Composition for thermal cycle system and thermal cycle system

Abstract

Provided are a composition for a thermal cycle system containing 1,1,2-trifluoroethylene, which includes a working medium that can suppress the impact of global warming and has cycle performance that can replace R410A, and a thermal cycle system using the composition. A composition for a thermal cycle system and a thermal cycle system using the composition are provided. The composition includes a thermal cycle working medium containing 1,1,2-trifluoroethylene, CF3I, and at least one compound selected from hydrofluorocarbons, hydrofluoroolefins other than 1,1,2-trifluoroethylene, and hydrocarbons, and has a temperature gradient of 7°C or less.

Description

[0001] This application is a divisional application of the Chinese patent application with the application date of October 1, 2019, application number 2019800651906, and invention name “Composition for thermal cycle system and thermal cycle system”. Technical Field

[0002] The present invention relates to a composition for a thermal cycle system and a thermal cycle system using the composition. Background Art

[0003] Traditionally, chlorofluorocarbons (CFCs) such as chlorotrifluoromethane and dichlorodifluoromethane, and hydrochlorofluorocarbons (HCFCs) such as chlorodifluoromethane have been used as refrigerants in refrigerators, air conditioners, power generation systems (such as waste heat recovery power generation), latent heat transfer devices (such as heat pipes), and secondary cooling media in heat circulation systems. However, CFCs and HCFCs have been cited for their potential impact on the stratospheric ozone layer and are now subject to regulation.

[0004] For this reason, hydrofluorocarbons (HFCs) such as difluoromethane (HFC-32), tetrafluoroethane, and pentafluoroethane (HFC-125), which have minimal impact on the ozone layer, have begun to be used as working fluids in heat cycle systems, replacing CFCs and HCFCs. For example, R410A (a pseudo-azeotropic mixture of HFC-32 and HFC-125 in a 1:1 mass ratio) has long been a widely used refrigerant. However, HFCs have been criticized for their potential to contribute to global warming.

[0005] R410A is widely used in conventional air conditioning equipment, such as so-called box air conditioners and room air conditioners, due to its high refrigeration capacity. However, its high Global Warming Potential (GWP) of 2088 necessitates the development of a lower-GWP working medium. This requires the development of a working medium that can replace only R410A while allowing existing equipment to continue to operate.

[0006] Hydrofluoroolefins (HFOs), or HFCs with carbon-carbon double bonds, have recently been highly anticipated as working media due to their carbon-carbon double bonds, which are easily decomposed by OH radicals in the atmosphere. These HFCs have minimal impact on the ozone layer and contribute to global warming. In this specification, unless otherwise specified, saturated HFCs are referred to as HFCs, distinguishing them from HFOs. Furthermore, HFCs are sometimes explicitly referred to as saturated hydrofluorocarbons.

[0007] For example, Patent Document 1 discloses technology using 1,1,2-trifluoroethylene (HFO-1123) as a working medium using HFO, which exhibits the aforementioned properties and offers excellent cycle performance. Patent Document 1 also attempts to combine HFO-1123 with various HFCs and HFOs as a working medium in order to further improve the working medium's non-flammability and cycle performance.

[0008] HFO-1123 is known to undergo so-called autodecomposition under high temperature or high pressure in the presence of an ignition source. Therefore, various studies have been conducted on technologies for adding stabilizers to inhibit the autodecomposition of HFO-1123. Working media containing CF3I as such a stabilizer are also known (see, for example, Patent Documents 2 and 3).

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: International Publication No. 2012 / 157764

[0012] Patent Document 2: International Publication No. 2015 / 125885

[0013] Patent Document 3: Japanese Patent Application Laid-Open No. 2018-104566 Summary of the Invention

[0014] Problems to be solved by the invention

[0015] However, although the combined use of HFO-1123 and CF3I can suppress the self-decomposition of HFO-1123 and utilize its high thermal cycle performance, increasing the CF3I content increases the temperature gradient of the working medium, causing composition fluctuations within the thermal cycle system, which sometimes becomes a practical problem.

[0016] Therefore, an object of the present invention is to provide a composition for a thermal cycle system comprising HFO-1123 and CF3I, which contains a working medium that effectively utilizes the high thermal cycle performance of the composition and keeps the temperature gradient within a predetermined range, and a thermal cycle system using the composition.

[0017] Furthermore, the present invention aims to provide a composition for a heat cycle system comprising a heat cycle working medium having properties of suppressing the global warming effect, imparting non-flammability, and being capable of replacing R410A, R407C, R404A, etc., and a heat cycle system using the composition.

[0018] Solutions for solving problems

[0019] The present invention provides a composition for a heat cycle system and a heat cycle system having the structures described in the following [1] to [9].

[0020] [1] A composition for a heat cycle system, characterized in that it contains a heat cycle working medium, wherein the heat cycle working medium contains 1,1,2-trifluoroethylene, CF3I and at least one compound selected from hydrofluorocarbons, hydrofluoroolefins other than the aforementioned 1,1,2-trifluoroethylene, and hydrocarbons, and the temperature gradient is 7°C or less.

[0021] [2] The composition for a thermal cycle system according to [1], wherein the hydrofluorocarbon is difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane or fluoroethane.

[0022] [3] The composition for a thermal cycle system according to [1] or [2], wherein the hydrofluorocarbon is difluoromethane.

[0023] [4] The composition for a thermal cycle system according to [1] or [2], wherein the hydrofluorocarbon is pentafluoroethane.

[0024] [5] The composition for a thermal cycle system according to [1] or [2], wherein the hydrofluorocarbon is 1,1,1,2-tetrafluoroethane.

[0025] [6] The composition for a thermal cycle system according to [1] or [2], wherein the hydrofluorocarbon is fluoroethane.

[0026] [7] The composition for a thermal cycle system according to any one of [1] to [6], wherein the hydrofluoroolefin is 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene, trans-1,2-difluoroethylene, or cis-1,2-difluoroethylene.

[0027] [8] The composition for a heat cycle system according to any one of [1] to [7], wherein the hydrocarbon is propane.

[0028] [9] The composition for a heat cycle system according to any one of [1] to [8], wherein the content of the hydrofluorocarbon is 10 to 30% by mass.

[0029]

[10] The composition for a heat cycle system according to any one of [1] to [9], which is non-flammable.

[0030]

[11] A thermal cycle system using the composition for a thermal cycle system according to any one of [1] to

[10] .

[0031]

[12] The heat cycle system according to

[11] , wherein the heat cycle system is a refrigeration / refrigeration equipment, an air conditioning equipment, a power generation system, a heat transfer device or a secondary cooler.

[0032] Effects of the Invention

[0033] The heat cycle system composition of the present invention can provide a heat cycle system composition containing a mixed working medium that utilizes the excellent cycle performance of 1,1,2-trifluoroethylene (HFO-1123) and has a low temperature gradient, and can replace R410A, R407C, and R404A.

[0034] According to the heat cycle system of the present invention, a heat cycle system having both high cycle performance and durability can be obtained by applying the composition for a heat cycle system of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a diagram schematically showing the configuration of a refrigeration cycle system as an example of the thermal cycle system of the present invention.

[0036] Figure 2 For the general Figure 1 The state changes of the working medium in the heat cycle of the refrigeration cycle system are recorded in the cycle diagram on the pressure-enthalpy diagram. DETAILED DESCRIPTION

[0037] Hereinafter, the present invention will be described in detail with reference to embodiments.

[0038] In the present specification, regarding halogenated hydrocarbons, the abbreviations of the compounds are described in parentheses after the compound names, and the abbreviations are used in place of the compound names as needed.

[0039] In this specification, when a compound name or a compound abbreviation is used without particular limitation, a compound that has Z- or E-form geometric isomers depending on the position of a substituent bonded to a carbon having a double bond represents either the Z- or E-form, or a mixture of the Z- or E-forms in any ratio. When a compound name or a compound abbreviation is followed by (Z) or (E), it represents either the Z- or E-form of the compound.

