present invention in a high-temperature heat pump cycle system, it is possible to generate hot water of 60 ° C. or higher, preferably 80 ° C. or higher of hot water, pressurized hot water or steam, More preferably, pressurized hot water or steam at 110 ° C. or higher can be generated.

In addition, the heat transfer medium of the present invention has a large global warming potential (GWP) containing 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) and an ozone depletion potential (ODP). It can be applied to high temperature heat pump cycle systems that use or are designed to use non-negligible heat transfer media (environmental heat transfer media). By replacing the environmental load type heat transfer medium including HCFC-123 in the high temperature heat pump cycle system with the heat transfer medium of the present invention, the GWP is reduced, the influence on the ozone layer is extremely reduced, and the environmental load is reduced. Can be reduced.

One aspect of the method for replacing the environmental load type heat transfer medium accommodated in the high-temperature heat pump cycle system with the heat transfer medium of the present invention is to use the environmental load type heat transfer medium accommodated in the refrigeration cycle system described above. This is substantially the same as the method for replacing the heat transfer medium of the present invention.

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

<Organic Rankine cycle system>
The organic Rankine cycle system is an evaporator in which heat energy is supplied from a heating source to a working medium, and the working medium that has become steam in a high-temperature and high-pressure state is adiabatically expanded by an expander. This is a device for generating electricity by driving a generator. The working medium vapor after adiabatic expansion is condensed into a liquid by the condenser and transferred to the evaporator by the pump. In addition, as heat energy of a heating source, you may use the exhaust heat of medium and low temperature of 200 degrees C or less, and renewable heat energy.

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

FIG. 2 is a schematic view showing an example of an organic Rankine cycle system applicable to the heat transfer medium of the present invention as a working medium. Hereinafter, the configuration and operation (repetition cycle) of the organic Rankine cycle 200 of FIG. 2 will be described.

The organic Rankine cycle system 200 of the present invention includes an evaporator 20 (boiler) that receives heat, and a condenser 21 (condenser) that supplies heat. Furthermore, the organic Rankine cycle system 200 includes an expander 22 that is operated by a working medium that circulates in the system, and a circulation pump 23 that increases the pressure of the liquid that has exited the condenser 21 and consumes power. The generator 24 that generates electric power is driven by the expander 22.

When the organic Rankine cycle is repeated using the heat transfer medium of the present invention as a working medium, the thermal energy is converted into mechanical energy through the following steps (a) to (e), and then converted into electrical energy through a generator. It can be taken out.
(A) The liquid working medium exchanges heat with the fluid to be cooled (heating source) in the heat exchanger (evaporator 20), and vaporizes (phase change from liquid to gas).
(B) Remove the vaporized working medium from the heat exchanger.
(C) The vaporized working medium is expanded through an expander (power generation turbine 22) and converted into mechanical (electrical) energy.
(D) The working medium exiting from the expander is passed through the condenser, and the gaseous working medium is condensed (phase change from gas to liquid).
(E) The liquefied working medium is pressurized and transferred by the pump 23 and recirculated to the step (a).

As described above, the organic Rankine cycle system containing the heat transfer medium of the present invention as a working medium includes at least one evaporator 20, an expander 22, a condenser 21, a circulation pump 23, and a combination of these elements. And a piping for transporting the working medium. The organic Rankine cycle system may include an internal heat exchanger, a dryer (dryer), a liquid separator, an oil recovery device, and a non-condensable gas separator in addition to the element devices.

The type of the expander is not particularly limited, but may be a single-stage or multi-stage centrifugal expander or a positive displacement expander. As the positive displacement expander, a rotary piston expander, a rotary vane expander, a scroll expander, a screw expander, or a piston / crank expander may be used.

If non-condensable gas is mixed in the high-temperature heat pump cycle system, the heat transfer failure in the condenser or evaporator and the operating pressure increase will be adversely affected. It is necessary to take. Therefore, it is preferable to provide a non-condensable gas separator or the like.

By using the heat transfer medium of the present invention as the working medium of the organic Rankine cycle system, heat energy of 50 ° C. or higher and 200 ° C. or lower, preferably 80 ° C. or higher and 150 ° C. or lower can be converted into mechanical energy. As a heating source of the evaporator 20, hot water, pressurized hot water or steam having a temperature of 50 ° C to 200 ° C, preferably 80 ° C to 120 ° C may be used. Mechanical energy may be converted into electrical energy by a generator.

The evaporation temperature of the heat transfer medium of the present invention is 50 ° C. or higher and 200 ° C. or lower, preferably 80 ° C. or higher and 150 ° C. or lower.

The evaporation pressure of the heat transfer medium of the present invention is determined by the composition of the heat transfer medium and the evaporation temperature. That is, the evaporation pressure is equal to the saturated vapor pressure of the heat transfer medium at the evaporation temperature. Generally, when the evaporation pressure exceeds 5.0 MPa, high pressure resistance is required for the compressor, the condenser and the piping parts, and these devices are expensive, which is not preferable. When the heat transfer medium according to the present invention is used, the evaporation pressure can be made lower than 5.0 MPa, and known expanders, condensers, pumps, and piping parts can be used.

In addition, the heat transfer medium of the present invention has a large global warming potential (GWP) containing 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) and an ozone depletion potential (ODP). It can be applied to organic Rankine cycle systems that use or are designed to use non-negligible working media (environmental working media). In the organic Rankine cycle system, the environmental load type working medium including HCFC-123 is replaced with the heat transfer medium of the present invention, thereby reducing the GWP, extremely reducing the influence on the ozone layer, and reducing the load on the environment. Can be reduced.

