COMPOSITION WITH COOLANT AND APPLICATION OF THE SAYEN COMPOSITION

Description

Technical Field

[0001]

[0001] The present invention relates to the use of a composition containing a refrigerant.Background Art

[0002] Fluorinated hydrocarbons that contain no chlorine in their molecular structure, such as difluoromethane (CH 2 F 2 , R32, boiling point: -52°C), pentafluoroethane (CF 3 CHF 2 , R125, boiling point: -48°C), 1,1,1-trifluoroethane (CF 3 CH 3 , R143a, boiling point: -47°C), 1,1,1,2-tetrafluoroethane (CF 3 CH 2 F, R134a, boiling point: -26°C), 1,1-difluoroethane (CHF 2 CH 3 , R152a, boiling point: -24°C), and 2,3,3,3-tetrafluoropropene (CF 3 CF=CH 2 , 1234yf, boiling point: -29°C), have been used as refrigerants for air conditioners, refrigerating machines, refrigerators, and other similar equipment.

[0003] Among such fluorinated hydrocarbons, a ternary mixed refrigerant of R32 / R125 / R134a in which their proportions are 23 / 25 / 52 wt% (R407C), a ternary mixed refrigerant of R125 / 143a / R134a in which their proportions are 44 / 52 / 4 wt% (R404A), etc., have been proposed, and R404A is currently widely used as a refrigerant for freezing and refrigerated storage (for example, JP-B-2869038 and US 8,168,077.

[0004] However, the global warming potential (GWP) of R404A is as extremely high as 3922, and is known to be even higher than that of CHClF 2 (R22, GWP = 1810), which is a chlorine-containing fluorinated hydrocarbon. There is thus a demand to develop, as an alternative refrigerant for R404A, refrigerants that have a refrigerating capacity equal to that of R404A, a ratio of refrigerating capacity to power consumed in a refrigeration cycle (coefficient of performance (COP)) equal or superior to that of R404A, a low GWP, a low compressor outlet temperature, and performance of non-flammable refrigerants (ASHRAE non-flammability (class 1 refrigerants defined in ANSI / ASHRAE 34-2013)), as with R404A.

[0005] There are still many refrigerating machines that use CHClF 2 (R22) as chlorine-containing fluorinated hydrocarbons (HCFCs), which were used as refrigerants for freezing and refrigerated storage before the use of R404A; however, under the Montreal Protocol, HCFCs are required to be abolished by 2020 in developed countries and to be phased out in a stepwise manner (first: 10%, second: 35%) in developing countries. For these refrigerating machines, there is also a demand to develop, as alternative refrigerants for R22, refrigerants that have a compressor outlet pressure equal to that of R22 used in a refrigeration cycle ("R22 retrofit refrigerants"), a low GWP, and performance of non-flammable refrigerants (ASHRAE non-flammability (class 1 refrigerants defined in ANSI / ASHRAE 34-2013)), as with R22.

[0006] There are, for example, JP-B-5689068 and JP-A-2013-529703 as other prior art relating to the present invention.

[0007] US 5,185,094 discloses ternary mixtures of 5-59 wt.% R125, 5-59 wt.% R32 and 5-35 wt.% R134a are useful as refrigerants, aerosol propellants, heat transfer media, gaseous dielectrics, fire extinguishing agents, expansion agents for polyolefins and polyurethanes, and power cycle working fluids.

[0008] EP-A-0 811 670 describes a ternary mixture refrigerant for a heat pump comprises R32 / R125 / R134a in a composition range defined by straight lines A (connecting points a1 (R32 / R134a=43 / 57 wt%) and a2 (R125 / R134a=73 / 27 wt%)), C (connecting points c1 (R32 / R134a=33 / 67 wt%) and c2 (R125 / R134a=65 / 35 wt%)), D (connecting point d1 (R32 / R125=60 / 40 wt%) and a vertex of R134a), and E (connecting points e1 (R32 / R125=53 / 47 wt%) and e2 (R32 / R134a=19 / 81 wt%)) in a ternary composition chart of R32, R125 and R134a.

[0009] EP-A-3 141 587 relates to mixtures comprising R32, R125, and R134a, wherein in a ternary composition diagram in which the sum of R32, R125 and R134a is 100 wt.-% the composition ratio (R32 / R125 / R134a) in the mixture falls within a triangle having the points A (37.3 / 17.0 / 45.7), F (30.7 / 10.9 / 58.4)and G (29.4 / 14.1 / 56.5) as vertices.Summary of InventionTechnical Problem

[0010] As alternative refrigerants for R404A, JP-B-5689068 and JP-A-2013-529703 report refrigerant compositions comprising difluoromethane (R32), pentafluoroethane (R125), 2,3,3,3-tetrafluoropropene (1234yf), and 1,1,1,2-tetrafluoroethane (R134a). However, no one has succeeded in developing a refrigerant composition that has a refrigerating capacity equal to that of R404A, a COP equal to or superior to that of R404A, a low GWP, a compressor outlet temperature of 130°C or lower, and ASHRAE non-flammability performance.