[0040] [Composition for thermal cycle system]

[0041] The composition for a thermal cycle system of this embodiment includes a thermal cycle working medium (hereinafter also referred to as "working medium"), wherein the thermal cycle working medium contains HFO-1123, CF3I, and at least one compound selected from hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs) other than HFO-1123, and hydrocarbons (HC), and has a temperature gradient of 7°C or less.

[0042] The composition for a heat cycle system according to the present embodiment contains a working medium with a suppressed temperature gradient, and can be used as a working medium that can replace R410A or R407C, for example.

[0043] <Working Medium>

[0044] As described above, the composition for a heat cycle system according to the present embodiment contains a working medium containing HFO-1123, CF3I, and at least one compound selected from the group consisting of HFC, HFO other than HFO-1123, and HC.

[0045] The HFO-1123 used in this embodiment is 1,1,2-trifluoroethylene, which is well known as a working medium. This HFO-1123 has high cycle performance for use in thermal cycles and has a low GWP, making it a preferred compound as a working medium considering the global environment. The relative cycle performance (relative coefficient of performance and relative refrigeration capacity) of this HFO-1123 is shown in Table 1. This relative cycle performance is a relative comparison with R410A (a pseudo-azeotropic refrigerant mixture with a mass ratio of HFC-32 to HFC-125 of 1:1). In this specification, the relative coefficient of performance is also referred to as relative COP, and the relative refrigeration capacity is also referred to as relative capacity. It should be noted that the composition for the circulation system of this embodiment is also considered from the perspective of replacing R407C (a mixed composition of HFC-32, HFC-125 and HFC-134a in a mass ratio of 23:25:52) and R134a. In Table 1, the numerical values ​​of R407C and R134a compared with R410A are also shown in the reference.

[0046] [Table 1]

[0047] R410A R407C HFO-1123 R134a Relative performance coefficient 1 1.05 0.94 1.08 Relative freezing capacity 1 0.71 1.12 0.45 Temperature gradient [℃] 0 5 0 0 GWP 1924 1624 <1 1300 Discharge pressure difference [kPa] 0 -866.9 656.2 -1569.9 Discharge temperature difference [℃] 0 -2.7 -8.8 -11.8

[0048] The CF3I used in this embodiment functions as a working medium and can suppress the autodecomposition of HFO-1123. Although the proportions of other components also have an impact, it is the component that can suppress the flammability of the heat cycle system composition containing the heat cycle working medium when released into the air.

[0049] The compound used in this embodiment is at least one compound selected from HFC, HFO other than HFO-1123, and HC. These compounds can improve the desired properties when used in combination with the above-mentioned HFO-1123 and CF3I. These compounds are described below.

[0050] (HFC)

[0051] The HFC used in this embodiment is preferably selected from the above-mentioned perspectives. Specifically, the HFC, when combined with HFO-1123 and CF3I, is suitably selected from the perspectives of improving the cycle performance of the working medium and controlling the temperature gradient within an appropriate range. Furthermore, it is preferably suitably selected from the perspectives of controlling the GWP within an acceptable range and suppressing flammability when used as a composition for a thermal cycle system.

[0052] Specifically, HFCs having little effect on the ozone layer and little effect on the global warming effect are preferably HFCs having a carbon number of 1 to 5. HFCs may be linear, branched, or cyclic.

[0053] Examples of HFC include difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane (HFC-125), pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, and heptafluorocyclopentane.

[0054] Among them, as HFCs, HFC-32, HFC-161, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), and HFC-125 are preferred from the viewpoints of having little effect on the ozone layer and excellent refrigeration cycle characteristics. HFC-32, HFC-161, HFC-152a, HFC-134a, and HFC-125 are more preferred, and HFC-32, HFC-134a, and HFC-125 are still more preferred.

[0055] HFCs may be used alone or in combination of two or more.

[0056] (HFO)

[0057] HFOs other than HFO-1123, as optional components, are preferably selected from the same perspective as the HFCs described above. It should be noted that HFOs other than HFO-1123 have a GWP that is orders of magnitude lower than that of HFCs. Therefore, rather than considering GWP, it is more preferable to select HFOs other than HFO-1123 that are combined with HFO-1123 by paying particular attention to improving the cycle performance of the working medium and controlling the temperature gradient and discharge temperature difference within appropriate ranges.

[0058] Examples of HFOs other than HFO-1123 include 2,3,3,3-tetrafluoropropylene (HFO-1234yf), 1,1-difluoroethylene (HFO-1132a), trans-1,2-difluoroethylene (HFO-1132(E)), cis-1,2-difluoroethylene (HFO-1132(Z)), 2-fluoropropylene (HFO-1261yf), 1,1,2-trifluoropropylene (HFO-1243yf), and 1,1,2-trifluoropropylene (HFO-1243yf). c), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), 3,3,3-trifluoropropene (HFO-1243zf), etc.

[0059] Among these, HFOs other than HFO-1123 are preferably HFO-1132(E), HFO-1132(Z), HFO-1234yf, HFO-1234ze(E), HFO-1234ze(Z), and HFO-1243zf, from the perspectives of having a high critical temperature, safety, and excellent coefficient of performance. HFO-1132(E), HFO-1132(Z), HFO-1234yf, HFO-1234ze(E), and HFO-1234ze(Z) are more preferred, and HFO-1234yf is even more preferred. HFOs other than HFO-1123 may be used alone or in combination of two or more.

[0060] (HC)

[0061] Examples of HC include propane, propylene, cyclopropane, butane, isobutane, pentane, and isopentane. Among these, propane is preferred as HC from the perspectives of safety, excellent coefficient of performance, and low GWP.

[0062] HC may be used alone or in combination of two or more.

[0063] The working medium used in this embodiment contains, in addition to the HFO-1123 and CF3I described above, compounds used in combination with these as essential components. The content of each component in the working medium will be described below.

[0064] When HFC is included, its content can be arbitrarily selected according to the required characteristics of the working medium. In the case of a working medium containing HFO-1123, CF3I, and HFC-125, a content of 40-60% by mass of HFO-1123, 10-30% by mass of CF3I, and 20-30% by mass of HFC-125 can reduce the temperature gradient and improve the relative performance coefficient, so it is preferred. Furthermore, from the perspective of further reducing the temperature gradient, a content of 50-60% by mass of HFO-1123, 10-20% by mass of CF3I, and 20-30% by mass of HFC-125 is more preferred. From the perspective of making the resulting working medium non-flammable, HFC-125 is also preferred.

[0065] When the working medium contains HFO-1123, CF3I, and HFC-134a, a working medium with an HFO-1123 content of 30-60% by mass, a CF3I content of 10-40% by mass, and an HFC-134a content of 20-40% by mass is preferred because it can reduce the temperature gradient. Furthermore, from the perspective of further improving performance, a working medium with an HFO-1123 content of 40-60% by mass, a CF3I content of 10-30% by mass, and an HFC-134a content of 20-40% by mass is more preferred. Furthermore, from the perspective of making the resulting working medium non-flammable, HFC-134a is also preferred.

[0066] In the case of a working medium containing HFO-1123, CF3I, and HFC-32, a working medium with an HFO-1123 content of greater than 0 and less than 60% by mass, a CF3I content of 10 to 60% by mass, and an HFC-32 content of 10% to less than 90% by mass is preferred because it can reduce the temperature gradient and improve the relative coefficient of performance. To reduce the GWP, a working medium with an HFO-1123 content of greater than 0 and less than 60% by mass, a CF3I content of greater than 10% to less than 50% by mass, and an HFC-32 content of 10% to less than 90% by mass is more preferred. Furthermore, HFC-32 is also preferred from the perspective of suppressing the GWP of the resulting working medium.

[0067] In the case of a working medium containing HFO-1123, CF3I, and HFC-161, a working medium containing 30-60% by mass of HFO-1123, 20-50% by mass of CF3I, and 10-30% by mass of HFC-161 is preferred because it can reduce the temperature gradient. Furthermore, from the perspective of further reducing the temperature gradient, a working medium containing 30-60% by mass of HFO-1123, 20-50% by mass of CF3I, and 20-30% by mass of HFC-161 is more preferred.