One aspect of the method for replacing the environmentally-loading working medium contained in the organic Rankine cycle system with the heat transfer medium of the present invention is to collect all of the contained environmental-loading working medium, and then the present invention. It is a method of filling the heat transfer medium. A method for replacing the working medium with the heat transfer medium of the present invention is not particularly limited, but it is desirable to perform the method when the operation of the organic Rankine cycle system is stopped. In order to reduce the environmental load, it is desirable to use a recovery device used when recovering the fluorocarbon refrigerant in order to recover the environmental load type working medium. After recovering the environmental load type working medium, the working medium container of the organic Rankine cycle system may be decompressed with a vacuum pump before filling the heat transfer medium of the present invention. The method of filling the heat transfer medium of the present invention is not particularly limited, but the heat transfer medium may be filled using a pressure difference between the heat transfer medium and the organic Rankine cycle system, or filled using mechanical power such as a pump. Also good.

The heat transfer medium of the present invention is a composition containing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe). Compared with 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), the environmental impact is extremely small. Moreover, the heat transfer medium of the present invention is excellent in heat transfer and thermal energy conversion characteristics, and can be suitably used for an organic Rankine cycle system.

Examples of indexes for evaluating the characteristics of the working medium used in the organic Rankine cycle system include a power generation cycle efficiency (η _cycle ) and an expander size parameter (SP).

Power generation cycle efficiency (η _cycle ) is a generally accepted measure of working medium performance and is particularly useful for representing the relative thermodynamic efficiency of the working medium in the Rankine cycle. The ratio of the electrical energy generated by the working medium in the expander and the generator to the thermal energy supplied from the heating source when the working medium evaporates is represented by η _cycle .

The expander size parameter (SP) is a scale for evaluating the size of the expander, and is generally accepted (Energy 2012, Vol.38, P136-143). When the working medium is replaced in the Rankine cycle under the same conditions, a larger SP value means that the working medium requires a larger size expander. That is, a smaller SP value is more preferable because a smaller expander can be employed and contributes to the miniaturization of the Rankine cycle system.

On the other hand, generally, when the value of the power generation cycle efficiency is high, the value of SP is also high. Conversely, when the value of the power generation cycle efficiency is low, the value of SP is low. That is, the value of the power generation cycle efficiency and the value of SP are in a trade-off relationship. In the working medium used in the organic Rankine cycle system, it is preferable that the power generation cycle efficiency is high, and in order to satisfy the demand for downsizing the Rankine cycle system, the SP value is preferably low. In the conventional working medium, it was difficult to satisfy this condition in a practical range.

Since the heat transfer medium of the present invention is a composition containing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), it has a power generation cycle efficiency (η _cycle ) within a practical range. It is a novel heat transfer medium that can adjust the value and the value of the expander size parameter (SP).

Further, the heat transfer medium of the present invention is a composition containing 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), so that when generating electric energy of the same capacity, The expander inlet volume flow rate and the expander outlet volume flow rate can be made lower than that of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), which is widely used, compared with the existing organic Rankine cycle system. Even the system can be miniaturized.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples described below.

The coefficient of performance (COP) is a generally accepted measure of refrigerant performance and represents the relative thermodynamic efficiency of a heat transfer medium during a particular heating or cooling cycle, including evaporation or condensation of the heat transfer medium. It is particularly beneficial to The ratio of the amount of heat that the heat transfer medium in the evaporator receives from the medium to be cooled 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 of the quantity of heat which the heat transfer medium in the condenser for the amount of work added by the compressor in compressing the vapor is released into the heated medium at COP _H.

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

[Example 1]
Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)), trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) ) Saturation vapor pressure was measured. First, 15 g of cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) was placed in a pressure vessel made of SUS316 having an internal volume of 25 ml connected to a pressure transducer. Thereafter, the pressure vessel was cooled with liquid nitrogen to solidify HCFO-1224xe (Z), and the air remaining in the vessel was removed with a vacuum pump. The pressure vessel was placed in a constant temperature bath (manufactured by LAUDA, RP1845) containing silicone oil, and HCFO-1224xe (Z) was controlled to a predetermined temperature. Measure the temperature of HCFO-1224xe (Z) using a platinum resistance thermometer (Yamazato Sangyo, JIS-A class), and sputter gauge pressure transducers (manufactured by Kyowa Dengyo, PHS-5KA and PHS-20KA) Was used to measure the pressure of HCFO-1224xe (Z). For trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)), cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe ( The saturated vapor pressure was measured in the same manner as in Z)). The results are shown in Table 1.

[Example 2]
3 mL of cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) was placed in a cell of a vibration type density meter (DMA4500M manufactured by Anton Paar), and the liquid density was measured. The liquid density of trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) was measured in the same manner. The results are shown in Table 2.

[Example 3]
2-Chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) (mixture of cis isomer and trans isomer, mass ratio is cis isomer / trans isomer = 98.9 / 1.01) A stability test was performed. In accordance with the shield tube test of JIS K2211 “Refrigerator Oil”, 1.0 g of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) and metal pieces (iron, copper, and aluminum) The sample was sealed in a glass test tube, heated to 150 ° C. and held for 1 week. After one week, the appearance of the refrigerant was visually observed, the purity gas chromatograph (manufactured by Shimadzu Corporation, GC-2010plus) measured at, acid content ^- by (Cl ion) ion chromatography (Nippon Dionex Ltd., ICS-2100) Measured and evaluated for thermal stability. The obtained results are shown in Table 3.