[0011] An object of the present invention is to provide a composition comprising a refrigerant, the composition having a refrigerating capacity equal to that of R404A, which has currently been widely used, a COP equal or superior to that of R404A, a GWP of 1500 or less, a compressor outlet temperature of 130°C or lower, and ASHRAE non-flammability performance. Another object of the present invention is to provide a composition comprising a refrigerant, the composition having a compressor outlet pressure equal to that of R22 and ASHRAE non-flammability performance.Solution to Problem

[0012] The present inventors conducted extensive research to achieve the above object, and consequently found that the object can be achieved by a composition comprising a refrigerant comprising difluoromethane (R32), pentafluoroethane (R125), and 1,1,1,2-tetrafluoroethane (R134a) at specific concentrations. The present invention has been completed based on these findings.

[0013] More specifically, the present invention provides the use of a composition as a drop-in alternative refrigerant for R22 or R404A or as a retrofit refrigerant for R22 or R404A (also referred to as "the present use" hereinafter), wherein the composition comprises a refrigerant, and wherein the refrigerant comprises a mixture of fluorinated hydrocarbons comprising difluoromethane (R32), pentafluoroethane (R125), and 1,1,1,2-tetrafluoroethane (R134a) in amounts such that the sum of the concentrations thereof is ≥ 99.5 wt.-%, and wherein the composition ratio of the fluorinated hydrocarbons contained in the mixture falls within a quadrilateral having, as vertices, the following four points in a ternary composition diagram in which the sum of the concentrations of R32, R125, and R134a is 100 wt.-%: point G'(R32 / R125 / R134a = 25.2 / 11.4 / 63.4 wt%),point T(R32 / R125 / R134a = 24.9 / 9.3 / 65.8 wt%),point R(R32 / R125 / R134a = 19.5 / 4.3 / 76.2 wt%), andpoint I'(R32 / R125 / R134a = 17.9 / 8.7 / 73.4 wt%); provided that composition ratios defined by the points G', T, R and I' and composition ratios falling on the lines connecting these points in a ternary composition diagram are not included.

[0014] Preferred embodiments of the invention are as defined in the appended dependent claims and / or in the following detailed description.Advantageous Effects of Invention

[0015] The composition comprising a refrigerant of the use of the present invention (also referred to as "the present composition" hereinafter) comprises a mixture comprising difluoromethane (R32), pentafluoroethane (R125), and 1,1,1,2-tetrafluoroethane (R134a) at specific concentrations. This composition is for use as an alternative refrigerant for R22, which is an HCFC refrigerant, or as an alternative refrigerant for R404A (R125 / R134a / R143a = 44 / 4 / 52 wt%), which is a mixed refrigerant. Further, the composition has a refrigerating capacity almost equal to that of R404A, a COP equal or superior to that of R404A, a GWP of 1475 or less, and ASHRAE non-flammability performance. Such a composition comprising a refrigerant of the present invention is suitable for use as a working fluid used in a refrigeration method that comprises operating a refrigeration cycle.Brief Description of Drawings

[0016] Fig. 1 shows the concentration of a mixture contained in the present composition (a quadrilateral surrounded by points G', T, R and I') in a ternary composition diagram of R32, R125, and R134a. Fig. 3 shows the relationship between Examples of the present invention and Comparative Examples in a tertiary composition diagram of R32, R125, and R134a. Fig. 4 shows the relationship between P: ASHRAE non-flammable border line and P': ASHRAE non-flammable border line in which allowable ranges are taken into consideration, in a ternary composition diagram of R32, R125, and R134a. Fig. 5 is a schematic view of a unit used in a flammability test. Description of EmbodimentsDefinition of Terms

[0017] In this specification, the term "refrigerant" includes at least compounds that are specified in ISO817 (International Organization for Standardization), and that are given a refrigerant number (ASHRAE number) representing the type of refrigerant with "R" at the beginning; and further includes refrigerants that have properties equivalent to those of such refrigerants, even though a refrigerant number is not yet given. Refrigerants are broadly divided into "fluorocarbon-based compounds" and "non-fluorocarbon-based compounds," in terms of the structure of the compounds. "Fluorocarbon-based compounds" include chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC), and hydrofluorocarbons (HFC). Examples of "non-fluorocarbon-based compounds" include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), and ammonia (R717).

[0018] The term "composition comprising a refrigerant" used in this specification at least includes: (1) a refrigerant itself (including a refrigerant mixture); (2) a composition that can be used for obtaining a working fluid for refrigerating machines by further comprising one or more other components and mixing with at least a refrigerant oil; and (3) a working fluid for refrigerating machines, containing a refrigerant oil.

[0019] Among these three modes, composition (2) is referred to as a "composition comprising a refrigerant" in this specification to distinguish it from a refrigerant itself (including a mixture of refrigerants).

[0020] In this specification, when the term "alternative" is used in the context in which the first refrigerant is replaced with the second refrigerant, the first type of "alternative" means that equipment designed for operation using the first refrigerant can be operated using the second refrigerant under optimum conditions, optionally with changes of only a few parts (at least one member of the refrigerant oil, gasket, packing, expansion valve, dryer, and other parts) and equipment adjustment. In other words, this type of alternative means that the same equipment is operated with an alternative refrigerant. Embodiments of this type of "alternative" include "drop-in alternative," "nearly drop-in alternative," and "retrofit," in the order in which the extent of changes and adjustment necessary for replacing the first refrigerant with the second refrigerant is smaller.