[0068] In addition, when HFC is contained, multiple HFCs may be contained. The content thereof can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium containing HFO-1123, CF3I, HFC-125 and HFC-32, the temperature gradient can be reduced by having an HFO-1123 content of 10 to 40% by mass, a CF3I content of 30 to 50% by mass, an HFC-125 content of 10 to 20% by mass, and an HFC-32 content of 10 to 40% by mass, so it is preferred. It should be noted that from the perspective of improving relative capacity, it is preferred that the HFO-1123 content is 10 to 40% by mass, the CF3I content is 20% or more and less than 40% by mass, the HFC-125 content is 10 to 20% by mass, and the HFC-32 content is 10 to 40% by mass.

[0069] For example, in the case of a working medium containing HFO-1123, CF3I, HFC-125, HFC-134a, and HFC-32, a content of 10 to 40% by mass of HFO-1123, 10 to 30% by mass of CF3I, 5 to 15% by mass of HFC-125, 10 to 30% by mass of HFC-134a, and 10 to 40% by mass of HFC-32 is preferred because the temperature gradient can be reduced. Furthermore, from the perspective of further reducing the temperature gradient, a content of 10 to 40% by mass of HFO-1123, a content of greater than 10% by mass and less than 30% by mass of CF3I, a content of 5 to 15% by mass of HFC-125, a content of 10% to less than 30% by mass of HFC-134a, and a content of 10 to 40% by mass of HFC-32 are more preferably used.

[0070] When HFOs other than HFO-1123 are included, their contents can be arbitrarily selected based on the required properties of the working medium. For example, in the case of a working medium containing HFO-1123, CF3I, and HFO-1234yf, a working medium containing HFO-1123 in the range of 10-40 mass%, CF3I in the range of 20-80 mass%, and HFO-1234yf in the range of 10-70 mass% preferably achieves a relative capacity (R410A ratio) of 0.45 relative to 134a refrigerant, providing sufficient capacity.

[0071] Furthermore, from the perspective of further reducing the temperature gradient, the HFO-1123 content is preferably 10-20% by mass, the CF3I content is 20-80% by mass, and the HFO-1234yf content is greater than 10% by mass and less than 70% by mass. On the other hand, from the perspective of improving relative performance, the HFO-1123 content is preferably 20-40% by mass, the CF3I content is 20-50% by mass, and the HFO-1234yf content is greater than 30% by mass and less than 60% by mass.

[0072] For example, in the case of a working medium containing HFO-1123, CF3I, and HFO-1234ze(E), if the HFO-1123 content is in the range of 10 to 20 mass%, the CF3I content is in the range of 30 to 70 mass%, and the HFO-1234ze(E) content is in the range of 20 to 60 mass%, then the relative capacity (R410A ratio) to the 134a refrigerant is 0.45, which is sufficient and is therefore preferred.

[0073] From the viewpoint of improving relative performance, the HFO-1123 content is preferably 15 to 20 mass%, the CF3I content is preferably 40 to 50 mass%, and the HFO-1234ze(E) content is preferably 30 to 40 mass%.

[0074] For example, in the case of a working medium containing HFO-1123, CF3I, and HFO-1132(E), if the HFO-1123 content is in the range of 10 to 90 mass%, the CF3I content is in the range of 10 to 40 mass%, and the HFO-1132(E) content is in the range of 10 to 80 mass%, then the relative capacity (R410A ratio) to the 134a refrigerant is 0.45, which is sufficient and is therefore preferred.

[0075] Furthermore, from the perspective of further reducing the temperature gradient, the HFO-1123 content is preferably in the range of 10 to 90 mass%, the CF3I content is 10 to 20 mass%, and the HFO-1132(E) content is preferably in the range of 10 to 80 mass%. On the other hand, from the perspective of improving relative performance, the HFO-1123 content is preferably in the range of 20 to 90 mass%, the CF3I content is preferably 10 to 30 mass%, and the HFO-1132(E) content is preferably in the range of 10 to 80 mass%.

[0076] HFO-1123 and HFO-1132(E) are known to undergo autolysis reactions. From the viewpoint of suppressing the autolysis reactions, the total content of HFO-1123 and HFO-1132(E) is preferably 60% by mass or less.

[0077] For example, in the case of a working medium containing HFO-1123, CF3I, and HFO-1132(Z), if the HFO-1123 content is in the range of 10 to 20 mass%, the CF3I content is in the range of 10 to 60 mass%, and the HFO-1132(Z) content is in the range of 10 to 80 mass%, then the relative capacity (R410A ratio) to the 134a refrigerant is 0.45, which is sufficient and is therefore preferred.

[0078] HFO-1123 and HFO-1132(Z) are known to undergo autolysis reactions. From the viewpoint of suppressing the autolysis reactions, the total content of HFO-1123 and HFO-1132(Z) is preferably 60% by mass or less.

[0079] For example, in the case of a working medium containing HFO-1123, CF3I, HFC-32, and HFO-1132(E), if the HFO-1123 content is 10 to 80 mass%, the CF3I content is 10 to 40 mass%, the HFC-32 content is 10 to 30 mass%, and the HFO-1132(E) content is 10 to 70 mass%, then the relative capacity (R410A ratio) to 134a refrigerant is 0.45, which is sufficient for achieving the desired performance.

[0080] Furthermore, from the perspective of further reducing the temperature gradient, it is preferred that the HFO-1123 content be 10 to 80% by mass, the CF3I content be 10 to 30% by mass, the HFC-32 content be 10 to 30% by mass, and the HFO-1132(E) content be 10 to 70% by mass or less. On the other hand, from the perspective of improving relative performance, it is preferred that the HFO-1123 content be 10 to 80% by mass, the CF3I content be 10 to 30% by mass, and the HFO-1132(E) content be 10 to 60% by mass or less.

[0081] HFO-1123 and HFO-1132(E) are known to undergo autolysis reactions. From the viewpoint of suppressing the autolysis reactions, the total content of HFO-1123 and HFO-1132(E) is preferably 60% by mass or less.

[0082] For example, in the case of a working medium containing HFO-1123, CF3I, HFO-1234yf, and HFO-1132(E), if the HFO-1123 content is in the range of 10 to 80 mass%, the CF3I content is in the range of 10 to 40 mass%, and the HFO-1132(E) content is in the range of 10 to 80 mass%, then the relative capacity (R410A ratio) to the 134a refrigerant is 0.45, which is sufficient for achieving the desired performance.

[0083] Furthermore, from the perspective of further reducing the temperature gradient, it is preferred that the HFO-1123 content be 10 to 80% by mass, the CF3I content be 10 to 20% by mass, and the HFO-1132(E) content be 10 to 80% by mass or less. On the other hand, from the perspective of improving relative performance, it is preferred that the HFO-1123 content be 10 to 80% by mass, the CF3I content be 10 to 30% by mass, and the HFO-1132(E) content be 10 to 80% by mass or less.

[0084] HFO-1123 and HFO-1132(E) are known to undergo autolysis reactions. From the viewpoint of suppressing the autolysis reactions, the total content of HFO-1123 and HFO-1132(E) is preferably 60% by mass or less.

[0085] For example, in the case of a working medium containing HFO-1123, CF3I, HFO-1132(E) and HFO-1132(Z), if the HFO-1123 content is in the range of 10 to 70 mass%, the CF3I content is in the range of 10 to 30 mass%, the HFO-1132(E) content is in the range of 10 to 70 mass%, and the HFO-1132(Z) content is in the range of 10 to 20 mass%, then the relative capacity (R410A ratio) to the 134a refrigerant is 0.45, which can provide sufficient capacity and is therefore preferred.