As is apparent from the results shown in Table 3, no thermal decomposition product of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) was observed. Further, the by-product acid content (Cl ⁻ ) after the thermal stability test was extremely small, and the hue after the test was maintained colorless and transparent, so that 2-chloro-1,3,3,3-tetra It can be seen that fluoropropene (HCFO-1224xe) is excellent in thermal stability even in a high temperature state and is suitable as a heat transfer medium.

In Example 3, metal specimens (iron, copper and aluminum) contacted with 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) were collected and visually observed. In all the metal tests, the metallic luster of the surface was maintained, and no corrosion was observed. Therefore, it can be seen that the heat transfer medium according to the present invention is highly compatible with metals even in a high temperature state.

[Example 4]
According to JIS-K-2211 Annex D, 1.0 g of cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) as a refrigerant (heat transfer medium) and lubrication 1.0 g of oil (mass ratio: refrigerant / lubricant = 85/15, 50/50, 15/85) is added to a thick glass test tube, cooled with liquid nitrogen, and a mixture of refrigerant and lubricant is added. Solidified. After the mixture of refrigerant and lubricating oil solidified, a vacuum pump was connected to the top of the test tube to remove the remaining air, and the top of the test tube was sealed with a gas burner. The sealed thick glass test tube was placed in a thermostat cooled to −40 ° C., and allowed to stand until the temperature of the thermostat and the composition in the glass test tube were equal. Thereafter, the temperature of the thermostatic bath was changed from −40 to + 120 ° C., and the compatibility between the refrigerant and the lubricating oil was visually evaluated. Table 4 shows the obtained results. In Table 4, it evaluated by (circle) when two-phase separation or the composition became cloudy when it was compatibilized uniformly, and x.

The following five types of lubricating oil were used for the compatibility test.
Mineral oil (MO): Suniso 4GS (manufactured by Nippon San Oil)
Polyol ester oil (POE): SUNICE T68 (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)

[Example 5]
Compatibility test of refrigerant and lubricating oil under the same conditions as in Example 4 except that trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) was used as the refrigerant Went. The results are shown in Table 5. In Table 5, when the solution was uniformly mixed, the evaluation was ○, and when the two-layer separation or the composition became turbid, the evaluation was ×.

[Comparative Example 1]
Except that the refrigerant was cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)), the compatibility test between the refrigerant and the lubricating oil was conducted in the same manner as in Example 4 and Example 5. went. The results obtained are shown in Table 6. In Table 6, it evaluated by (circle) when it was compatibilized uniformly, and x when two-layer separation or the composition became turbid.

As shown in Tables 4 and 5, cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetra Fluoropropene (HCFO-1224xe (E)) had good compatibility with POE, PAG and PVE, which are oxygenated lubricating oils. In addition, cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe ( It can be seen that E)) is compatible with MO and AB, which are lubricating oils not containing oxygen, at a temperature condition of 20 ° C. or higher. Referring to the results of Comparative Example 1 shown in Table 6, cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)) is compared to MO and AB which are lubricating oils not containing oxygen. There was complete two-phase separation under all temperature conditions. Therefore, when 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is used as a heat transfer medium in a refrigeration cycle system or a high-temperature heat pump cycle system, oxygen-containing lubricating oils such as POE, PAG It can be seen that MO and AB, which are lubricating oils not containing oxygen, can be applied as lubricating oils as well as PVE and PVE.

[Example 6]
In accordance with Japanese Industrial Standards JIS K2265-1 “How to Determine Flash Point—Part 1: Tag Sealing Method”, cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z )) And trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) were measured respectively. For the flash point measurement, an automatic flash point measuring device atg-8l (Tanaka Scientific Instruments Manufacturing Co., Ltd.) was used.

As a result, cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO— Both 1224xe (E)) were observed to have no flash point under atmospheric pressure conditions.

[Example 7]
In accordance with the 2002 edition of the American Society for Testing and Materials (ASTM) Standard E-681 and the 2010 edition of the American Society for Heating, Air Conditioning and Air Conditioning (ASHRAE) Standard 34-2010, cis-2-chloro-1,3,3,3-tetra The combustion ranges of fluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) were measured.

As a result, cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) has a combustion range at 23 ° C., 101.3 kPa, and relative humidity of 50%. It was nonflammable. Further, even under the conditions of 60 ° C., 101.3 kPa, and relative humidity of 50%, the combustion range was not seen and it was nonflammable.

In addition, trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) was also used under the conditions of 23 ° C., 101.3 kPa, and relative humidity of 50%, similar to the cis isomer. The combustion range was not seen and it was nonflammable. Further, even under the conditions of 60 ° C., 101.3 kPa, and relative humidity of 50%, the combustion range was not seen and it was nonflammable.

From the results of Example 7, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) is both a cis form (HCFO-1224xe (Z)) and a trans form (HCFO-1224xe (E)). It was determined to be a nonflammable compound. According to the refrigerant classification of the American Society of Heating, Cooling and Air Conditioning Engineers (ASHRAE), it can be seen that it falls under Category 1 (nonflammable refrigerant).

[Example 8]
<Refrigeration cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene>
In the performance evaluation of the refrigeration cycle system and the high temperature heat pump cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) as a heat transfer medium, the conditions shown in Table 7 The coefficient of performance (COPR, COPH) was calculated. The physical property values of the heat transfer medium are shown in REFPROP ver. It calculated | required by 9.0.

Refrigerating cycle system calculation condition 1 is shown in Table 7 below.

Refrigeration cycle system calculation condition 1 assumes the generation of 7 ° C. cold water by heat exchange between the heat transfer medium and the heat source water in the evaporator.