[0021] The term "alternative" also includes the second type of "alternative" that means that equipment designed for operation using the second refrigerant is operated for the same use as the existing use with the first refrigerant, using the second refrigerant. This type of alternative means that the same use is achieved with an alternative refrigerant.

[0022] In the present specification, the term "refrigerating machine (refrigerator)" refers to machines in general that draw heat from an object or space to make its temperature lower than the temperature of ambient air, and maintain the low temperature. In other words, refrigerating machines refer to conversion machines that gain energy from the outside to do work; and that perform energy conversion, in order to transfer heat from where the temperature is lower to where the temperature is higher.

[0023] In terms of the present composition, the refrigerant comprises a mixture of fluorinated hydrocarbons, and the mixture comprises difluoromethane (R32), pentafluoroethane (R125), and 1,1,1,2-tetrafluoroethane (R134a) in amounts such that the sum of the concentrations thereof is 99.5 wt% or more.

[0024] The composition ratio of the fluorinated hydrocarbons contained in the mixture falls within a quadrilateral having, as vertices, the following four points in a ternary composition diagram in which the sum of the concentrations of R32, R125, and R134a is 100 wt% (Fig. 1): point G'(R32 / R125 / R134a = 25.5 / 11.4 / 63.4 wt%),point T(R32 / R125 / R134a = 24.9 / 9.3 / 65.8 wt%),point R(R32 / R125 / R134a = 19.5 / 4.3 / 76.2 wt%), andpoint I'(R32 / R125 / R134a = 17.5 / 8.7 / 73.4 wt%); provided that composition ratios defined by the points G', T, R and I' and composition ratios falling on the lines connecting these points in a ternary composition diagram are not included.

[0025] The present composition is for use as an alternative refrigerant of R22, which is an HCFC refrigerant, or an alternative refrigerant for R404A (R125 / R134a / R143a = 44 / 4 / 52 wt%), which is a mixed refrigerant.

[0026] The present composition has a non-flammability similar to that of R404A, and has a refrigerating capacity that can replace that of R404A, a COP that is equal or superior to that of R404A, and a GWP of 1500 or less. More specifically, since the present composition is non-flammable according to ASHRAE (details of the definition, etc., are described later) like R404A, the present composition is safer than flammable refrigerants and can be used in a wide range of applications.

[0027] Because the GWP is 1475 or less, the present composition can notably reduce the burden on the environment from a global warming perspective, compared with other general-purpose refrigerants. Moreover, since the present composition is non-flammable according to ASHRAE, it is safer than flammable refrigerants and can be used in a wide range of applications.

[0028] The refrigerating capacity of the present composition can replace that of R404A. More specifically, the refrigerating capacity is 76.5% or more, preferably 80% or more, and more preferably 85% or more, relative to that of R404A. R404A is a refrigerant currently widely used as a refrigerant for freezing and refrigerated storage, and the present composition can be an alternative composition for a conventionally known refrigerant composition comprising R404A.

[0029] In terms of inhibiting deterioration of the unit or the refrigerant oil, the compressor outlet temperature in the refrigeration cycle is preferably 130°C or lower.

[0030] The COP may be equal or superior to that of R404A (100% or more), but is preferably 105% or more, more preferably 107.5% or more, still more preferably 110% or more, and particularly preferably 112% or more, relative to that of R404A.

[0031] In the mixture contained in the present composition, the compressor outlet pressure in a refrigeration cycle is preferably equal to that of R22 (R22 retrofit). R22 was widely used as a refrigerant for freezing and refrigerated storage before the spread of R404A. Many refrigerating machines using R22 as a refrigerant still remain. However, R22 will be abolished in developed countries in 2020 due to the regulation of HCFC, and there is thus a strong demand for alternative refrigerants. It is essential for alternative refrigerants for refrigerating machines using R22 that the compressor outlet pressure, which is the maximum pressure in a refrigeration cycle, is equal to that of R22. The compressor outlet pressure is preferably 110% or less, and more preferably 100% or less, relative to that of R22.

[0032] In the present composition, the refrigerant comprises a mixture of fluorinated hydrocarbons, and the mixture may consist only of three basic components, i.e., difluoromethane (R32), pentafluoroethane (R125), and 1,1,1,2-tetrafluoroethane (R134a).Mixture of Fluorinated Hydrocarbons

[0033] In a composition comprising a refrigerant according to an example of embodiments of the present invention (embodiment 1), the refrigerant comprises a mixture of fluorinated hydrocarbons, and the mixture comprises difluoromethane (R32), pentafluoroethane (R125), and 1,1,1,2-tetrafluoroethane (R134a) in amounts such that the sum of the concentrations thereof is 99.5 wt% or more.

[0034] The composition ratio of the fluorinated hydrocarbons contained in the mixture falls within a quadrilateral having, as vertices, the following four points in a ternary composition diagram in which the sum of the concentrations of R32, R125, and R134a is 100 wt% (Fig. 1): point G'(R32 / R125 / R134a = 25.5 / 11.4 / 63.4 wt%),point T(R32 / R125 / R134a = 24.9 / 9.3 / 65.7 wt%),point R(R32 / R125 / R134a = 19.5 / 4.3 / 76.2 wt%), andpoint I'(R32 / R125 / R134a = 17.5 / 8.7 / 73.4 wt%); provided that composition ratios defined by the points G', T, R and I' and composition ratios falling on the lines connecting these points in a ternary composition diagram are not included.