[0086] In addition, from the viewpoint of further reducing the temperature gradient, it is preferred that the content of HFO-1123 is 10 to 70 mass%, the content of CF3I is 10 to 20 mass%, the content of HFO-1132(E) is 10 to 70 mass%, and the content ratio of HFO-1132(Z) is in the range of 10 mass% or more and less than 20 mass%.

[0087] HFO-1123, HFO-1132(E), and HFO-1132(Z) are known to undergo autolysis reactions. From the viewpoint of suppressing the autolysis reactions, the total content of HFO-1123, HFO-1132(E), and HFO-1132(Z) is preferably 60% by mass or less.

[0088] When HC is included as a compound, its content can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium containing HFO-1123, CF3I, and propane, a content of 40-60% by mass of HFO-1123, 10-40% by mass of CF3I, and 15-30% by mass of propane is preferred because the temperature gradient can be reduced. In addition, propane is preferred because it can suppress the GWP of the resulting working medium to a low level. Furthermore, from the perspective of further reducing the temperature gradient, a content of 40-60% by mass of HFO-1123, 10-35% by mass of CF3I, and 20-30% by mass of propane are more preferred.

[0089] (Other optional ingredients)

[0090] The working medium used in the thermal cycle system composition of this embodiment may further contain other optional components such as chlorofluoroolefins (CFOs) and hydrochlorofluoroolefins (HCFOs). As such optional components, components that have little impact on the ozone layer and little impact on the global warming effect are preferred, as long as the effects of the present invention are not impaired.

[0091] Examples of CFOs include chlorofluoropropenes and chlorofluoroethylene. Preferred CFOs are 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb), and 1,2-dichloro-1,2-difluoroethylene (CFO-1112), as they do not significantly degrade the circulation performance of the working medium and can easily suppress the flammability of the working medium.

[0092] CFO may be used alone or in combination of two or more.

[0093] When the working medium contains CFO, its content is preferably less than 10% by mass, more preferably 1 to 8% by mass, and even more preferably 2 to 5% by mass, relative to 100% by mass of the working medium. When the CFO content is above the lower limit, the combustibility of the working medium is easily suppressed. When the CFO content is below the upper limit, good cycle performance is easily achieved.

[0094] Examples of HCFO include hydrochlorofluoropropene and hydrochlorofluoroethylene. Preferred HCFOs are 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) and 1-chloro-1,2-difluoroethylene (HCFO-1122) because they do not significantly degrade the circulation performance of the working medium and can easily suppress the flammability of the working medium.

[0095] HCFO may be used alone or in combination of two or more.

[0096] When the working medium contains HCFO, the HCFO content in 100% by mass of the working medium is preferably less than 10% by mass, more preferably 1 to 8% by mass, and even more preferably 2 to 5% by mass. When the HCFO content is above the lower limit, the combustibility of the working medium is easily suppressed. When the HCFO content is below the upper limit, good cycle performance is easily achieved.

[0097] When the working medium used in the thermal cycle system composition of the present invention contains other optional components as described above, the total content of the other optional components in the working medium is preferably less than 10% by mass, more preferably 8% by mass or less, and even more preferably 5% by mass or less, relative to 100% by mass of the working medium.

[0098] <Temperature Gradient>

[0099] The temperature gradient is a measure of the difference in composition between the liquid and vapor phases of a mixture's working medium. It's defined as the difference between the starting and ending temperatures of evaporation in a heat exchanger, such as an evaporator or condensation in a condenser. In an azeotropic mixture, the temperature gradient is zero, and pseudo-azeotropic mixtures like R410A have a temperature gradient very close to zero.

[0100] Large temperature gradients, for example, increase the likelihood of frost formation due to lower evaporator inlet temperatures. Furthermore, in heat cycle systems, to improve heat exchange efficiency, the working medium flowing through the heat exchanger is typically directed to flow in opposite directions from a heat source fluid such as water or air. Under stable operation, the temperature difference between these heat source fluids is small. Therefore, using a non-azeotropic mixture with a large temperature gradient makes it difficult to achieve a heat cycle system with high energy efficiency. Therefore, when using a mixture as a working medium, it is desirable to have a working medium with an appropriate temperature gradient.

[0101] Furthermore, non-azeotropic mixtures pose a problem of compositional changes when being filled from a pressure vessel into a refrigeration and air conditioning system. Furthermore, if refrigerant leaks from the refrigeration and air conditioning system, the refrigerant composition within the system is highly likely to change, making it difficult to restore the refrigerant composition to its original state. On the other hand, azeotropic or pseudo-azeotropic mixtures can avoid this problem.

[0102] Therefore, the temperature gradient of the thermal cycler composition of the present embodiment is 7° C. or less, more preferably 6° C. or less, further preferably 5° C. or less, and particularly preferably 3° C. or less.

[0103] <Global Warming Power (GWP)>

[0104] In this embodiment, the GWP is used as an indicator to measure the impact of the working medium on the global warming effect. In this specification, unless otherwise specified, the GWP is the 100-year value from the Fifth Assessment Report (2013) of the Intergovernmental Panel on Climate Change (IPCC). The GWP of a mixture is a weighted average based on the mass of its components.

[0105] The global warming potential (100 years) of HFO-1123 contained in the working medium of this embodiment is 1, as measured based on the IPCC Fifth Assessment Report.

[0106] Furthermore, the GWP of R410A (a 1:1 (by mass) composition of HFC-125 and HFC-32), which has excellent cycle performance and is intended to be replaced by the working fluid of this embodiment, is very high at 1924. The two HFCs contained in R410A and other representative HFCs, such as HFC-134a, also have high GWPs, as shown in Table 2 below. The GWP of R407C (a 23:25:52 (by mass) composition of HFC-32, HFC-125, and HFC-134a), which has excellent cycle performance and is intended to be replaced by the working fluid of this embodiment, is also very high at 1624.

[0107] [Table 2]

[0108] Compound GWP(AR5) R410A 1924 R407C 1624 HFO-1123 <1 HFO-1234yf <1 HFO-1234ze(E) <1 HFC-32 677 HFC-134a 1300 HFC-125 3170 <![CDATA[CF3I]]> <1 <![CDATA[CO2]]> 1

[0109] As mentioned above, HFO-1123 has a very low GWP. Therefore, for example, in order to improve cycle performance, when combined with an HFC having high cycle capacity and high GWP to obtain a mixed composition, it is advantageous in terms of suppressing the GWP to a low level and improving cycle performance compared to other HFOs. In this embodiment, CF3I is also contained to stabilize HFO-1123.

[0110] The GWP of the working medium used in this embodiment is preferably 1000 or less, more preferably 750 or less, further preferably 675 or less, further preferably 500 or less, further preferably 300 or less, further preferably 250 or less, and particularly preferably 150 or less.

[0111] <Cycle Performance>

[0112] Here, as properties required when the working medium is applied to a heat cycle, the cycle performance can be evaluated using the coefficient of performance (also referred to as "COP" in this specification) and the capacity (also referred to as "Q" in this specification). When the heat cycle system is a refrigeration cycle system, the capacity is the refrigeration capacity. As evaluation items when the working medium is applied to a refrigeration cycle system, in addition to the above-mentioned cycle performance, temperature gradient, compressor discharge gas temperature and compressor discharge pressure can be further cited. Specifically, using a reference refrigeration cycle with the temperature conditions shown below, for example, each item is measured using the method described later, and except for the temperature gradient, it is converted into a relative value based on the value of R410A as a substitute object and evaluated. The following evaluation items are described in detail.

[0113] (Temperature conditions of the standard refrigeration cycle)

[0114] Evaporation temperature: 10°C (For non-azeotropic mixtures, this is the average of the evaporation start and end temperatures)

[0115] Condensation end temperature: 45°C (in the case of a non-azeotropic mixture, the average temperature of the condensation start temperature and the condensation end temperature)

[0116] Subcooling (SC); 10℃

[0117] Superheat (SH); 10℃

[0118] Compressor efficiency: 0.7

[0119] 〈Relative performance coefficient〉

[0120] The coefficient of performance (COP) is the value obtained by dividing the output (kW) by the power (kW) consumed to obtain that output (kW), and is equivalent to energy consumption efficiency. The higher the COP, the greater the output can be obtained with less input. The relative COP relative to R410A can be calculated using the following formula (1). It should be noted that in formula (1), the test object represents the working medium for which relative evaluation is required.