In calculating the coefficient of performance (COP _R ) of the refrigeration cycle system, 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) Ignore heat loss and pressure loss in piping and heat exchangers.
(D) The compressor efficiency η is set to 0.7.

Below, the formula for calculating the coefficient of performance (COP _R ) of the refrigeration cycle system will be described in detail. The amount of heat input to the evaporator Q _EVA is
Q _EVA = G × (h ₁ −h ₄ ) (1)
The heat dissipation amount Q _CON in the condenser is
Q _CON = G × (h ₂ −h ₃ ) (2)
It becomes.

However, when the enthalpy of the heat transfer medium at the compressor outlet after isentropic compression is represented by h _2th , the enthalpy h ₂ of the heat transfer medium at the compressor outlet when considering the compressor efficiency is
h ₂ = h ₁ + (h _2th −h ₁ ) / η (3)
It becomes.

When compressing the vapor of the heat transfer medium, the work W applied by the compressor is
W = G × (h ₂ −h ₁ ) (4)
It becomes.

The coefficient of performance (COP _R ) of the refrigeration cycle system is
COP _R = Q _EVA / W = (h ₁ -h ₄ ) / (h ₂ -h ₁ ) (5)
It becomes.

The coefficient of performance (COP _H ) of the high-temperature heat pump cycle system is
COP _H = Q _CON / W = (h ₂ −h ₃ ) / (h ₂ −h ₁ ) (6)
It becomes.

Next, the formula for calculating the volume capacity (CAP) of the heat transfer medium will be described in detail. Since the vapor density of the heat transfer medium at the compressor suction port is ρ ₂ and the heat absorption amount Q _EVA in the evaporator, the volume capacity (CAP _R ) of the refrigeration cycle system is
CAP _R = ρ ₂ × Q _EVA = ρ ₂ × (h ₁ −h ₄ ) (7)
It becomes.

The volume capacity (CAP _H ) of the high-temperature heat pump cycle system is
CAP _H = ρ ₂ × Q _CON = ρ ₂ × (h ₂ −h ₃ ) (8)
It becomes.

In the above (1) to (8), various symbols mean the following.
G: Heat transfer medium circulation rate W: Compression work Q _EVA : Heat input Q _CON : Heat release amount COP _R : Coefficient of performance (cooling)
COP _H : Coefficient of performance (heating)
CAP _R : Volume capacity (cooling)
CAP _H : Volume capacity (heating)
h: Specific enthalpy
_{1, 2, 3, 4} : cycle point
_2th : Cycle point after isentropic compression

FIG. 3 shows a Ph diagram in Example 8 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z))). In the figure, cycle points 1, 2, 3, and 4 indicate refrigeration cycle system calculation condition 1.

[Example 9]
<Refrigeration cycle system using trans-2-chloro-1,3,3,3-tetrafluoropropene>
In the performance evaluation of the refrigeration cycle system using trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 7 did. FIG. 4 shows a Ph diagram in Example 9 (trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E))).

[Example 10]
<Refrigeration cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene and trans-2-chloro-1,3,3,3-tetrafluoropropene>
Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) In the performance evaluation of the refrigeration cycle system using the mixture of) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 7. FIG. 5 shows Example 10 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3- The Ph diagram in tetrafluoropropene (HCFO-1224xe (E)) having a mass ratio of 95: 5) is shown.

[Comparative Example 2]
<2,2-dichloro-1,1,1-trifluoroethane>
2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) is nonflammable and has an allowable concentration of 10 ppm. HCFC-123 has a boiling point of 27.8 ° C. under atmospheric pressure, an atmospheric life of 1.3 years, a global warming potential (GWP) of 77 (IPCC Fourth Assessment Report 2007), and an ozone depletion potential (ODP). Is 0.02.

Instead of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) which is the heat transfer medium of the present invention, 2,2-dichloro-1,1,1-trifluoroethane (HCFC- In the performance evaluation of the refrigeration cycle system using 123) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 7. FIG. 6 shows a Ph diagram in Comparative Example 2 (HCFC-123).

Table 8 shows the calculation results of the refrigeration cycle system coefficient of performance (COP _R ) of Examples 8, 9 and Comparative Example 2 described above.

The relative COP _R and the relative CAP _R of Example 8 and Example 9 shown in Table 8 and Table 9 are calculated as relative values with COP _R and CAP _R of Comparative Example 2 shown in Table 8 being 1.00, respectively. did.

Table 9 shows the calculation results of the refrigeration cycle system coefficient of performance (COP _R ) of Example 10. In Table 9, the values of the first component and the second component of the heat transfer medium are expressed as mass percentages. The first component of the heat transfer medium of the mixture is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and the second component is trans-2-chloro-1, 3,3,3-tetrafluoropropene (HCFO-1224xe (E)). The relative COP _R and relative CAP _R of Example 10 were calculated as relative values with COP _R and CAP _R of Comparative Example 2 shown in Table 8 being 1.00, respectively.

As shown in Tables 8 and 9, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), which is a heat transfer medium of the present invention, is 2,2-dichloro- It can be seen that it has a coefficient of performance (COP _R ) equivalent to 1,1,1-trifluoroethane (HCFC-123). In addition, the volume capacity of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), which is the heat transfer medium of the present invention, may be 16 to 45% larger than the volume capacity of HCFC-123. I understood. These results show that when designing a refrigeration cycle system for 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) that has the same level of cooling capacity as the refrigeration cycle system for HCFC-123. This means that the size of the entire system can be further reduced as compared with the system for HCFC-123.