[0035] This composition is for use as an alternative refrigerant for R22, which is an HCFC refrigerant, or as an alternative refrigerant for R404A, which is a mixed refrigerant.

[0036] In Fig. 1, a straight line (P') passing through two points, i.e., point T and point R, denotes an ASHRAE non-flammable border line when the allowable range (allowable concentration) is set to ±2.0% in the production of R32, R125, and R134a; and a straight line (L) passing through two points, i.e., point G and point I, denotes a line indicating a composition ratio in which GWP is 1500. Further, a straight line passing through two points, i.e., point I and point R, denotes a line indicating a composition ratio in which the refrigerating capacity is 76.5%, relative to R404A, and a straight line passing through two points, i.e., point G and point T, denotes a line at which the compressor outlet temperature is 130°C.

[0037] The quadrilateral surrounded by points G, T, R, and I represents a region that has a GWP of 1500 or less, shows ASHRAE non-flammability in which safety factors are taken into consideration, and has a compressor outlet temperature of 130°C or lower, and a refrigerating capacity of 76.5% or more of that of R404A.

[0038] The present composition comprises a refrigerant, the refrigerant comprises a mixture of fluorinated hydrocarbons, and the mixture comprises R32, R125, and R134a in amounts such that the sum of the concentrations thereof is 99.5 wt% or more.

[0039] The composition ratio of the fluorinated hydrocarbons contained in the mixture falls within a quadrilateral having, as vertices, the following four points in a ternary composition diagram in which the sum of the concentrations of R32, R125, and R134a is 100 wt% (Fig. 1): point G'(R32 / R125 / R134a = 25.2 / 11.4 / 63.4 wt%),point T(R32 / R125 / R134a = 24.9 / 9.3 / 65.8 wt%),point R(R32 / R125 / R134a = 19.5 / 4.3 / 76.2 wt%), andpoint I'(R32 / R125 / R134a = 17.9 / 8.7 / 73.4 wt%); provided that composition ratios defined by the points G', T, R and I' and composition ratios falling on the lines connecting these points in a ternary composition diagram are not included.

[0040] This composition is for use as an alternative refrigerant for R22, or an alternative refrigerant for R404A, which is a mixed refrigerant.

[0041] Point G' indicates a composition ratio in which GWP = 1475 (straight line L' in Fig. 1), based on AR4, and in which the compressor outlet temperature is 130°C. Further, point I' indicates a composition ratio in which GWP = 1475, based on AR4, and in which the refrigerating capacity is 76.5% of that of R404A.

[0042] The quadrilateral surrounded by points G', T, R, and I' represents a region that has a GWP of 1475 or less, shows ASHRAE non-flammability in which safety factors are taken into consideration, and that has a compressor outlet temperature of 130°C or lower and a refrigerating capacity of 76.5% or more of that of R404A.

[0043] Although the details are described later, in Fig. 1, the straight line P' passing through two points, i.e., point X and point Y, denotes an ASHRAE non-flammable border line when the allowable range (allowable concentration) is set to ±2.0% in the production of R32, R125, and R134a; a straight line L passing through two points, i.e., point A and point B, denotes a line indicating a composition ratio in which GWP is 1500, based on AR4; and a straight line passing through two points, i.e., point I and point J, denotes a line indicating a composition ratio in which the refrigerating capacity is 76.5% of that of R404A.

[0044] The technical meaning of each point in Figs. 1, 3 and 4 is described in detail below.

[0045] In Fig. 4, when the wt% of R32 = x, the wt% of R125 = y, and the wt% of R134a = z, a line segment indicating an ASHRAE non-flammable border line is approximated by a line segment represented by the following equations.

[0046] ASHRAE non-flammable border line: Line segment P of Fig. 4 y = 0.9286 x − 17.643 z = 100 − x − y 19.0 ≤ x ≤ 61.0

[0047] The ASHRAE flammability classification of refrigerants is described below.

[0048] The ASHRAE flammability classification of refrigerants is performed based on ANSI / ASHRAE Standard 34-2013. Refrigerants classified as Class 1 are non-flammable refrigerants. That is, the composition comprising a refrigerant of the present invention being non-flammable according to ASHRAE means that the mixture comprising fluorinated hydrocarbons used in the present invention (in particular, the three basic components) is classified as Class 1 in the flammability classification.

[0049] More specifically, a leak test during storage, transportation, and use is performed based on ANSI / ASHRAE 34-2013 to specify the worst case of fractionation for flammability (WCFF). When the WCFF composition can be identified as being non-flammable in a test based on ASTM E681-09 (a standard test method for concentration limits of flammability of chemicals (vapors and gases)), it is classified as Class 1.

[0050] In Fig. 1, the R125 side from the line segment XY is classified as a mixed refrigerant that is non-flammable according to ASHRAE, whereas the R32 side from the line segment XY is classified as a mixed refrigerant that is flammable according to ASHRAE (Class 2: slightly flammable mixed refrigerants, Class 3: flammable mixed refrigerants).