[0121]

[0122] Relative Freezing Capacity

[0123] The refrigeration capacity is the output of the refrigeration cycle system. The relative refrigeration capacity relative to R410A can be calculated using the following formula (2). It should be noted that in formula (2), the test object represents the working medium to be relatively evaluated.

[0124]

[0125] Compressor discharge pressure difference

[0126] The compressor discharge gas pressure (Px) of the working medium to be relatively evaluated is subtracted from the compressor discharge gas pressure (P R410A ) is evaluated using the value (PΔ) obtained by averaging the discharge pressure of the compressor in the refrigeration cycle (hereinafter also referred to as "discharge pressure"). The maximum pressure in the refrigeration cycle. Since this affects the design pressure of the compressor, a low discharge pressure is preferred. To replace R410A, the discharge pressure, whether lower or higher than that of R410A, must be a pressure that can be tolerated by the equipment that constitutes the thermal cycle system operating with R410A.

[0127] 〈Compressor discharge gas temperature difference〉

[0128] The compressor discharge gas temperature (Tx) of the working medium to be relatively evaluated is subtracted from the compressor discharge gas temperature (Tx) of the R410A compressor. R410A ) is evaluated by the value (TΔ) obtained by measuring the temperature of the compressor discharge gas in the refrigeration cycle (hereinafter also referred to as the "discharge temperature") is the highest temperature in the refrigeration cycle. The materials constituting the compressor and the composition for the heat cycle system will affect the heat resistance of the refrigeration oil and polymer materials usually contained in addition to the working medium, so it is preferred that the discharge temperature is low. In order to replace R410A, the discharge temperature, whether lower or higher than the discharge temperature of R410A, needs to be a temperature that can be tolerated by the equipment constituting the heat cycle system running with R410A.

[0129] For the working medium used in this embodiment, when replacing R410A, the relative refrigeration capacity RQ R410A It is preferably 0.70 to 1.50, more preferably 0.90 to 1.50, and particularly preferably 1.00 to 1.50. It should be noted that when replacing R407C, the denominators of the above formulas (1) and (2) can also be set to the performance coefficient and refrigeration capacity related to R407C instead of R410A, and the relative capacity can be evaluated.

[0130] In addition, the working medium used in this embodiment can not only replace R410A, but also can be used to replace R134a, especially when it contains HFO other than HFO-1123. R410A It is preferably 0.45 to 1.50, more preferably 0.50 to 1.50, and particularly preferably 0.55 to 1.50.

[0131] In addition, the relative coefficient of performance RCOP R410A , preferably 0.85 to 1.20, more preferably 0.90 to 1.20, and particularly preferably 0.95 to 1.20.

[0132] The discharge pressure difference PΔ is preferably 500 or less, more preferably 100 or less, and particularly preferably 0 or less.

[0133] The discharge temperature difference TΔ is preferably 30°C or less, more preferably 20°C or less, and particularly preferably 10°C or less.

[0134] As a refrigeration cycle system used for evaluating the above characteristics, for example, Figure 1 The following is a refrigeration cycle system using Figure 1 A method for evaluating cycle performance, temperature gradient, compressor discharge gas temperature (Tx), and compressor discharge pressure (Px) of the refrigeration cycle system shown in FIG.

[0135] Figure 1 The refrigeration cycle system 10 shown is a system having the following general structure: a compressor 11 that compresses the working medium vapor A to produce a high-temperature and high-pressure working medium vapor B; a condenser 12 that cools and liquefies the working medium vapor B discharged from the compressor 11 to produce a low-temperature and high-pressure working medium C; an expansion valve 13 that expands the working medium C discharged from the condenser 12 to produce a low-temperature and low-pressure working medium D; an evaporator 14 that heats the working medium D discharged from the expansion valve 13 to produce a high-temperature and low-pressure working medium vapor A; a pump 15 that supplies a load fluid E to the evaporator 14; and a pump 16 that supplies a fluid F to the condenser 12.

[0136] In the refrigeration cycle system 10 , the following cycles (i) to (iv) are repeated.

[0137] (i) The working medium vapor A discharged from the evaporator 14 is compressed by the compressor 11 to produce a high-temperature and high-pressure working medium vapor B (hereinafter referred to as the "AB process").

[0138] (ii) In condenser 12, working medium vapor B discharged from compressor 11 is cooled and liquefied by fluid F to produce low-temperature, high-pressure working medium C. At this time, fluid F is heated to become fluid F', which is discharged from condenser 12 (hereinafter referred to as "BC process").

[0139] (iii) The working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to produce a low-temperature and low-pressure working medium D (hereinafter referred to as "CD process").

[0140] (iv) In evaporator 14, working medium D discharged from expansion valve 13 is heated by load fluid E to produce high-temperature, low-pressure working medium vapor A. At this point, load fluid E is cooled to become load fluid E', which is then discharged from evaporator 14 (hereinafter referred to as the "DA process").

[0141] The refrigeration cycle system 10 is a circulation system that includes adiabatic / isentropic changes, isenthalpic changes, and isobaric changes. Figure 2 When shown on a pressure-enthalpy line (curve) diagram, it can be represented by a trapezoid with A, B, C, and D as vertices.

[0142] The AB process is a process in which the compressor 11 performs adiabatic compression to convert the high-temperature, low-pressure working medium vapor A into the high-temperature, high-pressure working medium vapor B. Figure 2 As will be described later, the working medium vapor A is introduced into the compressor 11 in a superheated state, and the obtained working medium vapor B is also a superheated vapor.

[0143] The compressor discharge gas temperature (discharge temperature) is Figure 2 The temperature (Tx) of state B is the highest temperature in the refrigeration cycle. The compressor discharge pressure (discharge pressure) is Figure 2 The pressure (Px) in state B is the highest pressure in the refrigeration cycle. It should be noted that the BC process is isobaric cooling, so the discharge pressure shows the same value as the condensation pressure. Therefore, Figure 2 For convenience, the condensation pressure is expressed as Px.

[0144] The BC process is a process in which the high-temperature and high-pressure working medium vapor B is converted into the low-temperature and high-pressure working medium C by isobaric cooling using the condenser 12. Figure 2 The BC line represents the pressure at this point. The pressure at this point is the condensing pressure. The intersection of the pressure-enthalpy line and the BC line, T1, on the high enthalpy side, is the condensing temperature, while the intersection of the low enthalpy side, T2, is the condensing boiling point. When the working medium is a non-azeotropic mixture, the temperature gradient is expressed as the difference between T1 and T2.

[0145] The CD process is a process in which the expansion valve 13 is used to perform isenthalpic expansion to convert the low-temperature and high-pressure working medium C into the low-temperature and low-pressure working medium D. Figure 2 It is indicated by the CD line. It should be noted that, if the temperature of the low-temperature and high-pressure working medium C is indicated by T3, then T2-T3 is the degree of subcooling (SC) of the working medium in the cycles (i) to (iv).

[0146] The DA process is a process in which the evaporator 14 is used to perform isobaric heating to convert the low-temperature and low-pressure working medium D into the high-temperature and low-pressure working medium vapor A. Figure 2 The DA line represents the pressure at this point. The pressure at this point is the vaporization pressure. The intersection T6, on the high-enthalpy side of the intersection of the pressure-enthalpy line and the DA line, is the evaporation temperature. If the temperature of the working medium vapor A is represented by T7, then T7-T6 is the superheat (SH) of the working medium in cycles (i) to (iv). Note that T4 represents the temperature of the working medium D.