The heat transfer medium of the present invention, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), is comparable to the operating pressure, pressure ratio, and pressure difference of HCFC-123. Is found to be used as a more environmentally friendly alternative composition.

[Example 11]
<High temperature heat pump cycle system (I) using cis-2-chloro-1,3,3,3-tetrafluoropropene>
In the performance evaluation of a high-temperature heat pump cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 10. Calculated. The physical property values of the heat transfer medium are shown in REFPROP ver. It calculated | required by 9.0.

High temperature heat pump cycle system calculation condition 2 is shown in Table 10 below.

High-temperature heat pump cycle system calculation condition 2 assumes that 80 ° C. hot water is generated by heat exchange between the heat transfer medium and the heat source water in the condenser.

In calculating the high temperature heat pump cycle system coefficient of performance (COP _H ), 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) Ignore heat loss and pressure loss in piping and heat exchangers.
(D) The compressor efficiency η is set to 0.7.

FIG. 7 shows a Ph diagram in Example 11 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z))). In the figure, cycle points 1, 2, 3, and 4 indicate a high-temperature heat pump cycle system calculation condition 2.

[Example 12]
<High-temperature heat pump cycle system using trans-2-chloro-1,3,3,3-tetrafluoropropene>
In the performance evaluation of a high-temperature heat pump cycle system using trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 10. Calculated. FIG. 8 shows a Ph diagram in Example 12 (trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E))).

[Example 13]
<High-temperature heat pump cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene and trans-2-chloro-1,3,3,3-tetrafluoropropene>
Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) In the performance evaluation of the high-temperature heat pump cycle system using the mixed heat transfer medium (1), the coefficient of performance was calculated under the conditions shown in Table 10. FIG. 9 shows the results obtained in Example 13 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3- The Ph diagram in tetrafluoropropene (HCFO-1224xe (E)) having a mass ratio of 95: 5) is shown.

[Comparative Example 3]
<High-temperature heat pump cycle system using 2,2-dichloro-1,1,1-trifluoroethane (I)>
Instead of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) which is the heat transfer medium of the present invention, 2,2-dichloro-1,1,1-trifluoroethane (HCFC- In the performance evaluation of the high-temperature heat pump cycle system using 123) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 10. FIG. 10 shows a Ph diagram in Comparative Example 3 (HCFC-123).

Table 11 below shows the calculation results of the high temperature heat pump cycle system coefficient of performance (COP _H ) of Example 11, Example 12, and Comparative Example 3.

Relative COP _H and relative CAP _H of Example 11 and Example 12 shown in Table 11 and Table 12 are calculated as relative values with COP _H and CAP _H of Comparative Example 3 shown in Table 11 being 1.00, respectively. did.

Table 12 shows the calculation result of the high temperature heat pump cycle system coefficient of performance (COP _H ) of Example 13. In Table 12, the values of the first component and the second component of the heat transfer medium are expressed as mass percentages. In the heat transfer medium of the mixture, the first component is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and the second component is trans-2-chloro-1 3,3,3-tetrafluoropropene (HCFO-1224xe (E)). The relative COP _H and relative CAP _H of Example 13 were calculated as relative values with COP _H and CAP _H of Comparative Example 3 shown in Table 11 being 1.00, respectively.

As shown in Tables 11 and 12, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), which is a heat transfer medium of the present invention, is a conventionally used 2,2-dichloro- It can be seen that the coefficient of performance (COP _H ) is equivalent to that of 1,1,1-trifluoroethane (HCFC-123). In addition, the volume capacity (CAP _H ) of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), which is the heat transfer medium of the present invention, is 13 to 36 more than the volume capacity of HCFC-123. % Was found to be larger. These results indicate the design of a high temperature heat pump cycle system for 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) that has the same level of heating capability as the high temperature heat pump cycle system for HCFC-123. In this case, it means that the size of the entire system can be further reduced as compared with the system for HCFC-123.

[Example 14]
<High temperature heat pump cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene (II)>
In the performance evaluation of a high temperature heat pump cycle using cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 13 did.

The high temperature heat pump cycle system calculation condition 3 is shown in Table 13 below.

High-temperature heat pump cycle system calculation condition 3 assumes that 120 ° C. hot water is generated by heat exchange between the heat transfer medium and the heat source water in the condenser.

FIG. 11 shows a Ph diagram in Example 14 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z))). In the figure, cycle points 1, 2, 3, and 4 indicate a high-temperature heat pump cycle system calculation condition 3.

[Example 15]
<High-temperature heat pump cycle system (II) using trans-2-chloro-1,3,3,3-tetrafluoropropene>
In the performance evaluation of a high-temperature heat pump cycle system using trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 13. Calculated. FIG. 12 shows a Ph diagram in Example 15 (trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E))).

[Example 16]
<High-temperature heat pump cycle system (II) using cis-2-chloro-1,3,3,3-tetrafluoropropene and trans-2-chloro-1,3,3,3-tetrafluoropropene>
Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) In the performance evaluation of the high-temperature heat pump cycle system using the mixed heat transfer medium (1), the coefficient of performance was calculated under the conditions shown in Table 13. FIG. 13 shows the results of Example 16 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3- The Ph diagram in tetrafluoropropene (HCFO-1224xe (E)) having a mass ratio of 95: 5) is shown.

[Comparative Example 4]
<High-temperature heat pump cycle system using 2,2-dichloro-1,1,1-trifluoroethane (II)>
Instead of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) which is the heat transfer medium of the present invention, 2,2-dichloro-1,1,1-trifluoroethane (HCFC- In the performance evaluation of the high-temperature heat pump cycle system using 123) as a heat transfer medium, the coefficient of performance was calculated under the conditions shown in Table 13. FIG. 14 shows a Ph diagram in Comparative Example 3 (HCFC-123).