[0051] However, in the production of a mixed refrigerant, an allowable range (including allowable error) is set for each refrigerant. Thus, even if the center composition of the mixed refrigerant is on the R125 side from the line segment XY of Fig. 1, when the allowable ranges are not all on the R125 side from the line segment XY, the mixed refrigerant is not defined as a mixed refrigerant that is non-flammable according to ASHRAE.

[0052] For example, in the case where R32 = 28.0 wt% ±2.0 wt%, R125 = 12.2 wt% ±2.0 wt%, and R134a = 59.8 wt% ±2.0 wt%, all of the allowable ranges are on the R125 side from the line segment XY as shown in Fig. 4, and thus, a mixed refrigerant in which these allowable ranges are set is classified as a mixed refrigerant that is non-flammable according to ASHRAE. In the case where R32 = 48.0 wt% ±2.0 wt%, R125 = 30.8 wt% ±2.0 wt%, and R134a = 21.2 wt% ±2.0 wt%, the allowable ranges are all on the R125 side from the line segment XY as shown in Fig. 4, and thus, a mixed refrigerant in which these allowable ranges are set is classified as a mixed refrigerant that is non-flammable according to ASHRAE.

[0053] When the allowable range of R32 is set to ±2.0 wt%, the allowable range of R125 is set to ±2.0 wt%, and the allowable range of R134a is set to ±2.0 wt%, the range in which all of the allowable ranges are on the R125 side from the line segment XY is regarded as the ASHRAE non-flammable border line in which the allowable ranges are taken into consideration. Fig. 4 shows the details.

[0054] In Fig. 4, the worst case of fractionation (WCF) denotes the most flammable point within the allowable ranges. When the center composition is (28.0 / 12.2 / 59.8), then the WCF is (30.0 / 10.2 / 59.8) on the line segment P. When the center composition is (48.0 / 30.8 / 21.2), then the WCF is (50.0 / 28.8 / 21.2) on the line segment P. Accordingly, when the allowable range of R32 is set to ±2.0 wt%, the allowable range of R125 is set to ±2.0 wt%, and the allowable range of R134a is set to ±2.0 wt%, the allowable ranges are all non-flammable according to ASHRAE on a straight line that passes through the center composition (28.0 / 12.2 / 59.8) and (48.0 / 30.8 / 21.2). This straight line has the same inclination as the ASHRAE non-flammable formula, i.e., 0.9286. The equations that represent a line passing through these center compositions represent the ASHRAE non-flammable border line in which the allowable ranges are taken into consideration, and is approximated by the following equations.

[0055] ASHRAE non-flammable border line in which the allowable ranges are taken into consideration: a straight line passing through two points, i.e., point X and point Y (line segment P' of Figs. 1, 3 and 4) y = 0.9286 x − 13.80 z = 100 − x − y 14.9 ≤ x ≤ 59.0

[0056] In Figs. 1 and 3, when the wt% of R32 = x, the wt% of R125 = y, and the wt% of R134a = z, a line segment indicating a composition ratio in which GWP = 1500 or GWP = 1475 is approximated by a line segment represented by the following equations.

[0057] A line segment indicating a composition ratio in which GWP = 1500: a straight line passing through two points, i.e., point A and point B (line segment L of Figs. 1 and 3 y = 0.3644 x + 3.400 z = 100 − x − y 0 ≤ x ≤ 70.8

[0058] A line segment indicating a composition ratio in which GWP = 1475: a straight line passing through two points, i.e., point A' and point B' (line segment L' of Figs. 1 and 3) y = 0.3644 x + 2.20 z = 100 − x − y 0 ≤ x ≤ 71.7

[0059] In addition, a line segment indicating a composition ratio in which the refrigerating capacity is 76.5% relative to that of R404A is approximated by a line segment represented by the following equations. The intersection with the ASHRAE non-flammable border line in which the allowable ranges are taken into consideration (y = 0.9286x - 13.80) is shown below.

[0060] A line segment indicating a composition ratio in which the refrigerating capacity is 76.5% relative to that of R404A: a straight line passing through two points, i.e., point I and point J (line segment IJ of Figs. 1 and 3) y = − 2.80 x + 58.80 z = 100 − x − y 17.5 ≤ x ≤ 21.0

[0061] The intersection with the ASHRAE non-flammable border line in which the allowable range is taken into consideration is represented by R = (19.2 / 4.3 / 76.2) (point R of Figs. 1 and 3). Further, the intersection with the line in which GWP = 1475 is represented by I' = (17.9 / 8.7 / 73.4).

[0062] Further, a line segment indicating a composition ratio in which the compressor outlet temperature is 130°C, 140°C, or 150°C is approximated by a line segment represented by the following equations. The intersection with the ASHRAE non-flammable border line in which the allowable range is taken into consideration (y = 0.9286x - 13.80) is shown below.

[0063] A line segment indicating a composition ratio in which the compressor outlet temperature is 130°C: a straight line passing through two points, i.e., point G and point H (line segment GH of Figs. 1 and 3) y = 5.2917 x − 122.24 z = 100 − x − y 23.1 ≤ x ≤ 25.5

[0064] The intersection with the ASHRAE non-flammable border line in which the allowable range is taken into consideration is represented by T = (24.9 / 9.3 / 65.8) (point T of Figs. 1 and 3).

[0065] Further, the intersection with GWP = 1475 is represented by G' = (25.2 / 11.4 / 63.4).Components other than the three basic components

[0066] The mixture contained in the present composition may further contain a tiny amount of water in addition to the three basic components (R32, R125, and R134a). The amount of water is preferably 0.1 wt% or less, per 100 wt% of the mixture. In one embodiment, the mixture contained in the present composition consists only of the basic three components and water. When the mixture contains a tiny amount of water, the double bonds in the molecules of unsaturated fluorinated hydrocarbons that may be contained in the present composition can be stably present, and oxidation of unsaturated fluorinated hydrocarbons is less likely to occur, resulting in improved stability of the mixture and the present composition.

[0067] The mixture contained in the present composition may contain other component(s) (fluorinated hydrocarbon(s) that are different from the three basic components) in addition to the three basic components (R32, R125, and R134a). The fluorinated hydrocarbon(s) as other component(s) are not limited, and, are, for example, at least one fluorinated hydrocarbon selected from HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

[0068] The mixture contained in the present composition may contain, in addition to the three basic components (R32, R125, and R134a), at least one halogenated organic compound of the formula C m H n X p (1), wherein each X independently is F, Cl or Br, m is 1 or 2, 2m + 2 ≥ n + p, and p ≥ 1, as other component(s). The at least one halogenated organic compound as other component(s) is not limited. Preferable examples include difluorochloromethane, chloromethane, 2-chloro-1,1,1,2,2-pentafluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, 2-chloro-1,1-difluoroethylene, and trifluoroethylene.

[0069] The mixture contained in the present composition present may contain, in addition to the three basic components (R32, R125, and R134a), at least one organic compound of the formula C m H n X p (2), wherein each X independently is an atom that is not a halogen atom, m is 1 or 2, 2m + 2 ≥ n + p, and p ≥ 1, as other component(s). The at least one organic compound as other component(s) is not limited. Preferable examples include propane and isobutane.

[0070] As described above, when the mixture contains other components (fluorinated hydrocarbon(s) that are different from the three basic components), the content of other components in the mixture, whether other components are used singly or in a combination of two or more, is preferably less than 0.5 wt%, more preferably 0.3 wt% or less, and even more preferably 0.1 wt% or less, as the total content amount.Optional Additives

[0071] The present composition may appropriately comprise various additives in addition to the mixture.

[0072] Further, by mixing with at least a refrigerant oil, the present composition can be used for obtaining a working fluid for refrigerating machines.

[0073] Specifically, the working fluid for refrigerating machines can be obtained by mixing together the present composition with a refrigerant oil used in a compressor of a refrigerating machine. The refrigerant oil is typically contained in an amount of 1-50 wt% in the working fluid for refrigerating machines, taking the total amount of the present composition and the refrigerant oil as 100 wt%.

[0074] The refrigerant oil is not limited, and can be suitably selected from typically used refrigerant oils. In this case, refrigerant oils that are superior in improving the miscibility with the mixture and stability of the mixture, for example, are suitably selected as necessary.

[0075] More specifically, the refrigerant oil is preferably, for example, at least one member selected from polyalkylene glycols (PAG), polyol esters (POE), and polyvinyl ethers (PVE).

[0076] For example, it is possible to use a refrigerant oil with a kinematic viscosity of 5-400 cSt at 40°C. The kinematic viscosity within this range is preferred from the standpoint of lubrication.

[0077] The present composition may further contain one or more tracers. The one or more tracers are incorporated in the present composition at a detectable concentration so that, when the present composition is diluted, contaminated, or undergoes any other change, the change can be traced. There is no limitation on the tracers. Preferable examples include hydrofluorocarbons (HFC), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N 2 O). Particularly preferred are hydrofluorocarbons or fluoroethers.

[0078] The present composition may further contain a compatibilizing agent. The type of compatibilizing agent is not limited. Preferable examples include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkans. Particularly preferred are polyoxyalkylene glycol ethers.

[0079] The present composition may further contain one or more ultraviolet fluorescent dyes. There is no limitation on the ultraviolet fluorescent dyes. Preferable examples include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, and derivatives thereof. Either naphthalimide or coumarin, or both are particularly preferable.

[0080] The present composition may further contain e.g. a stabilizer and a polymerization inhibitor, if necessary.

[0081] Examples of stabilizers include (i) aliphatic nitro compounds, such as nitromethane and nitroethane; and aromatic nitro compounds, such as nitrobenzene and nitrostyrene; (ii) ethers, such as 1,4-dioxane; amines, such as 2,2,3,3,3-pentafluoropropylamine and diphenylamine; butylhydroxyxylene, and benzotriazole. The stabilizers can be used singly or in a combination of two or more.

[0082] The concentration of the stabilizer varies depending on the type of stabilizer, but can be determined within a range in which the properties of the present composition are not impaired. The concentration of the stabilizer is generally preferably 0.01-5 parts by weight (pbw), and more preferably 0.05-2 pbw, per 100 pbw of the mixture.

[0083] The stability of the mixture can be evaluated by a commonly used method without limitation. Examples of such methods include an evaluation method using the amount of free fluorine ions as an index according to ASHRAE Standard 97-2007, and the like. There is, for example, another evaluation method using the total acid number as an index. This method can be performed, for example, according to ASTM D 974-06.

[0084] Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, hydroquinonemethyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0085] The concentration of the polymerization inhibitor is usually preferably 0.01-5 pbw, and more preferably 0.05-2 pbw, per 100 pbw of the mixture.

[0086] In the present invention, an object can be refrigerated by a method comprising the step of operating a refrigeration cycle using the present composition. For example, the present composition can be circulated via a compressor to form the refrigeration cycle.

[0087] It is also possible to produce a unit for forming a refrigeration cycle in which the present composition is circulated via a compressor.

[0088] Examples of refrigerating machines that can use the present composition include refrigerators, freezers, water coolers, ice makers, refrigerated showcases, freezing showcases, freezing and refrigerating units, refrigerating machines used, for example, for freezing and refrigerating warehouses, chillers (chilling units), turbo refrigerators, and screw refrigerators.Examples

[0089] The present invention is described in detail below with reference to Examples.Examples 1-9 and Comparative Examples 1-11

[0090] Examples 1-6 are reference examples not included in the subject matter defined in the claims.

[0091] The GWP of each of R404A and mixed refrigerants of R32, R125, and R134a was evaluated based on the values stated in the Intergovernmental Panel on Climate Change (IPCC) fourth report (AR4) .

[0092] The COP, refrigerating capacity, compressor outlet temperature, and compressor outlet pressure of each of R404A and the mixed refrigerants of R32, R125, and R134a were determined by performing refrigeration cycle theoretical calculations for the refrigerant and mixed refrigerants using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions. Evaporation temperature-40°CCondensation temperature40°CSuperheating temperature20 KSupercooling temperature0 KCompressor efficiency70%

[0093] In Fig. 3, the formulations of the compositions comprising a refrigerant of the Examples are indicated by circles (∘), and the formulations of the compositions comprising a refrigerant of the Comparative Examples are indicated by triangles (△).

[0094] Tables 1 and 2 show the GWP, COP, and refrigerating capacity calculated based on these results. Regarding the COP and refrigerating capacity, the percentages relative to those of R404A are shown.

[0095] The coefficient of performance (COP) was calculated according to the following equation.

[0096] The flammability of the mixture of the three basic components used in the composition comprising a refrigerant was evaluated according to U.S. ASHRAE Standard 34-2013. The flammable range was measured using the measurement device of Fig. 5 according to ASTM E681-09.

[0097] A 12-L spherical glass flask was used so that the combustion state could be visually observed and photographically recorded. When excessive pressure was generated by combustion, gas was allowed to escape from the upper lid. Ignition was achieved by electric discharge from electrodes disposed at one-third the distance from the bottom.Test conditions

[0098] Test vessel: 280 mm φ spherical (internal volume: 12 liters) Test temperature: 60°C ±3°C Pressure: 101.3 kPa ±0.7 kPa Water: 0.0088 g ±0.0005 g per gram of dry air Mixing ratio of composition comprising a refrigerant / air: 1 vol.% increments ±0.2 vol.% Composition mixture comprising a refrigerant: ±0.1 wt% Ignition method: AC discharge, voltage: 15 kV, electric current: 30 mA, neon transformer Electrode spacing: 6.4 mm (1 / 4 inch) Spark: 0.4 seconds ±0.05 seconds Evaluation criteria: When the flame propagation extends at an angle of 90° or more from the ignition point, it was evaluated as flammable (propagation).

[0099] The composition ratio of R32, R125, and R134a (x / y / z wt%) in the non-flammability limit almost satisfied the relationship represented by the following equations (1) to (3). 19.0 ≤ x ≤ 61.0 y = 0.9286 x − 17.643 z = 100 − x − y

[0100] The results revealed that the composition comprising a refrigerant of the present invention is non-flammable, and causes no combustion, even when mixed with air at any ratio. Table 1ItemUnitComparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Example 1Comparative Example 7Example 2Comparative Example 8Point APoint BPoint A'Point B'Point GPoint HPoint IPoint JConcentrationR32mass%R404AR2270.80.071.70.025.523.117.521.0R125mass%29.23.428.32.212.70.09.80.0R134amass%0.096.60.097.861.876.972.779.0GWP (AR4)year3922181015001500147514751500125615001271Relative to 404ACoefficient of performance(%)100117109114109114112114113114Refrigerating capacity(%)100.0104.8164.953.5165.353.288.279.176.576.5Compressor outlet temperature°C93149161104162104130130123128Compressor outlet pressureMpa1.821.532.462.461.091.041.661.431.411.39Flammability according to ASHRAENon-flammableNon-flammableFlammableNon-flammableFlammableNon-flammableNon-flammableFlammableNon-flammableFlammable Table 2 ItemUnitExample 3Example 4Example 5Example 6Example 7Example 8Example 9Comparative Example 9Comparative Example 10Comparative Example 11Point TPoint RPoint G'Point I'ConcentrationR32mass%24.919.525.217.924.522.520.022.535.015.0R125mass%9.34.311.48.710.510.09.020.05.05.0R134amass%65.876.263.473.465.067.571.057.560.080.0GWP (AR4)year1435137214761475146214671465167412691420Relative to 404ACoefficient of performance(%)113114112113113113113111113114Refrigerating capacity(%)85.776.587.176.585.883.078.588.096.271.5Compressor outlet temperature°C130126130123130128125126141121Compressor outlet pressureMpa1.531.401.561.411.541.501.441.591.661.33Flammability according to ASHRAENon-flammableNon-flammableNon-flammableNon-flammableNon-flammableNon-flammableNon-flammableNon-flammableNon-flammableFlammable

[0101] The compositions comprising a refrigerant of Comparative Examples 3, 5, 7, 9 and 11 were all flammable.