[0147] For the Q and COP of the working medium, the enthalpy and h of the working medium in each state A (after evaporation, high temperature and low pressure), B (after compression, high temperature and high pressure), C (after condensation, low temperature and high pressure), and D (after expansion, low temperature and low pressure) are used. A 、h B 、h C 、h D When , the following equations (11) and (12) are used to calculate the pressure drop. Losses due to equipment efficiency and pressure drops in piping and heat exchangers are ignored.

[0148] Thermodynamic properties required for calculating the cycle performance of the working medium can be calculated using the generalized equation of state (Soave-Redlich-Kwong equation) based on the corresponding state law and various thermodynamic relationships. When property values ​​are unavailable, they are estimated using the group contribution method.

[0149] Q=h A -h D …(11)

[0150] COP=Q / compression work=(h A -h D ) / (h B -h A )…(12)

[0151] The above (h A -h D ) is equivalent to the output of the refrigeration cycle (kW), (h B -h A ), for example, the amount of power required to operate a compressor is equivalent to the power consumed (kW). Furthermore, Q represents the ability to freeze a load fluid; a higher Q indicates more work can be performed within the same system. In other words, a higher Q means achieving target performance with a smaller amount of working medium, enabling system miniaturization.

[0152] As a heat cycle system to which the composition for a heat cycle system of this embodiment is applied, a heat cycle system using a heat exchanger such as a condenser or evaporator can be used without particular limitation. A heat cycle system, such as a refrigeration cycle, has a mechanism in which a gaseous working medium is compressed by a compressor, cooled by a condenser to produce a high-pressure liquid, the pressure is reduced by an expansion valve, and the liquid is vaporized at a low temperature by an evaporator, where heat is extracted through the heat of vaporization.

[0153] The thermal cycle composition of the present invention contains, in addition to the aforementioned working medium, the same refrigeration oil as conventional thermal cycle compositions. A thermal cycle composition containing the working medium and refrigeration oil may further contain known additives such as stabilizers and leak detection agents.

[0154] <Non-flammability>

[0155] It should be noted that the composition for a heat cycle system according to this embodiment is preferably non-flammable. Whether it is non-flammable can be evaluated by the following flammability test of the working medium contained therein.

[0156] Combustibility evaluation can be conducted using the equipment specified in ASTM E-681. The working medium to be evaluated is prepared by mixing the working media in a predetermined ratio. This working medium is then mixed with air at the predetermined ratio. Combustibility is evaluated at equilibrium at 10-90% by mass of the working medium in increments of 1% by mass.

[0157] After vacuum evacuation of a 12-liter flask placed in a thermostatic chamber controlled at 25°C, each working medium, mixed with air at the aforementioned ratios, was sealed until atmospheric pressure was reached. Next, a 15 kV, 30 mA discharge was applied to the gas phase near the center of the flask for 0.4 seconds to ignite the flask. The spread of the flame was visually observed. Flame spread was determined to be combustible if the upward spread angle was 90° or greater; non-combustible if it was less than 90°.

[0158] <Refrigeration Oil>

[0159] As the refrigeration oil, any known refrigeration oil used in working media containing halogenated hydrocarbons and compositions for heat circulation systems can be used without particular limitation. Specifically, examples of the refrigeration oil include oxygen-containing synthetic oils (ester refrigeration oils, ether refrigeration oils, etc.), fluorine-based refrigeration oils, mineral-based refrigeration oils, and hydrocarbon-based synthetic oils.

[0160] Examples of the ester-based refrigeration oil include dibasic acid ester oil, polyol ester oil, complex ester oil, and polyol carbonate oil.

[0161] Preferred dibasic acid ester oils include esters of dibasic acids having 5 to 10 carbon atoms (such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid) and monohydric alcohols having 1 to 15 carbon atoms and having a linear or branched alkyl group (such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, and pentadecyl alcohol). Specific examples include ditridecyl glutarate, di(2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, and di(3-ethylhexyl) sebacate.

[0162] Preferred polyol ester oils are esters of diols (such as ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, neopentyl glycol, 1,7-heptanediol, and 1,12-dodecanediol) or polyols having 3 to 20 hydroxyl groups (such as trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, glycerol, sorbitol, sorbitan, and sorbitol glycerol condensate) and fatty acids having 6 to 20 carbon atoms (such as linear or branched fatty acids such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, eicosanoic acid, and oleic acid, or so-called neo acids in which the α-carbon atom is a quaternary carbon).

[0163] In addition, these polyol ester oils may also have free hydroxyl groups.

[0164] Preferred polyol ester oils include esters of hindered alcohols (e.g., neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, and pentaerythritol) (e.g., trimethylolpropane trispelargonate, pentaerythritol 2-ethylhexanoate, and pentaerythritol tetrapelargonate).

[0165] Complex ester oils are esters of fatty acids, dibasic acids, monohydric alcohols, and polyhydric alcohols. The fatty acids, dibasic acids, monohydric alcohols, and polyhydric alcohols mentioned above can be used.

[0166] Polyol carbonate oils are esters of carbonic acid and polyols.

[0167] Examples of the polyol include the same diols and polyols as those mentioned above. In addition, the polyol carbonate oil may be a ring-opening polymer of a cyclic alkylene carbonate.

[0168] Examples of the ether-based refrigeration oil include polyvinyl ether oil and polyoxyalkylene oil.

[0169] Examples of the polyvinyl ether oil include polymers obtained by polymerizing vinyl ether monomers such as alkyl vinyl ether and copolymers obtained by copolymerizing vinyl ether monomers and hydrocarbon monomers having olefinic double bonds.

[0170] The vinyl ether monomers may be used alone or in combination of two or more.

[0171] Examples of hydrocarbon monomers having an olefinic double bond include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, α-methylstyrene, and various alkyl-substituted styrenes. The hydrocarbon monomers having an olefinic double bond may be used alone or in combination of two or more.

[0172] The polyvinyl ether copolymer may be a block copolymer or a random copolymer. The polyvinyl ether oil may be used alone or in combination of two or more.

[0173] Examples of the polyoxyalkylene oil include polyoxyalkylene monools, polyoxyalkylene polyols, alkyl ethers of polyoxyalkylene monools and / or polyoxyalkylene polyols, and esters of polyoxyalkylene monools and / or polyoxyalkylene polyols.

[0174] Examples of polyoxyalkylene monools and polyoxyalkylene polyols include compounds obtained by ring-opening addition polymerization of an alkylene oxide having 2 to 4 carbon atoms (such as ethylene oxide and propylene oxide) with an initiator such as water or a hydroxyl-containing compound in the presence of a catalyst such as an alkali metal hydroxide. The oxyalkylene units in the polyalkylene chain may be identical or contain two or more types of oxyalkylene units in a single molecule. Preferably, the molecule contains at least oxypropylene units.

[0175] Examples of the initiator used in the reaction include monohydric alcohols such as water, methanol, and butanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, pentaerythritol, and glycerin.

[0176] As the polyoxyalkylene oil, alkyl ethers and esters of polyoxyalkylene monoalcohols and / or polyoxyalkylene polyols are preferred. Furthermore, as the polyoxyalkylene polyol, polyoxyalkylene glycols are preferred. Alkyl ethers of polyoxyalkylene glycols, which are so-called polyglycol oils and are formed by capping the terminal hydroxyl groups of the polyoxyalkylene glycols with alkyl groups such as methyl groups, are particularly preferred.

[0177] Examples of the fluorine-based refrigeration oil include synthetic oils (mineral oils, poly-α-olefins, alkylbenzenes, alkylnaphthalenes, etc. described later) in which hydrogen atoms are substituted with fluorine atoms, perfluoropolyether oils, fluorinated silicone oils, and the like.

[0178] Examples of mineral-based refrigeration oils include paraffinic mineral oils and naphthenic mineral oils obtained by purifying refrigeration oil fractions obtained by atmospheric distillation or vacuum distillation of crude oil using an appropriate combination of purification treatments (desolventization, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydropurification, clay treatment, etc.).

[0179] Examples of the hydrocarbon-based synthetic oil include poly-α-olefins, alkylbenzenes, and alkylnaphthalenes.

[0180] The refrigeration oil may be used alone or in combination of two or more.

[0181] As the refrigeration oil, from the viewpoint of compatibility with the working medium, one or more selected from the group consisting of polyol ester oil, polyvinyl ether oil, and polyglycol oil are preferred.

[0182] The content of the refrigeration oil in the heat cycle composition may be within a range that does not significantly reduce the effects of the present invention, and is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the working medium.

[0183] <Other optional ingredients>

[0184] The stabilizer optionally contained in the thermal cycle system composition is a component that improves the thermal and oxidative stability of the working medium. The stabilizer can be any of the conventionally known stabilizers used in working media containing halogenated hydrocarbons and thermal cycle systems, such as oxidation resistance improvers, heat resistance improvers, and metal deactivators, without particular limitation.

[0185] Examples of oxidation resistance improvers and heat resistance improvers include N,N'-diphenylphenylenediamine, p-octyldiphenylamine, p,p'-dioctyldiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, N-(p-dodecyl)phenyl-2-naphthylamine, di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothiazines, 6-(tert-butyl)phenol, 2,6-di(tert-butyl)phenol, 4-methyl-2,6-di(tert-butyl)phenol, and 4,4'-methylenebis(2,6-di-tert-butylphenol). These oxidation resistance improvers and heat resistance improvers may be used alone or in combination of two or more.

[0186] Examples of the metal deactivator include imidazole, benzimidazole, 2-mercaptobenzothiazole, 2,5-dimethylmercaptothiadiazole, salicylidene-propylenediamine, pyrazole, benzotriazole, tolyltriazole, 2-methylbenzimidazole, 3,5-dimethylpyrazole, methylenebis-benzotriazole, organic acids or esters thereof, aliphatic primary, secondary or tertiary amines, amine salts of organic or inorganic acids, heterocyclic nitrogen-containing compounds, amine salts of alkyl phosphates or derivatives thereof.

[0187] The content of the stabilizer in the thermal cycle composition may be within a range that does not significantly reduce the effects of the present invention, and is preferably 5 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the working medium.

[0188] Examples of the leak detection substance that the thermal cycle system composition may optionally contain include ultraviolet fluorescent dyes, odorous gases, and odor-masking agents.

[0189] Examples of ultraviolet fluorescent dyes include those disclosed in U.S. Patent No. 4,249,412, JP-A-10-502737, JP-A-2007-511645, JP-A-2008-500437, and JP-A-2008-531836, which are known ultraviolet fluorescent dyes that have been used in thermal cycle systems together with working media containing halogenated hydrocarbons.

[0190] Examples of the odor masking agent include known fragrances described in JP-A-2008-500437 and JP-A-2008-531836, which have been conventionally used in heat cycle systems together with a working medium containing a halogenated hydrocarbon.

[0191] When a leak detection substance is used, a solubilizing agent may be used to increase the solubility of the leak detection substance in the working medium.

[0192] Examples of the solubilizing agent include those described in JP-A-2007-511645, JP-A-2008-500437, and JP-A-2008-531836.

[0193] The content of the leak detection substance in the thermal cycle system composition may be within a range that does not significantly reduce the effects of the present invention, and is preferably 2 parts by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the working medium.

[0194] [Thermal circulation system]

[0195] The heat cycle system of this embodiment is a system using the heat cycle system composition of this embodiment. The heat cycle system of this embodiment may be a heat pump system using warm water obtained by a condenser or a refrigeration cycle system using cold water obtained by an evaporator.

[0196] Specific examples of the thermal cycle system of this embodiment include refrigeration / refrigeration equipment, air conditioning equipment, power generation systems, heat transfer devices, and secondary coolers. The thermal cycle system of the present invention can stably and safely demonstrate its thermal cycle performance even in higher-temperature operating environments, making it suitable for use in air conditioning equipment, which is often installed outdoors. Furthermore, the thermal cycle system of this embodiment is also suitable for use in refrigeration / refrigeration equipment.

[0197] Specific examples of air conditioners include room air conditioners, box air conditioners (box air conditioners for shops, boxes air conditioners for buildings, boxes air conditioners for equipment, etc.), gas engine heat pumps, train air conditioners, and automobile air conditioners.

[0198] Specific examples of the freezing / refrigerating equipment include showcases (built-in showcases, stand-alone showcases, etc.), commercial freezers / refrigerators, vending machines, ice machines, and the like.

[0199] As the power generation system, a power generation system based on a Rankine cycle system is preferable.

[0200] Specifically, the following system can be exemplified as a power generation system: a working medium is heated in an evaporator by geothermal energy, solar heat, or waste heat in a medium to high temperature range of approximately 50 to 200°C, an expander is used to adiabatically expand the working medium, which is a vapor at a high temperature and high pressure, and the work generated by this adiabatic expansion is used to drive a generator, thereby generating electricity.

[0201] The heat cycle system of this embodiment may be a heat transport device. As the heat transport device, a latent heat transport device is preferable.

[0202] Examples of latent heat transport devices include heat pipes and two-phase enclosed thermosiphons, which utilize the evaporation, boiling, and condensation of the working medium enclosed within the device. Heat pipes are suitable for relatively small cooling devices, such as those used to cool the heat-generating components of semiconductor devices and electronic equipment. Two-phase enclosed thermosiphons, which require no wick and have a simple structure, are widely used in gas-to-gas heat exchangers, snow melting promotion, and antifreeze measures for roads.

[0203] Note that, in order to avoid the occurrence of malfunctions due to the incorporation of moisture or non-condensable gases such as oxygen during operation of the heat cycle system, it is preferable to provide a device for suppressing the incorporation of these gases.

[0204] Moisture in the heat circulation system can sometimes cause problems, especially when used at low temperatures. For example, this can lead to ice formation in the capillaries, hydrolysis of the working medium and refrigeration oil, material degradation caused by acidic components generated within the circulation, and the generation of contaminants. Refrigeration oils such as polyglycol and polyol ester oils are particularly hygroscopic and prone to hydrolysis, which can significantly reduce their performance as refrigeration oils and compromise the long-term reliability of the compressor. Therefore, to prevent hydrolysis of refrigeration oil, it is necessary to control the water concentration within the heat circulation system.

[0205] As a method for controlling the water concentration in the heat cycle system, a method using a moisture removal means such as a desiccant (silica gel, activated alumina, zeolite, etc.) can be mentioned. From the perspective of dehydration efficiency, it is preferable to place the desiccant in contact with the liquid heat cycle composition. For example, it is preferable to place a desiccant at the outlet of the condenser 12 or the inlet of the evaporator 14 so that it contacts the heat cycle composition.

[0206] As the desiccant, a zeolite-based desiccant is preferred from the viewpoint of chemical reactivity between the desiccant and the composition for a heat cycle system and the moisture absorption capacity of the desiccant.

[0207] The heat cycle system of the present invention described above uses the working medium of the present invention, which is highly safe, can suppress the impact of the global warming effect, can obtain practically sufficient cycle performance, and has almost no problem with temperature gradients.

[0208] Example

[0209] Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0210] [Examples 1-1~1-11]

[0211] In Examples 1-1 to 1-11, working fluids containing HFO-1123 and CF3I were prepared in the proportions shown in Table 3. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Table 3.

[0212] [Table 3]

[0213]

[0214] The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) of working media containing each compound shown in Table 4 below were measured, and the calculated results are as follows.

[0215] [Table 4]

[0216]

[0217] [Examples 1-12~1-50]

[0218] In Examples 1-12 to 1-50, working media containing HFO-1132(E) in addition to HFO-1123 and CF3I were prepared in the proportions shown in Table 5. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Table 5.

[0219] [Table 5]

[0220]

[0221] [Examples 1-51~1-89]

[0222] In Examples 1-51 to 1-89, working media containing HFO-1132(Z) in addition to HFO-1123 and CF3I were prepared in the proportions shown in Table 6. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Table 6.

[0223] [Table 6]

[0224]

[0225] [Example 1-90~1-134]

[0226] In Examples 1-90 to 1-134, working media containing HFO-1123 and CF3I, along with HFO-1132(E) and HFO-1132(Z), were prepared in the proportions shown in Table 7. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Table 7.

[0227] [Table 7]

[0228]

[0229] [Examples 2-1~2-32]

[0230] In Examples 2-1 to 2-32, working media containing HFC-125 in addition to HFO-1123 and CF3I were prepared in the proportions shown in Table 8. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods, and the calculated results are summarized in Table 8.

[0231] [Table 8]

[0232]

[0233] [Examples 3-1~3-27]

[0234] In Examples 3-1 to 3-27, working media were prepared that contained HFC-134a in addition to HFO-1123 and CF3I in the proportions shown in Table 9. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the methods described above. The calculated results are summarized in Table 9.

[0235] [Table 9]

[0236]

[0237] [Examples 4-1~4-39]

[0238] In Examples 4-1 to 4-39, working fluids were prepared that contained HFC-32 in addition to HFO-1123 and CF3I in the proportions shown in Table 10. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the methods described above. The calculated results are summarized in Table 10.

[0239] [Table 10]

[0240]

[0241] [Example 4-40~4-120]

[0242] In Examples 4-40 to 4-120, working media containing HFC-32 and HFO-1132(E) in addition to HFO-1123 and CF3I were prepared in the proportions shown in Tables 11 and 12. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Tables 11 and 12.

[0243] [Table 11]

[0244]

[0245] [Table 12]

[0246]

[0247] [Examples 5-1~5-34]

[0248] In Examples 5-1 to 5-34, working media containing HFO-1234yf in addition to HFO-1123 and CF3I were prepared in the proportions shown in Table 13. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Table 13.

[0249] [Table 13]

[0250]

[0251] [Examples 5-35~5-140]

[0252] In Examples 5-35 to 5-140, working media containing HFO-1123 and CF3I, along with HFO-1234yf and HFO-1132(E) in the proportions shown in Tables 14 to 16, were prepared. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Tables 14 to 16.

[0253] [Table 14]

[0254]

[0255] [Table 15]

[0256]

[0257] [Table 16]

[0258]

[0259] [Examples 6-1~6-25]

[0260] In Examples 6-1 to 6-25, working media were prepared that contained HFO-1234ze(E) in addition to HFO-1123 and CF3I in the proportions shown in Table 17. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Table 17.

[0261] [Table 17]

[0262]

[0263] [Examples 7-1~7-49]

[0264] In Examples 7-1 to 7-49, working fluids were prepared that contained propane in addition to HFO-1123 and CF3I in the proportions shown in Table 18. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods, and the calculated results are summarized in Table 18.

[0265] [Table 18]

[0266]

[0267] [Examples 8-1~8-49]

[0268] In Examples 8-1 to 8-49, working fluids were prepared that contained HFC-161 in addition to HFO-1123 and CF3I in the proportions shown in Table 19. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the methods described above. The calculated results are summarized in Table 19.

[0269] [Table 19]

[0270]

[0271] [Examples 9-1~9-18]

[0272] In Examples 9-1 to 9-18, working fluids were prepared containing HFC-125 and HFC-32 in addition to HFO-1123 and CF3I in the proportions shown in Table 20. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Table 20.

[0273] [Table 20]

[0274]

[0275] [Examples 10-1~10-12]

[0276] In Examples 10-1 to 10-12, working media containing HFC-125, HFC-134a, and HFC-32 in addition to HFO-1123 and CF3I were prepared in the proportions shown in Table 21. The temperature gradient, discharge temperature difference, and refrigeration cycle performance (relative refrigeration capacity and relative coefficient of performance) were measured using the above-described methods. The calculated results are summarized in Table 21.

[0277] [Table 21]

[0278]

[0279] [Examples 2-17, 3-21, 4-31, 5-28]

[0280] The non-flammability of the following working media, which contain HFC-125, HFC-134a, HFC-32, or HFO-1234yf in addition to HFO-1123 and CF3I in the proportions shown in Table 22, was measured by the above-mentioned method, and the calculated results are summarized in Table 22.

[0281] [Table 22]

[0282]

[0283] Industrial applicability

[0284] The composition for a heat cycle system of the present invention and the heat cycle system using the composition can be used in refrigeration / refrigeration equipment (built-in display cabinets, separate display cabinets, commercial freezers / refrigerators, vending machines, ice machines, etc.), air conditioning equipment (indoor air conditioners, cabinet air conditioners for shops, cabinet air conditioners for buildings, cabinet air conditioners for equipment, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.), power generation systems (waste heat recovery power generation, etc.), and heat transfer devices (heat pipes, etc.).

[0285] It should be noted that the entire contents of the specifications, claims, drawings, and abstracts of Japanese Patent Application No. 2018-186916 filed on October 1, 2018, and Japanese Patent Application No. 2018-193586 filed on October 12, 2018 are incorporated herein by reference and are incorporated as a disclosure of the specification of the present invention.

[0286] Description of Reference Numerals

[0287] 10...refrigeration cycle system, 11...compressor, 12...condenser, 13...expansion valve, 14...evaporator, 15, 16...pump

Claims

1. A composition for a thermal cycle system, characterized in that The invention relates to a heat cycle working medium comprising 1,1,2-trifluoroethylene, CF3I and any one compound selected from propane, trans-1,2-difluoroethylene, cis-1,2-difluoroethylene, pentafluoroethane and fluoroethane, and the temperature gradient is below 7°C. In the case of containing 1,1,2-trifluoroethylene, CF3I and propane, relative to 100 mass% of the working medium for the heat cycle, the content of 1,1,2-trifluoroethylene is 40-60 mass%, the content of CF3I is 10-40 mass%, and the content of propane is 15-30 mass%. In the case of containing 1,1,2-trifluoroethylene, CF3I and trans-1,2-difluoroethylene, relative to 100 mass% of the working medium for the heat cycle, the content of 1,1,2-trifluoroethylene is 10 to 90 mass%, the content of CF3I is 10 to 40 mass%, and the content of trans-1,2-difluoroethylene is 10 to 80 mass%. In the case of containing 1,1,2-trifluoroethylene, CF3I and cis-1,2-difluoroethylene, relative to 100% by mass of the working medium for the heat cycle, the content of 1,1,2-trifluoroethylene is 10 to 20% by mass, the content of CF3I is 10 to 60% by mass, and the content of cis-1,2-difluoroethylene is 10 to 80% by mass. In the case of containing 1,1,2-trifluoroethylene, CF3I and pentafluoroethane, relative to 100 mass% of the working medium for the heat cycle, the content of 1,1,2-trifluoroethylene is 40-60 mass%, the content of CF3I is 10-30 mass%, and the content of pentafluoroethane is 20-30 mass%. In the case of containing 1,1,2-trifluoroethylene, CF3I and fluoroethane, relative to 100 mass% of the working medium for the heat cycle, the content of 1,1,2-trifluoroethylene is 30-60 mass%, the content of CF3I is 20-50 mass%, and the content of fluoroethane is 10-30 mass%. The thermal cycle working medium does not include any other component or contains less than 10% by mass of any other component relative to 100% by mass of the thermal cycle working medium.

2. The composition for a thermal cycle system according to claim 1, wherein The working medium for the thermal cycle contains 1,1,2-trifluoroethylene, CF3I and any one compound selected from propane, trans-1,2-difluoroethylene, cis-1,2-difluoroethylene and fluoroethane. The composition for a heat cycle system according to claim 1 or 2, which is non-flammable. A thermal cycle system using the composition for a thermal cycle system according to any one of claims 1 to 3.

5. The thermal cycle system according to claim 4, wherein: The thermal cycle system is a freezing / refrigeration device or a power generation system. The thermal cycle system according to claim 4 , wherein: The thermal circulation system is a heat transport device.

7. The thermal cycle system according to claim 4, wherein: The thermal cycle system is an air conditioning device or a secondary cooler.

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