Table 14 shows the calculation results of the high-temperature heat pump cycle system coefficient of performance (COP _H ) of Examples 14, 15 and Comparative Example 4.

Relative COP _H and relative CAP _H of Example 14 and Example 15 shown in Table 14 and Table 15 are calculated as relative values with COP _H and CAP _H of Comparative Example 4 shown in Table 14 being 1.00, respectively. did.

Table 15 shows the calculation result of the high temperature heat pump cycle system coefficient of performance (COPH) of Example 16. In Table 15, the value of the 1st component of the heat transfer medium which is a mixture, and the 2nd component is shown by the mass percentage. The first component of the mixed heat transfer medium is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and the second component is trans-2-chloro-1,3 3,3-tetrafluoropropene (HCFO-1224xe (E)). Relative COP _H and relative CAP _H of Example 16 were calculated as relative values with COP _H and CAP _H of Comparative Example 4 shown in Table 14 being 1.00, respectively.

As shown in Tables 14 and 15, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), which is the heat transfer medium of the present invention, is a conventionally used 2,2-dichloro- It can be seen that the coefficient of performance (COP _H ) is equivalent to that of 1,1,1-trifluoroethane (HCFC-123). It was also found that the volume capacity (CAP _H ) of the heat transfer medium of the present invention was 8-24% greater than the volume capacity of HCFC-123. These results indicate the design of a high temperature heat pump cycle system for 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) that has the same level of heating capability as the high temperature heat pump cycle system for HCFC-123. In this case, it means that the size of the entire system can be further reduced as compared with the system for HCFC-123.

The heat transfer medium of the present invention, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), is comparable to the operating pressure, pressure ratio, and pressure difference of HCFC-123. Is found to be used as a more environmentally friendly alternative.

[Example 17]
<Organic Rankine Cycle System (I) Using Cis-2-Chloro-1,3,3,3-tetrafluoropropene>
In the performance evaluation of the organic Rankine cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) as a heat transfer medium (working medium), the conditions shown in Table 16 were used. The power generation cycle efficiency and expander size parameters were calculated.

Organic Rankine cycle system calculation condition 4 is shown in Table 16 below.

The organic Rankine cycle system calculation condition 4 assumes that the temperature of the heat source water supplied to the evaporator is 90 ° C. and the temperature of the cooling water supplied to the condenser is 30 ° C.

In calculating the power generation cycle efficiency (η _cycle ) and the expander size parameter (SP) of the organic Rankine cycle system, the following items were assumed.
(A) The ideal expansion process of Rankine cycle is isentropic expansion, and expander adiabatic efficiency η _T is introduced in consideration of actual machine loss.
(B) The generator loss due to the expander is taken into account by the generator efficiency η _G.
(C) The circulating pump power is driven by generated electricity, and the pump efficiency η _P including the motor efficiency is introduced. The pump is a can type and the loss is included in the cycle as heat.
(D) Since the circulating pump power of the bearing lubricating oil is very small, it is ignored.
(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 the power generation cycle efficiency (η _cycle ) of the organic Rankine cycle system 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.

The theoretically generated power L _Tth of the expander by the working medium circulation amount G is
L _Tth = G × (h ₁ −h _2th ) (9)
It becomes.

Generated in consideration of the expansion machine efficiency η _T power L _T is,
L _T = L _Tth × η _T = G × (h ₁ −h ₂ ) (10)
It becomes.

Power generation amount E _G considering the generator efficiency eta _G is
E _G = L _T × η _G (11)
It becomes.

Circulation pump, intended for feeding the working medium fluid of the condenser outlet to the condenser pressure P _C higher evaporator pressure of the pressure from the P _E, the theoretical power requirement L _Pth is
L _Pth = (P _E −P _C ) × G / ρ ₃ (12)
It becomes.

Required power E _P in consideration of pump efficiency eta _P is
E _P = L _Pth / η _P = G × (h ₄ −h ₃ ) (13)
It becomes.

The effective power generation amount E _cycle is
E _cycle = E _G -E _P (14)
It becomes.

The amount of heat Q _E supplied to the evaporator is
Q _E = G × (h ₁ −h ₄ )
= G × (h ₁ −h ₃₎ − (P _E −PC ₎ × G / (ρ ₃ × η _P ) (15)
It becomes.

Efficiency as a power generation cycle is
η _cycle = (E _G −E _P ) × 100 / Q _E (16)
It becomes.

Next, the expander size parameter (SP) will be described in detail. In addition, the calculation formula described in a nonpatent literature (Energy2012, Vol.38, P136-143) was used for the basic formula.

When the working medium circulation amount is G, the working medium volume flow rate V _{2th at the} expander outlet in the isentropic expansion is
V _2th = G / ρ _2th (17)
It becomes.

The theoretical heat drop ΔH _th of the expander is
_ΔH _th = h ₁ −h _2th (18)
It becomes.

The expander size parameter (SP) is
SP = (V _2th ) ^0.5 / ( _ΔH _th ) ^0.25 (19)
It becomes.