[0102] Although the compositions comprising a refrigerant of Comparative Example 4 and Comparative Example 6 were non-flammable, these compositions had a refrigerating capacity as low as 53.5% and 53.2%, respectively, relative to that of R404A.

[0103] Although the composition comprising a refrigerant of Comparative Example 10 was non-flammable, the GWP was 1674, which is much greater than 1500.

[0104] Although the composition comprising a refrigerant of Comparative Example 11 was non-flammable, the compressor outlet temperature was as high as 141°C.Description of References

[0105] A: Composition ratio in which GWP = 1500, based on AR4, and the concentration (wt%) of R134a is 0 wt% B: Composition ratio in which GWP = 1500, based on AR4, and the concentration (wt%) of R32 is 0 wt% A': Composition ratio in which GWP = 1475, based on AR4, and the concentration (wt%) of R134a is 0 wt% B': Composition ratio in which GWP = 1475, based on AR4, and the concentration (wt%) of R32 is 0 wt% C: Composition ratio in which GWP = 1500, based on AR4, and the compressor outlet temperature is 150°C D: Composition ratio in which the concentration (wt%) of R125 is 0 wt%, and the compressor outlet temperature is 150°C E: Composition ratio in which GWP = 1500, based on AR4, and the compressor outlet temperature is 140°C F: Composition ratio in which the concentration (wt%) of R125 is 0 wt%, and the compressor outlet temperature is 140°C G: Composition ratio in which GWP = 1500, based on AR4, and the compressor outlet temperature is 130°C G': Composition ratio in which GWP = 1475, based on AR4, and the compressor outlet temperature is 130°C H: Composition ratio in which the concentration (wt%) of R125 is 0 wt%, and the compressor outlet temperature is 130°C I: Composition ratio in which GWP = 1500, based on AR4, and the refrigerating capacity is 76.5% of that of R404A I': Composition ratio in which GWP = 1475, based on AR4, and the refrigerating capacity is 76.5% of that of R404A J: Composition ratio in which the concentration (wt%) of R125 is 0 wt%, and the refrigerating capacity is 76.5% of that of 404A R: Intersection of line segment IJ and line segment XY T: Intersection of line segment MN, line segment GH, and line segment XY P: ASHRAE non-flammable border line P': ASHRAE non-flammable border line when the allowable range (allowable concentration) is set to ±2.0% in the production of R32, R125, and R134a L: Approximation line segment of line segment indicating GWP = 1500 L': Approximation line segment of line segment indicating GWP = 1475

Claims

1. Use of a composition as a drop-in alternative refrigerant for R22 or R404A or as a retrofit refrigerant for R22 or R404A, wherein the composition comprises a refrigerant, and wherein the refrigerant comprises a mixture of fluorinated hydrocarbons comprising difluoromethane (R32), pentafluoroethane (R125), and 1,1,1,2-tetrafluoroethane (R134a) in amounts such that the sum of the concentrations thereof is ≥ 99.5 wt.-%, and wherein the composition ratio of the fluorinated hydrocarbons contained in the mixture falls within a quadrilateral having, as vertices, the following four points in a ternary composition diagram in which the sum of the concentrations of R32, R125, and R134a is 100 wt.-%: point G' (R32 / R125 / R134a = 25.2 / 11.4 / 63.4 wt%), point T (R32 / R125 / R134a = 24.9 / 9.3 / 65.8 wt%), point R (R32 / R125 / R134a = 19.5 / 4.3 / 76.2 wt%), and point I' (R32 / R125 / R134a = 17.9 / 8.7 / 73.4 wt%); provided that composition ratios defined by the points G', T, R and I' and composition ratios falling on the lines connecting these points in a ternary composition diagram are not included.

2. The use of claim 1, wherein the mixture further comprises water.

3. The use of claim 1 or 2, wherein the composition further comprises at least one substance selected from the group consisting of tracers, compatibilizing agents, ultraviolet fluorescent dyes, stabilizers, and polymerization inhibitors.

4. The use of any of claims 1-3, wherein the composition further comprises a refrigerant oil and is for use as a working fluid for refrigerating machines.

5. The use of claim 4, wherein the refrigerant oil contains at least one member selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

6. The use of any of claims 1-5 for at least one of refrigerators, freezers, water coolers, ice makers, refrigerated showcases, freezing showcases, freezing and refrigerating units, refrigerating machines for freezing and refrigerating warehouses, chillers (chilling units), turbo refrigerating machines, and screw refrigerating machines.