In the above (9) to (19), various symbols mean the following.
G: Working medium circulation amount L _Tth : _Expander theoretically generated power L _T : Expander generated power E _G : Power generation amount E _P : Circulation pump required power P _C : Condenser pressure P _E : Evaporator pressure L _Pth : Theoretical power required for operation of the circulation pump E _cycle : Effective power generation amount Q _E : Heat input amount η _cycle : Power generation cycle efficiency V _2th : Theoretical volume flow rate at the outlet of the expander _ΔH _th : Theoretical adiabatic heat drop SP of expansion Machine size parameter ρ: Working medium density h: Specific enthalpy
_1,2,3,4 : Cycle point

FIG. 15 shows a Ts diagram in Example 17 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z))). In the figure, cycle points 1, 2, 3, and 4 indicate organic Rankine cycle system calculation condition 4.

[Example 18]
<Organic Rankine cycle system (I) using trans-2-chloro-1,3,3,3-tetrafluoropropene>
In the performance evaluation of the organic Rankine cycle system using trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) as a heat transfer medium (working medium), the calculations shown in Table 16 were performed. The power generation cycle efficiency and expander size parameters were calculated under the conditions. FIG. 16 shows a Ts diagram in Example 18.

[Example 19]
<Organic Rankine cycle system (I) using cis-2-chloro-1,3,3,3-tetrafluoropropene and trans-2-chloro-1,3,3,3-tetrafluoropropene>
Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) In the performance evaluation of the organic Rankine cycle system using the mixed heat transfer medium (mixed working medium), the power generation cycle efficiency and the expander size parameter were calculated under the calculation conditions shown in Table 16. FIG. 17 shows Example 19 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)): trans-2-chloro-1,3,3,3- The Ts diagram in the tetrafluoropropene (HCFO-1224xe (E) mass ratio is 95: 5) is shown.

[Comparative Example 5]
<Organic Rankine cycle system using 2,2-dichloro-1,1,1-trifluoroethane (I)>
Instead of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) which is the heat transfer medium (working medium) of the present invention, 2,2-dichloro-1,1,1-trifluoro In the performance evaluation of the organic Rankine cycle system using ethane (HCFC-123) as a working medium, the power generation cycle efficiency and the expander size parameter were calculated under the calculation conditions shown in Table 16. In addition, in FIG. 18, the Ts diagram in the comparative example 5 is shown.

[Example 20]
<Organic Rankine cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene (II)>
In the performance evaluation of the organic Rankine cycle system using cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) as a heat transfer medium (working medium), the conditions shown in Table 17 The power generation cycle efficiency and expander size parameters were calculated. FIG. 19 shows a Ts diagram in Example 20.

The organic Rankine cycle system calculation conditions 5 are shown in Table 17 below.

[Example 21]
<Organic Rankine cycle system using trans-2-chloro-1,3,3,3-tetrafluoropropene (II)>
In the performance evaluation of the organic Rankine cycle system using trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) as a heat transfer medium (working medium), the calculations shown in Table 17 The power generation cycle efficiency and expander size parameters were calculated under the conditions. FIG. 20 shows a Ts diagram in Example 21.

[Example 22]
<Organic Rankine Cycle System (II) Using Cis-2-Chloro-1,3,3,3-tetrafluoropropene and Trans-2-Chloro-1,3,3,3-tetrafluoropropene>
Cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)) and trans-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)) In the performance evaluation of the organic Rankine cycle system using the mixed heat transfer medium (mixed working medium), the power generation cycle efficiency and the expander size parameter were calculated under the calculation conditions shown in Table 17. In FIG. 21, Example 22 (cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)): trans-2-chloro-1,3,3,3- The Ts diagram in the tetrafluoropropene (HCFO-1224xe (E) mass ratio is 95: 5) is shown.

[Comparative Example 6]
<Organic Rankine cycle system using 2,2-dichloro-1,1,1-trifluoroethane (II)>
Instead of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) which is the heat transfer medium (working medium) of the present invention, 2,2-dichloro-1,1,1-trifluoro In the performance evaluation of the organic Rankine cycle system using ethane (HCFC-123) as a working medium, the power generation cycle efficiency and the expander size parameter were calculated under the calculation conditions shown in Table 17. FIG. 22 shows a Ts diagram in Comparative Example 6.

Table 18 shows the calculation results of the organic Rankine cycle system performance (η _cycle and SP) of Examples 17 and 18 and Comparative Example 5 described above.

Table 19 shows the calculation results of the organic Rankine cycle system performance (η _cycle and SP) of Example 19. In Table 19, the values of the first component and the second component of the heat transfer medium (working medium) are expressed as mass percentages. The first component of the heat transfer medium (working medium) is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)), and the second component is trans-2-chloro- 1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)).

Regarding the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP value of Examples 17 and 18 shown in Table 18, the expander inlet volume flow rate, the expander outlet volume flow rate, and the power generation cycle of Comparative Example 5, respectively. Table 20 shows the relative values calculated with the efficiency and SP value as 1.

About the expander inlet volume flow rate, expander outlet volume flow rate, power generation cycle efficiency and SP value of Example 19 shown in Table 19, the expander inlet volume flow rate, expander outlet volume flow rate, power generation cycle efficiency and Table 21 shows the relative values calculated with an SP value of 1.

Table 22 shows the calculation results of the organic Rankine cycle system performance (η _cycle and SP) of Examples 20 and 21 and Comparative Example 6 described above.

Table 23 shows the calculation results of the organic Rankine cycle system performance (ηcycle and SP) of Example 22. In Table 23, the values of the first component and the second component of the heat transfer medium (working medium) are expressed as mass percentages. The first component of the heat transfer medium (working medium) is cis-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)), and the second component is trans-2-chloro- 1,3,3,3-tetrafluoropropene (HCFO-1224xe (E)).

About the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP value of Examples 20 and 21 shown in Table 22, the expander inlet volume flow rate, the expander outlet volume flow rate, and the power generation cycle of Comparative Example 6, respectively. The relative values calculated with the efficiency and SP value as 1 are shown in Table 24.

About the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency, and the SP value of Example 22 shown in Table 23, the expander inlet volume flow rate, the expander outlet volume flow rate, the power generation cycle efficiency of Comparative Example 6 and Table 25 shows the relative values calculated by setting the SP value to 1.

The heat transfer medium (working medium) of the present invention, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), and the existing working medium, 2,2-dichloro-1,1,1 -When compared with trifluoroethane, as shown in Table 18 to Table 25, the power generation cycle efficiency when applied to the organic Rankine cycle system was almost the same. On the other hand, the expander size parameter (SP) has a lower value when 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), which is the heat transfer medium (working medium) of the present invention, is used. It became. That is, 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), which is the heat transfer medium (working medium) of the present invention, is heated to 60 ° C. to 170 ° C. for mechanical energy (and electrical energy). When used as a working medium in an organic Rankine cycle system for converting to), the device is smaller while maintaining cycle efficiency than the working medium containing 2,2-dichloro-1,1,1-trifluoroethane. It is possible to make it.

The heat transfer medium for heat cycle of the present invention is a composition containing 50% by mass or more of 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe) that is nonflammable and has a low environmental impact. It has excellent thermal cycle characteristics and is useful as a heat transfer medium (working medium) for refrigeration cycle systems, high-temperature heat pump cycle systems, and organic Rankine cycle systems. In particular, it is suitable for a refrigeration cycle system equipped with a centrifugal compressor, and also suitable for a high-temperature heat pump system for the purpose of recovering geothermal energy from low to high temperature waste heat of about 50 to 200 ° C. Moreover, it is suitable also for the organic Rankine cycle system for recovering the thermal energy of the medium and low temperature waste heat and converting it into electric energy.

11: evaporator, 12: compressor, 13: condenser, 14: expansion valve, 100: refrigeration cycle system or high temperature heat pump cycle system, 20: evaporator, 21: condenser, 22: expander, 23: circulation pump , 24: generator, 200: organic Rankine cycle system

Claims

A heat transfer medium for a refrigeration cycle system, a heat pump cycle system or an organic Rankine cycle system characterized by containing 50% by mass or more of 2-chloro-1,3,3,3-tetrafluoropropene.
The heat transfer medium according to claim 1, wherein the heat transfer medium contains 90% by mass or more of cis-2-chloro-1,3,3,3-tetrafluoropropene.
The heat transfer medium is a mixture of a cis isomer and a trans isomer of 2-chloro-1,3,3,3-tetrafluoropropene, and the 2-chloro-1,3,3,3-tetrafluoropropene The mass ratio of the cis isomer to the trans isomer is such that the mass ratio of the cis isomer is 50% by mass to 99.9% by mass, and the mass ratio of the trans isomer is 0.1% by mass to 50% by mass. The heat transfer medium according to claim 1.
The heat transfer medium according to claim 1, wherein the heat transfer medium includes a lubricating oil.
The lubricating oil is a mineral oil including paraffinic oil or naphthenic oil, or alkylbenzenes (AB), poly-α-olefin (PAO), esters, polyol esters (POE), polyalkylene glycols, which are synthetic oils. The heat transfer medium according to claim 4, wherein the heat transfer medium is selected from the group (PAG), polyvinyl ethers (PVE), and combinations thereof.
The heat transfer medium according to claim 1, wherein the heat transfer medium further includes a stabilizer.
The stabilizer is a nitro compound, an epoxy compound, a phenol, an imidazole, an amine, a diene compound, a phosphate ester, an aromatic unsaturated hydrocarbon, an isoprene, a propadiene, a terpene, and the like. The heat transfer medium according to claim 6, wherein the heat transfer medium is selected from a combination.
A refrigeration cycle system using the heat transfer medium according to claim 1.
A heat pump cycle system using the heat transfer medium according to claim 1.
An organic Rankine cycle system using the heat transfer medium according to claim 1.
Vaporizing the heat transfer medium of claim 1;
Compressing the heat transfer medium;
Condensing the heat transfer medium;
Squeezing and expanding the heat transfer medium;
including,
A heat transfer method using a refrigeration cycle system containing the heat transfer medium.
Vaporizing the heat transfer medium of claim 1;
Compressing the heat transfer medium;
Condensing the heat transfer medium;
Squeezing and expanding the heat transfer medium;
including,
A heat transfer method using a high-temperature heat pump cycle system containing the heat transfer medium.
Vaporizing the heat transfer medium of claim 1;
Expanding the heat transfer medium;
Condensing the heat transfer medium;
Boosting and transferring the heat transfer medium with a pump;
including,
A method for converting thermal energy into mechanical energy using an organic Rankine cycle system containing the heat transfer medium.
Supplying the heat transfer medium according to claim 1 to a refrigeration cycle system using a heat transfer medium comprising 2,2-dichloro-1,1,1-trifluoroethane;
A method for replacing a heat transfer medium in a refrigeration cycle system comprising:
Supplying the heat transfer medium of claim 1 to a high temperature heat pump cycle system using a heat transfer medium comprising 2,2-dichloro-1,1,1-trifluoroethane;
A method for replacing a heat transfer medium in a high temperature heat pump cycle system comprising:
Supplying the heat transfer medium of claim 1 to an organic Rankine cycle system using a heat transfer medium comprising 2,2-dichloro-1,1,1-trifluoroethane;
A method for replacing a heat transfer medium in an organic Rankine cycle system comprising: