REFRIGERANT-CONTAINING COMPOSITION, USE THEREOF, REFRIGERATOR HAVING SAME, AND METHOD FOR OPERATING SAID REFRIGERATOR

Information

  • Patent Application
  • 20230323179
  • Publication Number
    20230323179
  • Date Filed
    June 13, 2023
    11 months ago
  • Date Published
    October 12, 2023
    7 months ago
Abstract
An object is to provide a novel low-GWP mixed refrigerant. As a solution to achieve the object, a composition containing a refrigerant that contains 1,1-difluoroethylene (HFO-1132a), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze) is provided.
Description
TECHNICAL FIELD

The present disclosure relates to a composition comprising a refrigerant, use of the composition, a refrigerating machine comprising the composition, and a method for operating the refrigerating machine.


BACKGROUND ART

R410A is currently used as an air conditioning refrigerant for home air conditioners etc. R410A is a two-component mixed refrigerant of difluoromethane (CH2F2; HFC-32 or R32) and pentafluoroethane (C2HF5; HFC-125 or R125) and is a pseudo-azeotropic composition.


However, the global warming potential (GWP) of R410A is 2088. Due to growing concerns about global warming, R32, which has a GWP of 675, has been increasingly used.


For this reason, various low-GWP mixed refrigerants that can replace R410A have been proposed (Patent Literature 1).


CITATION LIST
Patent Literature

PTL 1: WO2015/141678


SUMMARY

Item 1.


A composition comprising a refrigerant, the refrigerant comprising 1,1-difluoroethylene (HFO-1132a), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).


Advantageous Effects

The refrigerant according to the present disclosure has a low GWP.





BRIEF DESCRIPTION OF DRAWINGS


FIG. 1 is a diagram showing points A to J, A′, B′, and G′, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, HFO-1132a, and R1234ze is 100 mass %.



FIG. 2 is a diagram showing points A to H, P, A′, B′, C′, G′, and E′, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 98.5 mass % (HFO-1132a content is 1.5 mass %).



FIG. 3 is a diagram showing points A to H, P, A′, and B′, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 98.5 mass % (HFO-1132a content is 1.5 mass %).



FIG. 4 is a diagram showing points A to H, P, A′, and B′, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 97.0 mass % (HFO-1132a content is 3.0 mass %).



FIG. 5 is a diagram showing points A to H, P, A′, and B′, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 95.0 mass % (HFO-1132a content is 5.0 mass %).



FIG. 6 is a diagram showing points A to H, P, A′, and B′, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 92.5 mass % (HFO-1132a content is 7.5 mass %). FIG. 7 is a diagram showing points A to H, P, A′, and B′, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 90.0 mass % (HFO-1132a content: 10.0 mass %).



FIG. 8 is a diagram showing points A″, B″, L, M, S, and T, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, HFO-1132a, and R1234ze is 100 mass %.



FIG. 9 is a diagram showing points A″, B″, L, L′, M, and T, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 98.5 mass % (HFO-1132a content is 1.5 mass %).



FIG. 10 is a diagram showing points A″, B″, L, L′, M, and T, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 98.5 mass % (HFO-1132a content is 1.5 mass %).



FIG. 11 is a diagram showing points A″, B″, L, M, and T, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 98.1 mass % (HFO-1132a content is 1.9 mass %).



FIG. 12 is a diagram showing points A″, B″, L, and M, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 94.0 mass % (HFO-1132a content is 6.0 mass %).



FIG. 13 is a diagram showing points A″, B″, L, and M, and line segments that connect these points to each other in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is 90.0 mass % (HFO-1132a content is 10.0 mass %).





DESCRIPTION OF EMBODIMENTS

The present inventors conducted intensive study to solve the above problem, and consequently found that a mixed refrigerant comprising HFO-1132a, R32, and R1234ze has the above properties.


The present disclosure has been completed as a result of further research based on this finding. The present disclosure includes the following embodiments.


DEFINITION OF TERMS

In the present specification, the term “refrigerant” includes at least compounds that are specified in ISO 817 (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 compounds and non-fluorocarbon compounds in terms of the structure of the compounds. Fluorocarbon compounds include chlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC), and hydrofluorocarbons (HFC).


In the present specification, the phrase “composition comprising a refrigerant” at least includes (1) a refrigerant itself (including a mixture of refrigerants), (2) a composition that further comprises other components and that can be mixed with at least a refrigeration oil to obtain a working fluid for a refrigerating machine, and (3) a working fluid for a refrigerating machine containing a refrigeration oil. In the present specification, of these three embodiments, the composition (2) is referred to as a “refrigerant composition” so as to distinguish it from a refrigerant itself (including a mixture of refrigerants). Further, the working fluid for a refrigerating machine (3) is referred to as a “refrigeration oil-containing working fluid” so as to distinguish it from the “refrigerant composition.”


In the present specification, when the term “alternative” is used in a 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 of the following: refrigeration 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.


The term “alternative” also includes a second type of “alternative,” which means that equipment designed for operation using the second refrigerant is operated for the same use as the existing use with the first refrigerant by using the second refrigerant. This type of alternative means that the same use is achieved with an alternative refrigerant.


In the present specification, the term “refrigerating machine” 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 a 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.


In the present specification, the term “condensation temperature glide” refers to the temperature gradient in which the condensation start temperature and the condensation end temperature in a heat exchanger differ due to the difference in composition between the liquid phase and the gas phase in a non-azeotropic mixed refrigerant as described herein.


1. Refrigerant
1.1 Essential Refrigerant Components

The refrigerant according to the present disclosure comprises HFO-1132a, R32, and R1234ze.


The refrigerant according to the present disclosure is a low-GWP mixed refrigerant.


The refrigerant according to the present disclosure preferably comprises HFO-1132a in an amount of 1.5 to 10 mass % based on the entire refrigerant. The content of R32 is preferably 74 mass % or less, and more preferably 59 mass % or less, based on the entire refrigerant. When the refrigerant is an alternative refrigerant for R404A, the content of R32 is more preferably 21.8 mass % or less.


When the refrigerant according to the present disclosure comprises HFO-1132a, R32, R1234ze, and R1234yf, and when the refrigerant is an alternative refrigerant for R410A, the content of R32 is preferably 11.9 mass % or more, more preferably 29.1 mass % or more, and even more preferably 37.9 mass % or more, based on the entire refrigerant. The total content of R1234ze and R1234yf is preferably 14.5 mass % or more, more preferably 16.0 mass % or more, and even more preferably 31.0 mass % or more, based on the entire refrigerant. The content of R1234ze is preferably 71.8 mass % or less, more preferably 52.3 mass % or less, and even more preferably 32.6 mass % or less, based on the entire refrigerant. The content of R1234yf is preferably 78.1 mass % or less, more preferably 60.9 mass % or less, and even more preferably 60.6 mass % or less, based on the entire refrigerant.


When the refrigerant according to the present disclosure comprises HFO-1132a, R32, R1234ze, and R1234yf, and when the refrigerant is an alternative refrigerant for R404A, the content of R32 is preferably 0.9 mass % or more based on the entire refrigerant. The total content of R1234ze and R1234yf is preferably 68.2 mass % or more based on the entire refrigerant. The content of R1234ze is preferably 77.5 mass % or less based on the entire refrigerant. The content of R1234yf is preferably 89.6 mass % or less based on the entire refrigerant.


The refrigerant according to the present disclosure preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 500 or less and a refrigerating capacity ratio of 70% or more relative to that of R410A.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines IB, BC, CD, and DI that connect the following four points:

    • point I (10.0, 74.0, 16.0),
    • point B (1.5, 73.9, 24.6),
    • point C (1.5, 35.8, 62.7), and
    • point D (10.0, 18.2, 71.8),
    • or on the straight lines.


The refrigerant according to the present disclosure preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 500 or less and a refrigerating capacity ratio of 85% or more relative to that of R410A.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines IB, BE, EF, and FI that connect the following four points:

    • point I (10.0, 74.0, 16.0),
    • point B (1.5, 73.9, 24.6),
    • point E (1.5, 56.2, 42.3), and
    • point F (10.0, 37.7, 52.3),
    • or on the straight lines.


The refrigerant according to the present disclosure preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 500 or less and a condensation temperature glide of 5° C. or less.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines G′B, BG, and GG′ that connect the following three points:

    • point G′ (8.6, 73.9, 17.5),
    • point B (1.5, 73.9, 24.6), and
    • point G (1.5, 65.9, 32.6),
    • or on the straight lines.


The refrigerant according to the present disclosure preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 400 or less and a refrigerating capacity ratio of 70% or more relative to that of R410A.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines JB′, B′C, CD, and DJ that connect the following four points:

    • point J (10.0, 59.0, 31.0),
    • point B′ (1.5, 58.9, 39.6),
    • point C (1.5, 35.8, 62.7), and
    • point D (10.0, 18.2, 71.8),
    • or on the straight lines.


The refrigerant according to the present disclosure preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 400 or less and a refrigerating capacity ratio of 85% or more relative to that of R410A.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines JB′, B′E, EF, and FJ that connect the following four points:

    • point J (10.0, 59.0, 31.0),
    • point B′ (1.5, 58.9, 39.6),
    • point E (1.5, 56.2, 42.3), and
    • point F (10.0, 37.7, 52.3),
    • or on the straight lines.


The refrigerant according to the present disclosure may further comprise 2,3,3,3-tetrafluoro-1-propene (R1234yf).


When the refrigerant according to the present disclosure further comprises R1234yf, the refrigerant preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 500 or less and a refrigerating capacity ratio of 70% or more relative to that of R410A.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BC, CD, and DA that connect the following four points:

    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point D (0.0098a2−2.1856a+39.064, 0.0, −0.0098a2+1.1856a+60.936), and
    • point C (0.0138a2−1.6252a+26.785, −0.0138a2+0.6252a+73.215, 0.0),
    • or on the straight lines AB and CD (excluding the points A, B, C, and D).


When the refrigerant according to the present disclosure further comprises R1234yf, the refrigerant preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 500 or less and a refrigerating capacity ratio of 85% or more relative to that of R410A.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BF, FE, and EA that connect the following four points:

    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point F (0.0102a2−2.2922a+59.604, 0.0, −0.0102a2+1.2922a+40.396), and
    • point E (0.0208a2−2.0723a+47.748, −0.0208a2+1.0723a+52.252, 0.0),
    • or on the straight lines AB and FE (excluding the points A, B, F, and E).


When the refrigerant according to the present disclosure further comprises R1234yf, the refrigerant preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 500 or less and a condensation temperature glide of 5° C. or less.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,

    • if 5.0≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BH, HG, and GA that connect the following four points:
    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point H (−0.1143a2+2.3143a+62.686, 0.0, 0.1143a2−3.3143a+37.314), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AB and HG (excluding the points A, B, H, and G);
    • if 7.5≥x≥5.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AB, BH, HG, and GA that connect the following four points:
    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point H (−0.072a2+1.9a+63.7, 0.0, 0.072a2−2.9a+36.3), and
    • point G (−0.0505a=+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AB and HG (excluding the points A, B, H, and G); or
    • if 10.0≥x>7.5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AR, RG, and GA that connect the following three points:
    • point A (74.0, −a+26.0, 0.0),
    • point R (73.9, 1.12a−8.4, −2.12a+34.5), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AR and RG (excluding the points A and G).


When the refrigerant according to the present disclosure further comprises R1234yf, the refrigerant preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 400 or less and a refrigerating capacity ratio of 70% or more relative to that of R410A.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′B′, B′D, DC, and CA′ that connect the following four points:

    • point A′ (59.0, −a+41.0, 0),
    • point B′ (58.9, 0.0, −a+41.1),
    • point D (0.0098a2−2.1856a+39.064, 0.0, −0.0098a2+1.1856a+60.936), and point C (0.0138a=−1.6252a+26.785, −0.0138a=+0.6252a+73.215, 0.0),
    • or on the straight lines A′B′ and DC (excluding the points A′, B′, D, and C).


When the refrigerant according to the present disclosure further comprises R1234yf, the refrigerant preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 400 or less and a refrigerating capacity ratio of 85% or more relative to that of R410A.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′B′, B′F, FE, and EA′ that connect the following four points:

    • point A′ (59.0, −a+41.0, 0.0),
    • point B′ (58.9, 0.0, −a+41.1),
    • point F (0.0102a2−2.2922a+59.604, 0.0, −0.0102a2+1.2922a+40.396), and
    • point E (0.0208a=−2.0723a+47.748, −0.0208a2+1.0723a+52.252, 0.0),
    • or on the straight lines A′B′ and FE (excluding the points A′, B′, F, and E).


When the refrigerant according to the present disclosure further comprises R1234yf, the refrigerant preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 400 or less and a condensation temperature glide of 5° C. or less.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,

    • if 5.0≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′P, PG, and GA′ that connect the following three points:
    • point A′ (59.0, −a+41.0, 0.0),
    • point P (−0.019a2+0.1524a+58.714, −0.2571a2+4.1571a+9.5429, 0.2761a2−5.3095a+31.7431), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines A′P and PG (excluding the points A′ and G); or
    • if 10.0≥x≥5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines A′P, PG, and GA′ that connect the following three points:
    • point A′ (59.0, −a+41.0, 0.0),
    • point P (59.0, −0.136a2+2.94a+12.6, 0.136a=−3.94a+28.4), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines A′P and PG (excluding the points A′ and G).


The refrigerants described above can be preferably used as working fluids in a refrigerating machine and are particularly suitable as alternative refrigerants for R410A.


The refrigerants described below can be preferably used as working fluids in a refrigerating machine and are particularly suitable as alternative refrigerants for R404A.


The refrigerant according to the present disclosure also preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 150 or less, a condensation temperature glide of 5° C. or less, and a refrigerating capacity ratio of 70% or more relative to that of R404A.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines ST, TM, and MS that connect the following three points:

    • point S (10.0, 21.5, 68.5),
    • point T (1.9, 21.5, 76.6), and
    • point M (10.0, 12.5, 77.5),
    • or on the straight lines.


The refrigerant according to the present disclosure also preferably satisfies the following requirements. In this case, the refrigerant according to the present disclosure has a GWP of 150 or less and a refrigerating capacity ratio of 70% or more relative to that of R404A


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,

    • if 1.9≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A″T, TM, and MA″ that connect the following three points:
    • point A″ (21.8, −a+78.2, 0.0),
    • point T (21.5, −15.0a+28.5, 14.0a+50.0), and
    • point M (0.0035a2−0.9809a+10.358, −0.0035a2−0.0191a+89.642, 0.0),
    • or on the straight lines A″T and TM (excluding the points A″ and M); or
    • if 10.0≥x>1.9, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines A″B″, B″L, LM, and MA″ that connect the following four points:
    • point A″ (21.8, −a+78.2, 0.0),
    • point B″ (0.0108a+21.473, 0.0, −1.0108a+78.527),
    • point L (0.0098a=−1.2237a+23.804, 0.0, −0.0098a2+0.2237a+76.196), and
    • point M (0.0035a2−0.9809a+10.358, −0.0035a2−0.0191a+89.642, 0.0),
    • or on the straight lines A″B″ and LM (excluding the points A″, B″, L, and M).


1.2 Additional Refrigerant Components

Additional refrigerants that may be contained in the refrigerant according to the present disclosure are described below. The refrigerant according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132a, R32, and R1234ze as long as the above properties and effects are not impaired. In this respect, in an embodiment, the refrigerant according to the present disclosure preferably comprises HFO-1132a, R32, and R1234ze in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, even more preferably 99.9 mass % or more, still even more preferably 99.99 mass % or more, and most preferably 99.9999 mass % or more, based on the entire refrigerant. The refrigerant according to the present disclosure may consist essentially of HFO-1132a, R32, and R1234ze or may consist of HFO-1132a, R32, and R1234ze. When the refrigerant according to the present disclosure consists essentially of HFO-1132a, R32, and R1234ze, the refrigerant according to the present disclosure may consist of HFO-1132a, R32, R1234ze, and inevitable impurities. In another embodiments, the refrigerant according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132a, R32, R1234ze, and R1234yf as long as the above properties and effects are not impaired. The refrigerant according to the present disclosure preferably comprises HFO-1132a, R32, R1234ze, and R1234yf in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, even more preferably 99.9 mass % or more, still even more preferably 99.99 mass % or more, and most preferably 99.9999 mass % or more, based on the entire refrigerant. The refrigerant according to the present disclosure may consist essentially of HFO-1132a, R32, R1234ze, and R1234yf or may consist of HFO-1132a, R32, R1234ze, and R1234yf. When the refrigerant according to the present disclosure consists essentially of HFO-1132a, R32, R1234ze, and R1234yf, the refrigerant according to the present disclosure may consist of HFO-1132a, R32, R1234ze, R1234yf, and inevitable impurities.


Such additional refrigerants are not limited, and can be selected from a wide range of refrigerants. The mixed refrigerant may contain a single additional refrigerant, or two or more additional refrigerants.


2. Refrigerant Composition

The refrigerant composition according to the present disclosure comprises at least the refrigerant according to the present disclosure, and can be used for the same use as the refrigerant according to the present disclosure. Moreover, the refrigerant composition according to the present disclosure can be further mixed with at least a refrigeration oil to thereby obtain a working fluid for a refrigerating machine.


The refrigerant composition according to the present disclosure further comprises at least one other component in addition to the refrigerant according to the present disclosure. The refrigerant composition according to the present disclosure may comprise at least one of the following other components, if necessary. As described above, when the refrigerant composition according to the present disclosure is used as a working fluid in a refrigerating machine, it is generally used as a mixture with at least a refrigeration oil. Therefore, it is preferable that the refrigerant composition according to the present disclosure does not substantially comprise a refrigeration oil. Specifically, in the refrigerant composition according to the present disclosure, the content of the refrigeration oil based on the entire refrigerant composition is preferably 0 to 1 mass %, and more preferably 0 to 0.1 mass %.


2.1 Water

The refrigerant composition according to the present disclosure may contain a small amount of water. The water content of the refrigerant composition is preferably 0.1 mass % or less based on the entire refrigerant. A small amount of water contained in the refrigerant composition stabilizes double bonds in the molecules of unsaturated fluorocarbon compounds that can be present in the refrigerant, and makes it less likely that the unsaturated fluorocarbon compounds will be oxidized, thus increasing the stability of the refrigerant composition.


2.2. Tracer A tracer is added to the refrigerant composition according to the present disclosure at a detectable concentration such that when the refrigerant composition has been diluted, contaminated, or undergone other changes, the tracer can trace the changes.


The refrigerant composition according to the present disclosure may comprise a single tracer, or two or more tracers.


The tracer is not limited, and can be suitably selected from commonly used tracers.


Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). The tracer is particularly preferably a hydrofluorocarbon, a hydrochlorofluorocarbon, a chlorofluorocarbon, a hydrochlorocarbon, a fluorocarbon, or a fluoroether.


The following compounds are preferable as the tracer.

    • FC-14 (tetrafluoromethane, CF4)
    • HCC-40 (chloromethane, CH3Cl)
    • HFC-23 (trifluoromethane, CHF3)
    • HFC-41 (fluoromethane, CH3Cl)
    • HFC-125 (pentafluoroethane, CF3CHF2)
    • HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)
    • HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)
    • HFC-143a (1,1,1-trifluoroethane, CF3CH3)
    • HFC-143 (1,1,2-trifluoroethane, CHF2CH2F)
    • HFC-152a (1,1-difluoroethane, CHF2CH3)
    • HFC-152 (1,2-difluoroethane, CH2FCH2F)
    • HFC-161 (fluoroethane, CH3CH2F)
    • HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)
    • HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)
    • HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)
    • HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3)
    • HCFC-22 (chlorodifluoromethane, CHClF2)
    • HCFC-31 (chlorofluoromethane, CH3ClF)
    • CFC-1113 (chlorotrifluoroethylene, CF2═CClF)
    • HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2)
    • HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F)
    • HFE-143a (trifluoromethyl-methyl ether, CF3OCH3)
    • HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)
    • HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)


The refrigerant composition of the present disclosure may contain the tracer in a total amount of about 10 parts per million by weight (ppm) to about 1000 ppm based on the entire refrigerant composition. The refrigerant composition of the present disclosure may contain the tracer in a total amount of preferably about 30 ppm to about 500 ppm, and more preferably about 50 ppm to about 300 ppm, based on the entire refrigerant composition.


2.3. Ultraviolet Fluorescent Dye

The refrigerant composition according to the present disclosure may comprise a single ultraviolet fluorescent dye, or two or more ultraviolet fluorescent dyes.


The ultraviolet fluorescent dye is not limited, and can be suitably selected from commonly used ultraviolet fluorescent dyes.


Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof. The ultraviolet fluorescent dye is particularly preferably either naphthalimide or coumarin, or both.


2.4. Stabilizer

The refrigerant composition according to the present disclosure may comprise a single stabilizer, or two or more stabilizers.


The stabilizer is not limited, and can be suitably selected from commonly used stabilizers.


Examples of stabilizers include nitro compounds, ethers, and amines.


Examples of nitro compounds include aliphatic nitro compounds, such as nitromethane and nitroethane; and aromatic nitro compounds, such as nitro benzene and nitro styrene.


Examples of ethers include 1,4-dioxane.


Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.


Examples of stabilizers also include butylhydroxyxylene and benzotriazole.


The content of the stabilizer is not limited. Generally, the content of the stabilizer is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.


2.5. Polymerization Inhibitor

The refrigerant composition according to the present disclosure may comprise a single polymerization inhibitor, or two or more polymerization inhibitors.


The polymerization inhibitor is not limited, and can be suitably selected from commonly used polymerization inhibitors.


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


The content of the polymerization inhibitor is not limited. Generally, the content of the polymerization inhibitor is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.


3. Refrigeration Oil-Containing Working Fluid

The refrigeration oil-containing working fluid according to the present disclosure comprises at least the refrigerant or refrigerant composition according to the present disclosure and a refrigeration oil, for use as a working fluid in a refrigerating machine. Specifically, the refrigeration oil-containing working fluid according to the present disclosure is obtained by mixing a refrigeration oil used in a compressor of a refrigerating machine with the refrigerant or the refrigerant composition. The refrigeration oil-containing working fluid generally comprises 10 to 50 mass % of refrigeration oil.


3.1. Refrigeration Oil

The composition according to the present disclosure may comprise a single refrigeration oil, or two or more refrigeration oils.


The refrigeration oil is not limited, and can be suitably selected from commonly used refrigeration oils. In this case, refrigeration oils that are superior in the action of increasing the miscibility with the mixture and the stability of the mixture, for example, can be suitably selected as necessary.


The base oil of the refrigeration oil is preferably, for example, at least one member selected from the group consisting of polyalkylene glycols (PAG), polyol esters (POE), and polyvinyl ethers (PVE).


The refrigeration oil may further contain additives in addition to the base oil. The additive may be at least one member selected from the group consisting of antioxidants, extreme-pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oil agents, and antifoaming agents.


A refrigeration oil with a kinematic viscosity of 5 to 400 cSt at 40° C. is preferable from the standpoint of lubrication.


The refrigeration oil-containing working fluid according to the present disclosure may further optionally contain at least one additive. Examples of additives include compatibilizing agents described below.


3.2. Compatibilizing Agent

The refrigeration oil-containing working fluid according to the present disclosure may comprise a single compatibilizing agent, or two or more compatibilizing agents.


The compatibilizing agent is not limited, and can be suitably selected from commonly used compatibilizing agents.


Examples of compatibilizing agents include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. The compatibilizing agent is particularly preferably a polyoxyalkylene glycol ether.


4. Method for Operating Refrigerating Machine

The method for operating a refrigerating machine according to the present disclosure is a method for operating a refrigerating machine using the refrigerant according to the present disclosure.


Specifically, the method for operating a refrigerating machine according to the present disclosure comprises the step of circulating the refrigerant according to the present disclosure in a refrigerating machine.


The embodiments are described above; however, it will be understood that various changes in forms and details can be made without departing from the spirit and scope of the claims.


Item 1.


A composition comprising a refrigerant, the refrigerant comprising 1,1-difluoroethylene (HFO-1132a), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).


Item 2.


The composition according to Item 1, wherein the refrigerant comprises HFO-1132a in an amount of 1.5 to 10 mass % based on the entire refrigerant.


Item 3.


The composition according to Item 1, wherein

    • when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines IB, BC, CD, and DI that connect the following four points:
    • point I (10.0, 74.0, 16.0),
    • point B (1.5, 73.9, 24.6),
    • point C (1.5, 35.8, 62.7), and
    • point D (10.0, 18.2, 71.8),
    • or on the straight lines.


Item 4.


The composition according to Item 1, wherein

    • when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines IB, BE, EF, and FI that connect the following four points:
    • point I (10.0, 74.0, 16.0),
    • point B (1.5, 73.9, 24.6),
    • point E (1.5, 56.2, 42.3), and
    • point F (10.0, 37.7, 52.3),
    • or on the straight lines.


Item 5.


The composition according to Item 1, wherein

    • when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines G′B, BG, and GG′ that connect the following three points:
    • point G′ (8.6, 73.9, 17.5),
    • point B (1.5, 73.9, 24.6), and
    • point G (1.5, 65.9, 32.6),
    • or on the straight lines.


Item 6.


The composition according to Item 1, wherein

    • when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines JB′, B′C, CD, and DJ that connect the following four points:
    • point J (10.0, 59.0, 31.0),
    • point B′ (1.5, 58.9, 39.6),
    • point C (1.5, 35.8, 62.7), and
    • point D (10.0, 18.2, 71.8),
    • or on the straight lines.


Item 7.


The composition according to Item 1, wherein

    • when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines JB′, B′E, EF, and FJ that connect the following four points:
    • point J (10.0, 59.0, 31.0),
    • point B′ (1.5, 58.9, 39.6),
    • point E (1.5, 56.2, 42.3), and
    • point F (10.0, 37.7, 52.3),
    • or on the straight lines.


Item 8.


The composition according to any one of Items 1 to 7, wherein the refrigerant further comprises 2,3,3,3-tetrafluoro-1-propene (R1234yf).


Item 9.


The composition according to Item 8, wherein

    • when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BC, CD, and DA that connect the following four points:
    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point D (0.0098a2−2.1856a+39.064, 0.0, −0.0098a2+1.1856a+60.936), and
    • point C (0.0138a2−1.6252a+26.785, −0.0138a2+0.6252a+73.215, 0.0),
    • or on the straight lines AB and CD (excluding the points A, B, C, and D).


Item 10.


The composition according to Item 8, wherein

    • when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BF, FE, and EA that connect the following four points:
    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point F (0.0102a=−2.2922a+59.604, 0.0, −0.0102a2+1.2922a+40.396), and
    • point E (0.0208a2−2.0723a+47.748, −0.0208a2+1.0723a+52.252, 0.0),
    • or on the straight lines AB and FE (excluding the points A, B, F, and E).


Item 11.


The composition according to Item 8, wherein

    • when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,
    • if 5.0≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BH, HG, and GA that connect the following four points:
    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point H (−0.1143a2+2.3143a+62.686, 0.0, 0.1143a2−3.3143a+37.314), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AB and HG (excluding the points A, B, H, and G);
    • if 7.5≥x≥5.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AB, BH, HG, and GA that connect the following four points:
    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point H (−0.072a2+1.9a+63.7, 0.0, 0.072a2−2.9a+36.3), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AB and HG (excluding the points A, B, H, and G); or
    • if 10.0≥x≥7.5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AR, RG, and GA that connect the following three points:
    • point A (74.0, −a+26.0, 0.0),
    • point R (73.9, 1.12a−8.4, −2.12a+34.5), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AR and RG (excluding the points A and G).


Item 12.


The composition according to Item 8, wherein

    • when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′B′, B′D, DC, and CA′ that connect the following four points:
    • point A′ (59.0, −a+41.0, 0),
    • point B′ (58.9, 0.0, −a+41.1),
    • point D (0.0098a2−2.1856a+39.064, 0.0, −0.0098a2+1.1856a+60.936), and
    • point C (0.0138a2−1.6252a+26.785, −0.0138a2+0.6252a+73.215, 0.0),
    • or on the straight lines A′B′ and DC (excluding the points A′, B′, D, and C).


Item 13.


The composition according to Item 8, wherein

    • when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′B′, B′F, FE, and EA′ that connect the following four points:
    • point A′ (59.0, −a+41.0, 0.0),
    • point B′ (58.9, 0.0, −a+41.1),
    • point F (0.0102a2−2.2922a+59.604, 0.0, −0.0102a2+1.2922a+40.396), and
    • point E (0.0208a2−2.0723a+47.748, −0.0208a=+1.0723a+52.252, 0.0),
    • or on the straight lines A′B′ and FE (excluding the points A′, B′, F, and E).


Item 14.


The composition according to Item 8, wherein

    • when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,
    • if 5.0≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′P, PG, and GA′ that connect the following three points:
    • point A′ (59.0, −a+41.0, 0.0),
    • point P (−0.019a2+0.1524a+58.714, −0.2571a2+4.1571a+9.5429, 0.2761a2−5.3095a+31.7431), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines A′P and PG (excluding the points A′ and G); or
    • if 10.0≥x≥5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines A′P, PG, and GA′ that connect the following three points:
    • point A′ (59.0, −a+41.0, 0.0),
    • point P (59.0, −0.136a2+2.94a+12.6, 0.136a2−3.94a+28.4), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a=−3.6396a+65.951, 0.0),
    • or on the straight lines A′P and PG (excluding the points A′ and G).


Item 15.


The composition according to any one of Items 1 to 14, which is for use as an alternative refrigerant for R410A.


Item 16.


The composition according to Item 2, wherein

    • when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines ST, TM, and MS that connect the following three points:
    • point S (10.0, 21.5, 68.5),
    • point T (1.9, 21.5, 76.6), and
    • point M (10.0, 12.5, 77.5),
    • or on the straight lines.


Item 17.


The composition according to Item 8, wherein

    • when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,
    • if 1.9≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A″T, TM, and MA″ that connect the following three points:
    • point A″ (21.8, −a+78.2, 0.0),
    • point T (21.5, −15.0a+28.5, 14.0a+50.0), and
    • point M (0.0035a2−0.9809a+10.358, −0.0035a2−0.0191a+89.642, 0.0),
    • or on the straight lines A″T and TM (excluding the points A″ and M); or
    • if 10.0≥x>1.9, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines A″B″, B″L, LM, and MA″ that connect the following four points:
    • point A″ (21.8, −a+78.2, 0.0),
    • point B″ (0.0108a+21.473, 0.0, −1.0108a+78.527),
    • point L (0.0098a2−1.2237a+23.804, 0.0, −0.0098a2+0.2237a+76.196), and
    • point M (0.0035a2−0.9809a+10.358, −0.0035a2−0.0191a+89.642, 0.0),
    • or on the straight lines A″B″ and LM (excluding the points A″, B″, L, and M).


Item 18.


The composition according to Item 16 or 17, which is for use as an alternative refrigerant for R404A.


Item 19.


The composition according to any one of Items 1 to 18, which is for use as a working fluid for a refrigerating machine, the composition further comprising a refrigeration oil.


Item 20.


A refrigerating machine comprising the composition according to any one of Items 1 to 14, 16, 17, and 19 as a working fluid.


Item 21.


A method for operating a refrigerating machine, comprising circulating the composition according to any one of Items 1 to 14, 16, 17, and 19 as a working fluid in a refrigerating machine.


Item 22.


Use of the composition according to any one of Items 1 to 14 as an alternative refrigerant for R410A.


Item 23.


Use of the composition according to Item 16 or 17 as an alternative refrigerant for R404A.


EXAMPLES

The present disclosure is described in more detail below with reference to Examples. However, the present disclosure is not limited to the Examples.


Mixed refrigerants were prepared by mixing HFO-1132a, R32, and R1234ze at the mass % shown in Table 1 based on their sum.


The GWPs of R410A (R32=50%/R125=50%) and the above mixed refrigerants were evaluated based on the values stated in the Intergovernmental Panel on Climate Change (IPCC), fourth report. The GWP of HFO-1132a was assumed to be 1. The refrigerating capacities of R410A and the above mixed refrigerants were determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants by using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.


For each of these mixed refrigerants, the COP ratio and refrigerating capacity ratio relative to those of R410A were determined. The calculation conditions were as follows:

    • Evaporating temperature: 5° C.
    • Condensation temperature: 45° C.
    • Superheating temperature: 5 K
    • Subcooling temperature: 5 K
    • Compressor efficiency: 70%


Table 1 shows these values together with the GWP of each mixed refrigerant. The COP and refrigerating capacity are ratios relative to R410A.


The coefficient of performance (COP) was determined according to the following formula.





COP=(refrigerating capacity or heating capacity)/power consumption




















TABLE 1









Comp.
Comp.
Comp.





Comp.
Comp.


Item
Unit
Ex. 1
Ex. 2
Ex. 3
Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5
Ex. 4
Ex. 5





HFO-1132a
mass %
R410A
0.0
0.75
1.5
3.0
5.0
7.5
10.0
12.5
15.0


R32
mass %

50.0
50.0
50.0
50.0
50.0
50.0
50.0
50.0
50.0


R1234ze
mass %

50.0
49.25
48.5
47.0
45.0
42.5
40.0
37.5
35.0


GWP

2088
341
340
340
340
340
340
340
340
340


COP ratio
% (relative to
100.0
104.7
104.4
104.0
103.4
102.5
101.6
100.7
99.8
98.9



R410A)


Refrigerating
% (relative to
100.0
78.2
79.4
80.6
83.0
86.1
90.0
93.8
97.5
101.1


capacity ratio
R410A)


Condensation
° C.
0
7.2
7.7
8.1
8.9
9.7
10.3
10.8
11.0
11.0


temperature glide





















Comp.

Comp.









Ex. 6
Ex. 6
Ex. 7
Ex. 7
Ex. 8
Ex. 9
Ex. 10
Ex. 11


Item
Unit
A
B
A′
B′
C
D
E
F





HFO-1132a
mass %
26.0
1.5
41.0
1.5
1.5
10.0
1.5
10.0


R32
mass %
74.0
73.9
59.0
58.9
35.8
18.2
56.2
37.7


R1234ze
mass %
0.0
24.6
0.0
39.6
62.7
71.8
42.3
52.3


GWP

500
500
399
400
245
127
382
258


COP ratio
% (relative to
94.9
102.9
89.0
103.5
105.4
103.2
103.6
101.5



R410A)


Refrigerating
% (relative to
131.0
97.0
139.0
86.9
70.0
70.0
85.0
85.0


capacity ratio
R410A)


Condensation
° C.
4.6
3.6
3.9
6.3
11.0
21.4
6.9
14.5


temperature glide






















Comp.







Ex. 12
Ex. 13
Ex. 8
Ex. 14
Ex. 15



item
Unit
G
G′
H
I
J







HFO-1132a
mass %
1.5
8.6
10.0
10.0
10.0



R32
mass %
65.9
73.9
75.5
74.0
59.0



R1234ze
mass %
32.6
17.5
14.5
16.0
31.0



GWP

447
500
511
501
400



COP ratio
% (relative to
103.1
100.5
100.0
100.1
100.4




R410A)



Refrigerating
% (relative to
91.7
107.7
110.7
109.8
100.1



capacity ratio
R410A)



Condensation
° C.
5.0
5.1
5.0
5.3
8.4



temperature glide










These results indicate that the mixed refrigerants have a GWP of 500 or less and a refrigerating capacity ratio of 70% or more relative to that of R410A when they satisfy the following requirements.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines IB, BC, CD, and DI that connect the following four points:

    • point I (10.0, 74.0, 16.0),
    • point B (1.5, 73.9, 24.6),
    • point C (1.5, 35.8, 62.7), and
    • point D (10.0, 18.2, 71.8),
    • or on the straight lines.


These results indicate that the mixed refrigerants have a GWP of 500 or less and a refrigerating capacity ratio of 85% or more relative to that of R410A when they satisfy the following requirements.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines IB, BE, EF, and FI that connect the following four points:

    • point I (10.0, 74.0, 16.0),
    • point B (1.5, 73.9, 24.6),
    • point E (1.5, 56.2, 42.3), and
    • point F (10.0, 37.7, 52.3),
    • or on the straight lines.


These results indicate that the mixed refrigerants have a GWP of 500 or less and a condensation temperature glide of 5° C. or less when they satisfy the following requirements.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines G′B, BG, and GG′ that connect the following three points:

    • point G′ (8.6, 73.9, 17.5),
    • point B (1.5, 73.9, 24.6), and
    • point G (1.5, 65.9, 32.6),
    • or on the straight lines.


These results indicate that the mixed refrigerants have a GWP of 400 or less and a refrigerating capacity ratio of 70% or more relative to that of R410A when they satisfy the following requirements.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines JB′, B′C, CD, and DJ that connect the following four points:

    • point J (10.0, 59.0, 31.0),
    • point B′ (1.5, 58.9, 39.6),
    • point C (1.5, 35.8, 62.7), and
    • point D (10.0, 18.2, 71.8),
    • or on the straight lines.


These results indicate that the mixed refrigerants have a GWP of 400 or less and a refrigerating capacity ratio of 85% or more relative to that of R410A when they satisfy the following requirements.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines JB′, B′E, EF, and FJ that connect the following four points:

    • point J (10.0, 59.0, 31.0),
    • point B′ (1.5, 58.9, 39.6),
    • point E (1.5, 56.2, 42.3), and
    • point F (10.0, 37.7, 52.3),
    • or on the straight lines.


Mixed refrigerants further comprising R1234yf in addition to HFO-1132a, R32, and R1234ze were evaluated in the same manner as described above. Tables 2 to 4 shows the results.



















TABLE 2









Comp.
Comp.





Comp.
Comp.


Item
Unit
Ex. 9
Ex. 10
Ex. 16
Ex. 17
Ex. 18
Ex. 19
Ex. 20
Ex. 11
Ex. 12





HFO-1132a
mass %
0.0
0.75
1.5
3.0
5.0
7.5
10.0
12.5
15.0


R32
mass %
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0


R1234yf
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0


R1234ze
mass %
15.0
14.25
13.5
12.0
10.0
7.5
5.0
2.5
0.0


GWP

440
440
440
440
440
440
440
440
440


COP ratio
% (relative to
102.9
102.7
102.4
101.9
101.2
100.4
99.6
98.8
97.9



R410A)


Refrigerating
% (relative to
92.4
93.6
94.7
97.0
100.0
103.7
107.3
110.8
114.2


capacity ratio
R410A)


Condensation
° C.
2.7
3.0
3.2
3.6
4.0
4.4
4.7
4.8
4.8


temperature glide







Comp.
Comp.





Comp.
Comp.


Item
Unit
Ex. 13
Ex. 14
Ex. 21
Ex. 22
Ex. 23
Ex. 24
Ex. 25
Ex. 15
Ex. 16





HFO-11328
mass %
0.0
0.8
1.5
3.0
5.0
7.5
10.0
12.5
15.0


R32
mass %
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0
65.0


R1234yf
mass %
20.0
19.3
18.5
17.0
15.0
12.5
10.0
7.5
5.0


R1234ze
mass %
15.0
15.00
15.0
15.0
15.0
15.0
15.0
15.0
15.0


GWP

440
440
440
440
440
440
440
440
440


COP ratio
% (relative to
102.9
102.7
102.4
102.0
101.4
100.6
99.9
99.2
98.5



R410A)


Refrigerating
% (relative to
92.4
93.4
94.5
96.5
99.2
102.5
105.7
108.9
112.1


capacity ratio
R410A)


Condensation
° C.
2.7
3.0
3.3
3.9
4.6
5.2
5.8
6.2
6.5


temperature glide







Comp.
Comp.





Comp.
Comp.


Item
Unit
Ex. 17
Ex. 18
Ex. 26
Ex. 27
Ex. 28
Ex. 29
Ex. 30
Ex. 19
Ex. 20





HFO-1132a
mass %
0.0
0.75
1.5
3.0
5.0
7.5
10.0
10.0
15.0


R32
mass %
65.0
64.3
63.5
62.0
60.0
57.5
55.0
52.5
50.0


R1234yf
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0


R1234ze
mass %
15.0
15.00
15.0
15.0
15.0
15.0
15.0
15.0
15.0


GWP

440
435
430
420
407
390
373
356
339


COP ratio
% (relative to
102.9
102.7
102.4
101.9
101.3
100.5
99.8
99.7
98.2



R410A)


Refrigerating
% (relative to
92.4
93.1
93.7
94.9
96.6
98.5
100.4
100.0
104.0


capacity ratio
R410A)


Condensation
° C.
2.7
3.1
3.4
4.1
5.0
5.9
6.7
7.0
8.0


temperature glide

























TABLE 3









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




Ex. 21
Ex. 22
Ex. 23
Ex. 24
Ex. 25
Ex. 26
Ex. 27
Ex. 28


Item
Unit
A
B
A′
B′
C
D
E
F





HFO-11328
mass %
1.9
1.5
1.5
1.5
3.5
1.5
1.5
1.5


R32
mass %
74.0
73.9
59.0
58.9
24.4
35.8
44.7
56.2


R1234yf
mass %
24.5
0.0
39.5
0.0
74.1
0.0
53.8
0.0


R1234ze
mass %
0.0
24.6
0.0
39.6
0.0
62.7
0.0
42.3


GWP

500
500
400
400
168
245
304
382


COP ratio
% (relative to
101.9
102.9
101.8
103.5
102.6
105.4
101.7
103.6



R410A)


Refrigerating
% (relative to
101.4
97.0
93.7
85.9
70.0
70.0
85.0
85.0


capacity ratio
R410A)


Condensation
° C.
1.5
3.6
2.5
6.3
7.1
11.0
4.0
6.9


temperature glide



















Comp.

Comp.
Comp.
Comp.
Comp.




Ex. 29
Ex. 31
Ex. 30
Ex. 31
Ex. 32
Ex. 33


Item
Unit
G
P
H
C′
E′
G′





HFO-1132a
mass %
1.5
1.5
1.5
1.5
1.5
1.5


R32
mass %
37.9
58.9
65.9
30.1
50.4
51.9


R1234yf
mass %
60.6
15.2
0.0
32.6
24.9
26.2


R1234ze
mass %
0.0
24.4
32.6
35.8
23.2
20.4


GWP

258
400
447
207
343
353


COP ratio
% (relative to
101.8
102.8
103.1
104.1
102.8
102.6



R410A)


Refrigerating
% (relative to
80.3
89.6
91.7
70.0
85.0
86.4


capacity ratio
R410A)


Condensation
° C.
5.0
4.7
5.0
9.0
5.4
5.0


temperature glide





















Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




Ex. 34
Ex. 35
Ex. 36
Ex. 37
Ex. 38
Ex. 39
Ex. 40
Ex. 41


Item
Unit
A
B
A′
B′
C
D
E
F





HFO-1132a
mass %
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0


R32
mass %
74.0
73.9
59.0
58.9
22.0
32.6
41.7
52.8


R1234yf
mass %
23.0
0.0
38.0
0.0
75.0
0.0
55.3
0.0


R1234ze
mass %
0.0
23.1
0.0
38.1
0.0
64.4
0.0
44.2


GWP

500
500
400
400
152
224
284
359


COP ratio
% (relative to
101.5
102.3
101.3
102.8
102.4
104.9
101.3
103.2



R410A)


Refrigerating
% (relative to
103.3
99.3
95.7
89.3
70.0
70.0
85.0
85.0


capacity ratio
R410A)


Condensation
° C.
2.0
4.1
3.0
6.9
8.1
12.9
5.0
8.2


temperature glide







Comp.

Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




Ex. 42
Ex. 32
Ex. 43
Ex. 44
Ex. 45
Ex. 46
Ex. 47
Ex. 48


Item
Unit
G
P
H
A
B
A′
B′
C





HFO-11328
mass %
3.0
3.0
3.0
5.0
.0
5.0
5.0
5.0


R32
mass %
41.5
59.0
68.6
74.0
73.9
59.0
58.9
19.0


R1234yf
mass %
55.5
19.7
0.0
21.0
0.0
36.0
0.0
76.0


R1234ze
mass %
0.0
18.3
28.4
0.0
21.0
0.0
36.1
0.0


GWP

282
400
466
500
500
400
400
131


COP ratio
% (relative to
101.3
102.1
102.5
100.9
101.7
100.7
102.1
102.1



R410A)


Refrigerating
% (relative to
84.8
92.8
95.9
105.9
102.4
98.4
92.4
70.0


capacity ratio
R410A)


Condensation
° C.
5.0
4.7
5.0
2.5
4.6
3.6
7.5
9.5


temperature glide



















Comp.
Comp.
Comp.
Comp.

Comp.




Ex. 49
Ex. 50
Ex. 51
Ex. 52
Ex. 33
Ex. 53


Item
Unit
D
E
F
G
P
H





HFO-1132a
mass %
5.0
5.0
5.0
5.0
5.0
5.0


R32
mass %
28.4
37.9
48.4
46.0
59.0
73.4


R1234yf
mass %
0.0
57.1
0.0
49.0
23.9
0.0


R1234ze
mass %
66.6
0.0
46.6
0.0
12.1
23.6


GWP

196
258
330
313
400
483


COP ratio
% (relative to
104.3
100.7
102.6
100.6
101.2
101.7



R410A)


Refrigerating
% (relative to
70.0
85.0
85.0
90.5
96.5
100.8


capacity ratio
R410A


Condensation
° C.
15.3
6.2
10.1
5.6
4.8
5.0


temperature glide

























TABLE 4









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




Ex. 54
Ex. 55
Ex. 56
Ex. 57
Ex. 58
Ex. 59
Ex. 60
Ex. 61


Item
Unit
A
B = H
A′
B′
C
D
E
F





HFO-1132a
mass %
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5


R32
mass %
74.0
73.9
59.0
58.9
15.4
23.2
33.4
43.0


R1234yf
mass %
18.5
0.0
33.5
0.0
77.1
0.0
59.1
0.0


R1234ze
mass %
0.0
18.6
0.0
33.6
0.0
69.3
0.0
49.5


GWP

500
500
400
400
107
161
228
293


COP ratio
% (relative to
100.2
100.8
100.0
101.2
101.8
103.7
100.2
102.0



R410A)


Refrigerating
% (relative to
109.1
106.1
101.6
96.2
70.0
70.0
85.0
85.0


capacity ratio
R410A)


Condensation
° C.
3.1
5.0
4.2
8.1
11.1
18.4
7.7
12.3


temperature glide







Comp.

Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




Ex. 62
Ex. 34
Ex. 63
Ex. 64
Ex. 65
Ex. 66
Ex. 67
Ex. 68


Item
Unit
G
P
A
B
A′
B′
C
D





HFO-1132a
mass %
7.5
7.5
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
51.0
59.0
74.0
73.9
59.0
58.9
11.9
18.2


R1234yf
mass %
41.5
27.0
16.0
0.0
31.0
0.0
78.1
0.0


R1234ze
mass %
0.0
6.5
0.0
16.1
0.0
31.1
0.0
71.8


GWP

346
400
500
500
400
400
84
127


COP ratio
% (relative to
99.9
100.2
99.5
100.1
99.3
100.4
101.6
103.2



R410A)


Refrigerating
% (relative to
97.0
100.7
112.3
109.7
104.8
100.0
70.0
70.0


capacity ratio
R410A)


Condensation
° C.
5.0
4.8
3.6
5.3
4.6
8.4
12.5
21.4


temperature glide



















Comp.
Comp.
Comp.

Comp.
Comp.




Ex. 69
Ex. 70
Ex. 71
Ex. 35
Ex. 72
Ex. 73


Item
Unit
E
F
G
P
R
H





HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
29.1
37.7
55.4
59.0
73.9
75.5


R1234yf
mass %
60.9
0.0
34.6
28.4
2.8
0.0


R1234ze
mass %
0.0
52.3
0.0
2.6
13.3
14.5


GWP

199
258
375
400
500
511


COP ratio
% (relative to
99.7
101.5
99.2
99.4
100.0
100.0



R410A)


Refrigerating
% (relative to
85.0
85.0
102.8
104.5
110.2
110.7


capacity ratio
R410A)


Condensation
° C.
9.1
14.5
5.0
4.9
5.0
5.0


temperature glide









These results indicate that the mixed refrigerants have a GWP of 500 or less and a refrigerating capacity ratio of 70% or more relative to that of R410A when they satisfy the following requirements.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BC, CD, and DA that connect the following four points:

    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point D (0.0098a2−2.1856a+39.064, 0.0, −0.0098a2+1.1856a+60.936), and
    • point C (0.0138a2−1.6252a+26.785, −0.0138a2+0.6252a+73.215, 0.0),
    • or on the straight lines AB and CD (excluding the points A, B, C, and D).


These results indicate that the mixed refrigerants have a GWP of 500 or less and a refrigerating capacity ratio of 85% or more relative to that of R410A when they satisfy the following requirements.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BF, FE, and EA that connect the following four points:

    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point F (0.0102a2−2.2922a+59.604, 0.0, −0.0102a2+1.2922a+40.396), and
    • point E (0.0208a2−2.0723a+47.748, −0.0208a2+1.0723a+52.252, 0.0),
    • or on the straight lines AB and FE (excluding the points A, B, F, and E).


These results indicate that the mixed refrigerants have a GWP of 500 or less and a condensation temperature glide of 5° C. or less when they satisfy the following requirements.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,

    • if 5.0≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BH, HG, and GA that connect the following four points:
    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point H (−0.1143a2+2.3143a+62.686, 0.0, 0.1143a=−3.3143a+37.314), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AB and HG (excluding the points A, B, H, and G);
    • if 7.5≥x>5.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AB, BH, HG, and GA that connect the following four points:
    • point A (74.0, −a+26.0, 0.0),
    • point B (73.9, 0.0, −a+26.1),
    • point H (−0.072a2+1.9a+63.7, 0.0, 0.072a2−2.9a+36.3), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AB and HG (excluding the points A, B, H, and G); or
    • if 10.0≥x≥7.5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AR, RG, and GA that connect the following three points:
    • point A (74.0, −a+26.0, 0.0),
    • point R (73.9, 1.12a−8.4, −2.12a+34.5), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines AR and RG (excluding the points A and G).


These results indicate that the mixed refrigerants have a GWP of 400 or less and a refrigerating capacity ratio of 70% or more relative to that of R410A when they satisfy the following requirements.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′B′, B′D, DC, and CA′ that connect the following four points:

    • point A′ (59.0, −a+41.0, 0),
    • point B′ (58.9, 0.0, −a+41.1),
    • point D (0.0098a=−2.1856a+39.064, 0.0, −0.0098a2+1.1856a+60.936), and
    • point C (0.0138a2−1.6252a+26.785, −0.0138a2+0.6252a+73.215, 0.0),
    • or on the straight lines A′B′ and DC (excluding the points A′, B′, D, and C).


These results indicate that the mixed refrigerants have a GWP of 400 or less and a refrigerating capacity ratio of 85% or more relative to that of R410A when they satisfy the following requirements.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′B′, B′F, FE, and EA′ that connect the following four points:

    • point A′ (59.0, −a+41.0, 0.0),
    • point B′ (58.9, 0.0, −a+41.1),
    • point F (0.0102a2−2.2922a+59.604, 0.0, −0.0102a2+1.2922a+40.396), and
    • point E (0.0208a2−2.0723a+47.748, −0.0208a2+1.0723a+52.252, 0.0),
    • or on the straight lines A′B′ and FE (excluding the points A′, B′, F, and E).


These results indicate that the mixed refrigerants have a GWP of 400 or less and a condensation temperature glide of 5° C. or less when they satisfy the following requirements.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,

    • if 5.0≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′P, PG, and GA′ that connect the following three points:
    • point A′ (59.0, −a+41.0, 0.0),
    • point P (−0.019a2+0.1524a+58.714, −0.2571a2+4.1571a+9.5429, 0.2761a2−5.3095a+31.7431), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines A′P and PG (excluding the points A′ and G), or
    • if 10.0≥x≥5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines A′P, PG, and GA′ that connect the following three points:
    • point A′ (59.0, −a+41.0, 0.0),
    • point P (59.0, −0.136a2+2.94a+12.6, 0.136a=−3.94a+28.4), and
    • point G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),
    • or on the straight lines A′P and PG (excluding the points A′ and G).


Approximate expressions indicating the coordinates of each point were obtained by determining approximate expressions for the curves connecting three points, as shown in Tables 5 and 6.









TABLE 5







Point A













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
74.0
74.0
74.0
74.0
74.0


R1234yf
mass %
24.5
23.0
21.0
18.5
16.0


R1234ze
mass %
0.0
0.0
0.0
0.0
0.0








R32 approximate expression
74.0


R1234yf approximate expression
−a + 26


R1234ze approximate expression
0.0










Point B













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
73.9
73.9
73.9
73.9
73.9


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
24.6
23.1
21.1
18.6
16.1








R32 approximate expression
73.9


R1234yf approximate expression
0.0


R1234ze approximate expression
−a + 26.1










Point A′













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
59.0
59.0
59.0
59.0
59.0


R1234yf
mass %
39.5
38.0
36.0
33.5
31.0


R1234ze
mass %
0.0
0.0
0.0
0.0
0.0








R32 approximate expression
59.0


R1234yf approximate expression
−a + 41.0


R1234ze approximate expression
0.0










Point B′













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
58.9
58.9
58.9
58.9
58.9


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
39.6
38.1
36.1
33.6
31.1








R32 approximate expression
58.9


R1234yf approximate expression
0.0


R1234ze approximate expression
−a + 41.1










Point C













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
24.4
22.0
19.0
15.4
11.9


R1234yf
mass %
74.1
75.0
76.0
77.1
78.1


R1234ze
mass %
0.0
0.0
0.0
0.0
0.0








R32 approximate expression
0.0138a2 − 1.6252a + 26.785


R1234yf approximate expression
−0.0138a2 + 0.6252a + 73.215


R1234ze approximate expression
0.0










Point D













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
35.8
32.6
28.4
23.2
18.2


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
62.7
64.4
66.6
69.3
71.8








R32 approximate expression
0.0098a2 − 2.1856a + 39.064


R1234yf approximate expression
0.0


R1234ze approximate expression
−0.0098a2 + 1.1856a + 60.936
















TABLE 6







Point E













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
44.7
41.7
37.9
33.4
29.1


R1234yf
mass %
53.8
55.3
57.1
59.1
60.9


R1234ze
mass %
0.0
0.0
0.0
0.0
0.0








R32 approximate expression
0.0208a2 − 2.0723a + 47.748


R1234yf approximate expression
−0.0208a2 + 1.0723a + 52.252


R1234ze approximate expression
0.0










Point F













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
56.2
52.8
48.4
43.0
37.7


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
42.3
44.2
46.6
49.5
52.3








R32 approximate expression
0.0102a2 − 2.2922a + 59.604


R1234yf approximate expression
0.0


R1234ze approximate expression
−0.0102a2 + 1.2922a + 40.396










Point G













a = HFO-1132a
mass %
1.5
3.0
5.0
7.5
10.0


R32
mass %
37.9
41.5
46.0
51.0
55.4


R1234yf
mass %
60.6
55.5
49.0
41.5
34.6


R1234ze
mass %
0.0
0.0
0.0
0.0
0.0








R32 approximate expression
−0.0505a2 + 2.6396a + 34.049


R1234yf approximate expression
0.0505a2 − 3.6396a + 65.951


R1234ze approximate expression
0.0










Point H














a = HFO-1132a
mass %
1.5
3.0
5.0
5.0
7.5
10.0


R32
mass %
65.9
68.6
71.4
71.4
73.9
75.5


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
32.6
28.4
23.6
23.6
18.6
14.5









R32 approximate expression
−0.1143a2 + 2.3143a + 62.686
−0.072a2 + 1.9a + 63.7


R1234yf approximate expression
0.0
0.0


R1234ze approximate expression
0.1143a2 − 3.3143a + 37.314
0.072a2 − 2.9a + 36.3










Point P














a = HFO-1132a
mass %
1.5
3.0
5.0
5.0
7.5
10.0


R32
mass %
58.9
59.0
59.0
59.0
59.0
59.0


R1234yf
mass %
15.2
19.7
23.9
23.9
27.0
28.4


R1234ze
mass %
24.4
18.3
12.1
12.1
6.5
2.6









R32 approximate expression
−0.019a2 + 0.1524a + 58.714
59.0


R1234yf approximate expression
−0.2571a2 + 4.1571a + 9.5429
−0.136a2 + 2.94a + 12.6


R1234ze approximate expression
0.2761a2 − 5.3095a + 31.7431
0.136a2 − 3.94a + 28.4










Point R












x = HFO-1132a
mass %
7.5
10.0



R32
mass %
73.9
73.9



R1234yf
mass %
0.0
2.8



R1234ze
mass %
18.6
13.3










R32 approximate expression
73.9



R1234yf approximate expression
1.12a − 8.4



R1234ze approximate expression
−2.12a + 34.5










For each mixed refrigerant, the COP ratio and refrigerating capacity ratio relative to those of R404A were determined. The calculation conditions were as follows:

    • Evaporating temperature: −40° C.
    • Condensation temperature: 40° C.
    • Superheating temperature: 20 K
    • Subcooling temperature: 0 K
    • Compressor efficiency: 70%


Tables 7 and 8 show these values together with the GWP of each mixed refrigerant. The COP and refrigerating capacity are ratios relative to R404A.


The coefficient of performance (COP) was determined according the following formula.





COP=(refrigerating capacity or heating capacity)/power consumption


Various properties of the mixed refrigerants were evaluated as shown in Tables 7 and 8 while changing the concentration of HFO-1132a.




















TABLE 7







Comp.
Comp.
Comp.





Comp.
Comp.


Item
Unit
Ex. 56
Ex. 74
Ex. 75
Ex. 36
Ex. 37
Ex. 38
Ex. 39
Ex. 40
Ex. 76
Ex. 77


























HFO-1132a
mass %
R404A
0.0
0.75
1.5
3.0
5.0
7.5
10.0
12.5
15.0


R32
mass %

21.5
21.5
21.5
21.5
21.5
21.5
21.5
21.5
21.5


R1234ze
mass %

78.5
77.75
77.0
75.5
73.5
71.0
68.5
66.0
63.5


GWP

2088
150
150
150
150
150
149
149
149
149


COP ratio
% (relative to
100.0
113.1
112.6
112.0
111.0
109.6
108.0
106.5
105.0
103.6



R404A)


Refrigerating
% (relative to
100.0
66.4
67.9
69.3
72.1
75.8
80.6
85.3
90.2
95.2


capacity ratio
R404A)


Condensation
° C.
0
10.9
12.3
13.5
15.6
17.8
19.8
21.1
21.9
22.3


temperature glide


Evaporation
° C.
0.1
6.4
6.7
7.0
7.7
8.5
9.6
10.5
11.5
12.4


temperature glide























TABLE 8









Comp.


Comp.

Comp.




Ex. 78
Ex. 41
Ex. 42
Ex. 79
Ex. 43
Ex. 80


Item
Unit
L
T
M
A″
S
B″





HFO-1132a
mass %
1.5
1.9
10.0
77.9
10.0
1.5


R32
mass %
22.0
21.5
12.5
22.1
21.5
21.5


R1234ze
mass %
76.5
76.6
77.5
0.0
68.5
77.0


GWP

153
150
89
150
149
150


COP ratio
% (relative to
112.0
111.7
105.7

106.5
112.0



R410A)


Refrigerating
% (relative to
70.0
70.0
70.0

85.3
69.3


capacity ratio
R410A)


Condensation
° C.
13.4
14.1
24.5

21.1
13.5


temperature glide


Evaporation
° C.
7.1
7.2
8.4

10.5
7.0


temperature glide






















Comp.
Comp.
Comp.
Comp.
Comp.

Comp.

Comp.




Ex. 81
Ex. 82
Ex. 83
Ex. 84
Ex. 85
Ex. 44
Ex. 86
Ex. 45
Ex. 87


Item
Unit
A″
B″
L
L′
M
T
A″
B″ = L = T
M





HFO-1132a
mass %
1.5
1.5
1.5
1.5
1.5
1.5
1.9
1.9
1.9


ER32
mass %
21.8
21.5
21.8
21.5
8.9
21.5
21.8
21.5
8.5


R1234yf
mass %
76.7
0.00
76.7
0.0
89.6
6.0
76.3
0.0
89.6


R1234ze
mass %
0.0
77.00
0.0
77.0
0.0
71.0
0.0
76.6
0.0


GWP

150
150
153
109
64
150
150
150
61


COP ratio
% (relative to
107.4
112.0
112.0
109.5
106.7
111.7
107.3
111.7
106.5



R404A)


Refrigerating
% (relative to
91.7
69.3
70.0
70.0
70.0
70.9
92.4
70.0
70.0


capacity ratio
R404A)


Condensation
° C.
7.7
13.5
13.4
10.8
7.7
13.0
7.9
14.1
7.9


temperature glide


Evaporation
° C.
4.4
7.0
7.1
5.2
2.5
7.0
4.5
7.2
2.5


temperature glide





















Comp.


Comp.
Comp.


Comp.




Ex. 88
Ex. 46
Ex. 47
Ex. 89
Ex. 90
Ex. 48
Ex. 49
Ex. 91


Item
Unit
A″
B″
L
M
A″
B″
L
M





HFO-1132a
mass %
6.0
6.0
6.0
6.0
10.0
10.0
10.0
10.0


R32
mass %
21.8
21.5
16.8
4.6
21.8
21.6
12.5
0.9


R1234yf
mass %
72.2
0.00
0.0
89.4
68.2
0.0
0.0
89.1


R1234ze
mass %
0.0
72.50
77.2
0.0
0.0
68.4
77.5
0.0


GWP

150
150
118
35
150
150
89
10


COP ratio
% (relative to
105.9
109.0
108.7
105.3
104.5
106.5
105.7
104.3



R404A)


Refrigerating
% (relative to
100.2
77.7
70.0
70.0
108.0
85.5
70.0
70.0


capacity ratio
R404A)


Condensation
° C.
9.9
18.6
19.9
10.5
11.3
21.1
24.5
12.4


temperature glide


Evaporation
° C.
5.5
8.9
7.9
2.7
6.
10.6
8.4
3.0


temperature glide









Tables 7 and 8 indicate that the mixed refrigerants have a GWP of 150 or less and a refrigerating capacity ratio of 70% or more relative to that of R404A when they satisfy the following requirements.


Requirements

When the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines ST, TM, and MS that connect the following three points:

    • point S (10.0, 21.5, 68.5),
    • point T (1.9, 21.5, 76.6), and
    • point M (10.0, 12.5, 77.5),
    • or on the straight lines.


Tables 7 and 8 indicate that the mixed refrigerants have a GWP of 150 or less and a refrigerating capacity ratio of 70% or more relative to that of R404A when they satisfy the following requirements.


Requirements

When the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,

    • if 1.9≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A″T, TM, and MA″ that connect the following three points:
    • point A″ (21.8, −a+78.2, 0.0),
    • point T (21.5, −15.0a+28.5, 14.0a+50.0), and
    • point M (0.0035a2−0.9809a+10.358, −0.0035a2−0.0191a+89.642, 0.0),
    • or on the straight lines A″T and TM (excluding the points A″ and M), or
    • if 10.0≥x≥1.9, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines A″B″, B″L, LM, and MA″ that connect the following four points:
    • point A″ (21.8, −a+78.2, 0.0),
    • point B″ (0.0108a+21.473, 0.0, −1.0108a+78.527),
    • point L (0.0098a2−1.2237a+23.804, 0.0, −0.0098a2+0.2237a+76.196), and
    • point M (0.0035a2−0.9809a+10.358, −0.0035a=−0.0191a+89.642, 0.0),
    • or on the straight lines A″B″ and LM (excluding the points A″, B″, L, and M).


Approximate expressions indicating the coordinates of each point were obtained by determining approximate expressions for the curves connecting three points, as shown in Table 9.









TABLE 9







A″















a = HFO-1132a
mass %
1.5
1.9
6.0
10.0


R32
mass %
21.8
21.8
21.8
21.8


R1234yf
mass %
76.7
76.3
72.2
68.2


R1234ze
mass %
0.0
0.0
0.0
0.0








R32 approximate expression
21.8


R1234yf approximate expression
−a + 78.2


R1234ze approximate expression
0.0










B″















a = HFO-1132a
mass %
1.5
1.9
6.0
10.0


R32
mass %
21.5
21.5
21.5
21.6


R1234yf
mass %
0.0
0.0
0.0
0.0


R1234ze
mass %
77.0
76.6
72.5
68.4








R32 approximate expression
0.0108a + 21.473


R1234yf approximate expression
0.0


R1234ze approximate expression
−1.0108a + 78.527










L















a = HFO-1132a
mass %
1.5
1.9
6.0
10.0


R32
mass %
22.0
21.5
16.8
12.5


R1234yf
mass %
0.0
0.0
0.0
0.0


R1234ze
mass %
76.5
76.6
77.2
77.5








R32 approximate expression
0.0098a2-1.2237a + 23.804


R1234yf approximate expression
0.0


R1234ze approximate expression
−0.0098a2 + 0.2237a + 76.196










M















a = HFO-1132a
mass %
1.5
1.9
6.0
10.0


R32
mass %
8.9
8.5
4.6
0.9


R1234yf
mass %
89.6
89.6
89.4
89.1


R1234ze
mass %
0.0
0.0
0.0
0.0








R32 approximate expression
0.0035a2-0.9809a + 10.358


R1234yf approximate expression
−0.0035a2-0.0191a + 89.642


R1234ze approximate expression
0.0










T













a = HFO-1132a
mass %
1.5
1.9


R32
mass %
21.5
21.5


R1234yf
mass %
6.0
0.0


R1234ze
mass %
71.0
76.6








R32 approximate expression
21.5


R1234yf approximate expression
−15.0a + 28.5


R1234ze approximate expression
14.0a + 50.0









The following mixed refrigerants were also evaluated in the same manner.


















TABLE 10









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.


Item
Unit
Ex. 92
Ex. 93
Ex. 94
Ex. 95
Ex. 96
Ex. 97
Ex. 98
Ex. 99





HFO-1132a
mass %
3.0
5.0
7.0
12.5
3.0
5.0
7.0
12.5


R32
mass %
15.0
15.0
15.0
15.0
20.0
20.0
20.0
20.0


R1234y
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
82.0
80.0
78.0
72.5
77.0
75.0
73.0
67.5


GWP

106
106
106
106
140
140
139
139


COP ratio
% (relative to
105.6
104.7
104.1
102.7
105.7
104.8
104.1
102.4



R410A)


Refrigerating
% (relative to
54.9
58.5
62.1
71.5
59.5
63.0
66.5
75.6


capacity ratio
R410A)


Condensation
° C.
15.7
18.4
20.5
23.6
15.2
17.4
19.0
21.5


temperature glide







Comp.
Comp.

Comp.
Comp.


Comp.


Item
Unit
Ex. 100
Ex. 101
Ex. 50
Ex. 102
Ex 103
Ex. 51
Ex. 52
Ex. 104





HFO-11328
mass %
3.0
5.0
7.0
12.5
3.0
5.0
7.0
12.5


R32
mass %
25.0
25.0
25.0
25.0
30.0
30.0
30.0
30.0


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
72.0
70.0
68.0
62.5
67.0
65.0
63.0
57.5


GWP

173
173
173
173
207
206
206
206


COP ratio
% (relative to
105.5
104.6
103.8
101.9
105.1
104.2
103.4
101.3



R410A)


Refrigerating
% (relative to
63.8
67.3
70.6
79.4
67.9
71.3
74.5
83.1


capacity ratio
R410A)


Condensation
° C.
14.4
16.2
17.5
19.5
13.4
14.9
16.0
17.6


temperature glide










Comp.



Comp.


Item
Unit
Ex. 53
Ex. 54
Ex. 55
Ex. 105
Ex. 56
Ex. 57
Ex. 58
Ex. 106





HFO-11328
mass %
3.0
5.0
7.0
12.5
3.0
5.0
7.0
12.5


R32
mass %
35.0
35.0
35.0
35.0
40.0
40.0
40.0
40.0


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
62.0
60.0
58.0
52.5
57.0
55.0
53.0
47.5


GWP

240
240
240
240
273
273
273
273


COP ratio
% (relative to
104.7
103.7
102.9
100.8
104.2
103.3
102.5
100.4



R410A)


Refrigerating
% (relative to
71.8
75.1
78.3
86.8
75.6
78.8
82.0
90.4


capacity ratio
R410A)


Condensation
° C.
12.3
13.6
14.5
15.8
11.2
12.2
13.0
14.1


temperature glide










Comp.



Comp.


Item
Unit
Ex. 59
Ex. 60
Ex. 61
Ex. 107
Ex. 62
Ex. 63
Ex. 64
Ex. 108





HFO-11323
mass %
3.0
5.0
7.0
12.5
3.0
5.0
7.0
12.5


R32
mass %
45.0
45.0
45.0
45.0
50.0
50.0
50.0
50.0


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
52.0
50.0
48.0
42.5
47.0
45.0
43.0
37.5


GWP

307
307
307
306
340
340
340
340


COP ratio
% (relative to
103.7
102.9
102.1
100.0
103.4
102.5
101.8
99.8



R410A)


Refrigerating
% (relative to
79.3
82.5
85.6
94.0
83.0
86.1
89.2
97.5


capacity ratio
R410A)


Condensation
° C.
10.0
10.9
11.6
12.5
8.9
9.7
10.2
11.0


temperature glide










Comp.



Comp.


Item
Unit
Ex. 65
Ex. 66
Ex. 67
Ex. 109
Ex. 68
Ex. 69
Ex. 70
Ex. 110





HFO-1132a
mass %
3.0
5.0
7.0
12.5
3.0
5.0
7.0
12.5


R32
mass %
55.0
55.0
55.0
55.0
60.0
60.0
60.0
60.0


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
42.0
40.0
38.0
32.5
37.0
35.0
33.0
27.5


GWP

374
374
374
373
407
407
407
407


COP ratio
% (relative to
103.0
102.3
101.5
99.6
102.8
102.0
101.3
99.5



R410A)


Refrigerating
% (relative to
86.5
89.7
92.8
101.0
90.0
93.2
96.2
104.4


capacity ratio
R410A)


Condensation
° C.
7.7
8.4
8.9
9.6
6.7
7.3
7.8
8.3


temperature glide










Comp.



Comp.


Item
Unit
Ex. 71
Ex. 72
Ex. 73
Ex. 111
Ex. 74
Ex. 75
Ex. 76
Ex. 112





HFO-1132a
mass %
3.0
5.0
7.0
12.5
3.0
5.0
7.0
12.5


R32
mass %
65.0
65.0
65.0
65.0
70.0
70.0
70.0
70.0


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
32.0
30.0
28.0
22.5
27.0
25.0
23.0
17.5


GWP

441
441
441
440
474
474
474
474


COP ratio
% (relative to
102.6
101.9
101.2
99.4
102.4
101.8
101.1
99.3



R410A)


Refrigerating
% (relative to
93.5
96.6
99.6
107.7
96.8
99.9
102.9
110.9


capacity ratio
R410A)


Condensation
° C.
5.7
6.2
6.7
7.2
4.8
5.3
5.6
6.1


temperature glide



















Comp.
Comp.
Comp.
Comp.



Item
Unit
Ex. 113
Ex. 114
Ex. 115
Ex. 116







HFO-1132a
mass %
3.0
5.0
7.0
12.5



R32
mass %
80.0
80.0
80.0
80.0



R1234yf
mass %
0.0
0.0
0.0
0.0



R1234ze
mass %
17.0
15.0
13.0
7.5



GWP

541
541
541
541



COP ratio
% (relative to
102.2
101.5
100.9
99.2




R410A)



Refrigerating
% (relative to
103.1
106.1
109.0
116.8



capacity ratio
R410A)



Condensation
° C.
3.1
3.5
3.9
4.4



temperature glide


























TABLE 11









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Item
Unit
Ex. 117
Ex. 118
Ex. 119
Ex. 120
Ex. 121
Ex. 122
Ex. 123
Ex. 77





HFO-1132a
mass %
1.6
1.5
1.5
1.5
1.5
1.5
1.5
1.5


R32
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
30.0


R1234yf
mass %
68.5
58.5
48.5
38.5
28.5
18.5
8.5
58.5


R1234ze
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0


GWP

138
139
139
139
139
139
140
205


COP ratio
% (relative
103.5
103.9
104.4
104.9
105.4
105.8
106.3
102.7



to R410A)


Refrigerating
% (relative
65.2
64.1
63.0
61.7
60.5
59.2
57.9
73.3


capacity ratio
to R410A)


Condensation
° C.
8.1
8.8
9.4
10.1
10.9
11.7
12.4
6.9


temperature glide









Comp.
Comp.
Comp.





Item
Unit
Ex. 78
Ex. 79
Ex. 124
Ex. 125
Ex. 126
Ex. 80
Ex. 81
Ex. 82





HFO-1132a
mass %
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5


R32
mass %
30.0
30.0
30.0
30.0
30.0
40.0
40.0
40.0


R1234yf
mass %
48.5
38.5
28.5
18.5
8.5
48.5
38.5
28.5


R1234ze
mass %
20.0
30.0
40.0
50.0
60.0
10.0
20.0
30.0


GWP

206
206
206
206
206
273
273
273


COP ratio
% (relative
103.3
103.8
104.4
104.9
105.5
102.3
102.8
103.3



to R410A)


Refrigerating
% (relative
72.0
70.7
69.4
68.0
66.6
80.5
79.0
77.5


capacity ratio
to R410A)


Condensation
° C.
7.7
8.5
9.4
10.3
11.2
5.5
6.4
7.3


temperature glide





Item
Unit
Ex. 83
Ex. 84
Ex. 85
Ex. 86
Ex. 87
Ex. 88
Ex. 89
Ex. 90





HFO-1132a
mass %
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5


R32
mass %
40.0
40.0
50.0
50.0
50.0
50.0
60.0
60.0


R1234yf
mass %
18.5
8.5
38.5
28.5
18.5
8.5
28.5
18.5


R1234ze
mass %
40.0
50.0
10.0
20.0
30.0
40.0
10.0
20.0


GWP

273
273
340
340
340
340
407
407


COP ratio
% (relative
103.9
104.4
102.2
102.6
103.1
103.6
102.2
102.6



to R410A)


Refrigerating
% (relative
76.0
74.5
86.9
85.3
83.6
82.0
92.7
91.0


capacity ratio
to R410A)


Condensation
° C.
8.3
9.3
4.2
5.2
6.2
7.2
3.3
4.2


temperature glide






















Comp.



Item
Unit
Ex. 91
Ex. 92
Ex. 93
Ex. 127







HFO-1132a
mass %
1.5
1.5
1.5
1.5



R32
mass %
60.0
70.0
70.0
80.0



R1234yf
mass %
8.5
18.5
8.5
8.5



R1234ze
mass %
30.0
10.0
20.0
10.0



GWP

407
474
474
541



COP ratio
% (relative
103.0
102.3
102.7
102.4




to R410A)



Refrigerating
% (relative
89.2
97.8
96.0
102.4



capacity ratio
to R410A)



Condensation
° C.
5.2
2.5
3.4
2.0



temperature glide


























TABLE 12









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Item
Unit
Ex. 128
Ex. 129
Ex. 130
Ex. 131
Ex. 132
Ex. 133
Ex. 134
Ex. 94





HFO-1132a
mass %
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0


R32
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
30.0


R1234y1
mass %
67.0
57.0
47.0
37.0
27.0
17.0
7.0
57.0


R1234ze
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0


GWP

138
139
139
139
139
139
140
205


COP ratio
% (relative to
103.0
103.4
103.9
104.3
104.7
105.1
105.5
102.2



R410A)


Refrigerating
% (relative to
67.3
66.2
65.1
64.0
62.8
61.6
60.4
75.3


capacity ratio
R410A)


Condensation
° C.
9.0
9.8
10.6
11.5
12.4
13.4
14.4
7.6


temperature glide










Comp.






Item
Unit
Ex. 95
Ex. 96
Ex. 97
Ex. 135
Ex. 98
Ex. 99
Ex. 100
Ex. 101





HFO-1132a
mass %
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0


R32
mass %
30.0
30.0
30.0
30.0
40.0
40.0
40.0
40.0


R1234yt
mass %
47.0
37.0
27.0
7.0
47.0
37.0
27.0
17.0


R1234ze
mass %
20.0
30.0
40.0
60.0
10.0
20.0
30.0
40.0


GWP

206
206
206
206
273
273
273
273


COP ratio
% (relative to
102.7
103.2
103.8
104.8
101.8
102.3
102.8
103.3



R410A)


Refrigerating
% (relative to
74.1
72.8
71.5
68.9
82.5
81.1
79.6
78.1


capacity ratio
R410A)


Condensation
° C.
8.5
9.5
10.5
12.6
6.1
7.1
8.1
9.2


temperature glide





Item
Unit
Ex. 102
Ex. 103
Ex. 104
Ex. 105
Ex. 106
Ex. 107
Ex. 108
Ex. 109





HFO-1132a
mass %
3.0
3.0
3.0
3.0
3.0
3.0
3.0
3.0


R32
mass %
40.0
50.0
50.0
50.0
50.0
60.0
60.0
60.0


R1234yt
mass %
7.0
37.0
27.0
17.0
7.0
27.0
17.0
7.0


R1234ze
mass %
50.0
10.0
20.0
30.0
40.0
10.0
20.0
30.0


GWP

273
340
340
340
340
407
407
407


COP ratio
% (relative to
103.8
101.7
102.1
102.6
103.0
101.7
102.1
102.5



R410A)


Refrigerating
% (relative to
76.7
88.9
87.4
85.7
84.1
94.7
93.0
91.3


capacity ratio
R410A)


Condensation
° C.
10.4
4.8
5.8
6.9
8.1
3.8
4.8
5.9


temperature glide




















Comp.



Item
Unit
Ex. 110
Ex. 111
Ex. 136







HFO-1132a
mass %
3.0
3.0
3.0



R32
mass %
70.0
70.0
80.0



R1234yf
mass %
17.0
7.0
7.0



R1234ze
mass %
10.0
20.0
10.0



GWP

474
474
541



COP ratio
% (relative to
101.8
102.2
101.9




R410A)



Refrigerating
% (relative to
99.8
98.1
104.3



capacity ratio
R410A)



Condensation
° C.
3.1
4.0
2.5



temperature glide


























TABLE 13









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.




Item
Unit
Ex. 137
Ex. 138
Ex. 139
Ex. 140
Ex. 141
Ex. 142
Ex. 112
Ex. 113





HFO-1132a
mass %
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0


R32
mass %
20.0
20.0
20.0
20.0
20.0
20.0
30.0
30.0


R1234yf
mass %
55.0
45.0
35.0
25.0
15.0
5.0
55.0
45.0


R1234ze
mass %
20.0
30.0
40.0
50.0
60.0
70.0
10.0
20.0


GWP

138
139
139
139
139
139
205
206


COP ratio
% (relative to
102.8
103.2
103.6
104.0
104.3
104.7
101.6
102.1



R410A)


Refrigerating
% (relative to
69.0
68.0
66.9
65.8
64.7
63.6
78.0
76.9


capacity ratio
R410A)


Condensation
° C.
11.0
12.0
13.0
14.2
15.4
16.7
8.4
9.4


temperature glide





Item
Unit
Ex. 114
Ex. 115
Ex. 116
Ex. 117
Ex. 118
Ex. 119
Ex. 120
Ex. 121





HFO-11328
mass %
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0


R32
mass %
30.0
30.0
30.0
30.0
40.0
40.0
40.0
40.0


R1234yf
mass %
35.0
25.0
15.0
5.0
45.0
35.0
25.0
15.0


R1234ze
mass %
30.0
40.0
50.0
60.0
10.0
20.0
30.0
40.0


GWP

206
206
206
206
272
273
273
273


COP ratio
% (relative to
102.5
103.0
103.5
104.0
101.1
101.6
102.1
102.5



R410A)


Refrigerating
% (relative to
75.7
74.4
73.1
71.9
85.2
83.8
82.4
81.0


capacity ratio
R410A)


Condensation
° C.
10.5
11.7
13.0
14.2
6.8
7.9
9.1
10.3


temperature glide





Item
Unit
Ex. 122
Ex. 123
Ex. 124
Ex. 125
Ex. 126
Ex. 127
Ex. 128
Ex. 129





HFO-1132a
mass %
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0


R32
mass %
40.0
50.0
50.0
50.0
50.0
60.0
60.0
60.0


R1234yf
mass %
5.0
35.0
25.0
15.0
5.0
25.0
15.0
5.0


R1234ze
mass %
50.0
10.0
20.0
30.0
40.0
10.0
20.0
30.0


GWP

273
340
340
340
340
407
407
407


COP ratio
% (relative to
103.0
101.1
101.5
101.9
102.3
101.1
101.5
101.9



R410A)


Refrigerating
% (relative to
79.6
91.6
90.1
88.5
86.9
97.4
95.7
94.0


capacity ratio
R410A)


Condensation
° C.
11.6
5.5
6.6
7.8
9.0
4.5
5.5
6.7


temperature glide




















Comp.



Item
Unit
Ex. 130
Ex. 131
Ex. 143







HFO-11328
mass %
5.0
5.0
5.0



R32
mass %
70.0
70.0
80.0



R1234yf
mass %
15.0
5.0
5.0



R1234ze
mass %
10.0
20.0
10.0



GWP

474
474
541



COP ratio
% (relative to
101.2
101.6
101.3




R410A)



Refrigerating
% (relative to
102.4
100.7
107.0



capacity ratio
R410A)



Condensation
° C.
3.7
4.7
3.1



temperature glide


























TABLE 14









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.


Hten
Unit
Ex. 144
Ex. 145
Ex. 146
Ex. 147
Ex. 148
Ex. 149
Ex. 150
Ex. 151





HFO-1132a
mass %
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5


R32
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R1234yf
mass %
72.5
62.5
52.5
42.5
32.5
22.5
12.5
2.5


R1234zł
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0


GWP

71
71
71
72
72
72
72
72


COP ratio
% (relative to
102.5
102.7
102.9
103.1
103.3
103.4
103.5
103.6



R410A)


Refrigerating
% (relative to
63.9
63.3
62.5
61.8
61.0
60.1
59.3
58.5


capacity ratio
R410A)


Condensation
° C.
12.4
13.3
14.4
15.6
16.9
18.4
20.1
21.8


temperature glide










Comp.
Comp.
Comp.




Item
Unit
Ex. 132
Ex. 133
Ex. 134
Ex. 152
Ex. 153
Ex. 154
Ex. 135
Ex. 136





HFO-11323
mass %
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5


R32
mass %
20.0
20.0
20.0
20.0
20.0
20.0
30.0
30.0


R1234yf
mass %
62.5
52.5
42.5
22.5
12.5
2.5
52.5
42.5


R1234ze
mass %
10.0
20.0
30.0
50.0
60.0
70.0
30.0
20.0


GWP

138
138
139
139
139
139
205
205


COP ratio
% (relative to
101.7
102.0
102.4
103.2
103.5
103.8
100.8
101.2



R410A)


Refrigerating
9% (relative to
73.4
72.5
71.6
69.6
68.6
67.6
81.4
80.3


capacity ratio
R410A)


Condensation
° C.
11.2
12.2
13.3
15.9
17.4
19.0
9.3
10.4


temperature glide





Item
Unit
Ex. 137
Ex. 138
Ex. 139
Ex. 140
Ex. 141
Ex. 142
Ex. 143
Ex. 144





HFO-1132a
mass %
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5


R32
mass %
30.0
30.0
30.0
30.0
40.0
40.0
40.0
40.0


R1234yf
mass %
32.5
22.5
12.5
2.5
42.5
32.5
22.5
12.5


R1234ze
mass %
30.0
40.0
50.0
60.0
10.0
20.0
30.0
40.0


GWP

206
206
206
206
272
273
273
273


COP ratio
% (relative to
101.7
102.1
102.6
103.1
100.4
100.8
101.2
101.7



R410A)


Refrigerating
% (relative to
79.1
78.0
76.8
75.6
88.5
87.2
85.9
84.5


capacity ratio
R410A)


Condensation
° C.
11.6
13.0
14.4
15.9
7.6
8.7
10.0
11.4


temperature glide





Item
Unit
Ex. 145
Ex. 146
Ex. 147
Ex. 148
Ex. 149
Ex. 150
Ex. 151
Ex. 152





HFO-1132a
mass %
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5


R32
mass %
40.0
50.0
50.0
50.0
50.0
60.0
60.0
60.0


R1234yf
mass %
2.5
32.5
22.5
12.5
2.5
22.5
12.5
2.5


R1234ze
mass %
50.0
10.0
20.0
30.0
40.0
10.0
20.0
30.0


GWP

273
339
340
340
340
407
407
407


COP ratio
% (relative to
102.2
100.3
100.7
101.1
101.5
100.4
100.7
101.1



R410A)


Refrigerating
% (relative to
83.1
95.0
93.5
91.9
90.4
100.7
99.1
97.4


capacity ratio
R410A)


Condensation
° C.
12.8
6.2
7.3
8.6
10.0
5.1
6.3
7.5


temperature glide




















Comp.



Item
Unit
Ex. 153
Ex. 154
Ex. 155







HFO-11328
mass %
7.5
7.5
7.5



ER32
mass %
70.0
70.0
80.0



R1234yf
mass %
12.5
2.5
2.5



R1234ze
mass %
10.0
20.0
10.0



GWP

474
474
541



COP ratio
% (relative to
100.5
100.8
100.6




R410A)



Refrigerating
% (relative to
105.7
104.1
110.2



capacity ratio
R410A)



Condensation
° C.
4.3
5.4
3.7



temperature glide


























TABLE 15









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.
Comp.



Item
Unit
Ex. 156
Ex. 157
Ex. 158
Ex. 159
Ex. 160
Ex. 161
Ex. 162
Ex. 155





HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
20.0


R1234yf
mass %
70.0
60.0
50.0
40.0
30.0
20.0
10.0
60.0


R1234ze
mass %
10.0
20.0
30.0
40.0
50.0
60.0
70.0
10.0


GWP

71
71
71
72
72
72
72
138


COP ratio
% (relative
101.9
102.1
102.3
102.5
102.7
102.9
103.0
101.0



to R410A)


Refrigerating
% (relative
67.5
66.9
66.2
65.5
64.9
64.2
63.5
76.8


capacity ratio
to R410A)


Condensation
° C.
13.6
14.7
15.9
17.3
18.8
20.5
22.3
12.0


temperature glide





Item
Unit
Ex. 156
Ex. 157
Ex. 158
Ex. 159
Ex. 160
Ex. 161
Ex. 162
Ex. 163





HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
20.0
20.0
20.0
20.0
20.0
30.0
30.0
30.0


R1234yf
mass %
50.0
40.0
30.0
20.0
10.0
50.0
40.0
30.0


R1234ze
mass %
20.0
30.0
40.0
50.0
60.0
10.0
20.0
30.0


GWP

138
139
139
139
139
205
205
206


COP ratio
% (relative
101.3
101.7
102.0
102.4
102.8
100.0
100.4
100.9



to R410A)


Refrigerating
% (relative
76.0
75.1
74.2
73.3
72.4
84.7
83.7
82.6


capacity ratio
to R410A)


Condensation
° C.
13.1
14.4
15.8
17.3
18.9
10.0
11.2
12.5


temperature glide





Item
Unit
Ex. 164
Ex. 165
Ex. 166
Ex. 167
Ex. 168
Ex. 169
Ex. 170
Ex. 171





HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
30.0
30.0
40.0
40.0
40.0
40.0
50.0
50.0


R1234yf
mass %
20.0
10.0
40.0
30.0
20.0
10.0
30.0
20.0


R1234ze
mass %
40.0
50.0
10.0
20.0
30.0
40.0
10.0
20.0


GWP

206
206
272
273
273
273
339
340


COP ratio
% (relative
101.3
101.8
99.6
100.0
100.4
100.9
99.6
99.9



to R410A)


Refrigerating
% (relative
81.5
80.4
91.8
90.6
89.3
87.9
98.2
96.8


capacity ratio
to R410A)


Condensation
° C.
13.9
15.5
8.1
9.4
10.8
12.2
6.7
8.0


temperature glide
























Comp.



Item
Unit
Ex. 172
Ex. 173
Ex. 174
Ex. 175
Ex. 163







HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0



R32
mass %
50.0
60.0
60.0
70.0
80.0



R1234yf
mass %
10.0
20.0
10.0
10.0
5.0



R1234ze
mass %
30.0
10.0
20.0
10.0
5.0



GWP

340
407
407
474
541



COP ratio
% (relative
100.3
99.7
100.0
99.8
99.8




to R410A)



Refrigerating
% (relative
95.3
103.9
102.4
108.9
114.1



capacity ratio
to R410A)



Condensation
° C.
9.3
5.6
6.9
4.9
3.7



temperature glide


























TABLE 16









Comp.
Comp.
Comp.
Comp.
Comp.

Comp.
Comp.


Item
Unit
Ex. 164
Ex. 165
Ex. 166
Ex. 167
Ex. 168
Ex. 176
Ex. 169
Ex. 170





HFO-1132a
mass %
10.0
12.5
7.5
12.5
6.3
8.8
11.3
4.0


R32
mass %
10.0
10.0
12.5
12.5
15.0
15.0
15.0
17.5


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
80.0
77.5
80.0
75.0
78.8
76.3
73.8
78.5


GWP

72
72
89
89
106
106
106
123


COP ratio
% (relative to
105.6
103.9
107.4
104.1
108.4
106.7
105.2
110.1



R404A)


Refrigerating
% (relative to
66.0
70.0
65.9
74.2
67.7
72.0
76.4
67.6


capacity ratio
R404A)


Condensation
° C.
25.5
26.9
22.6
25.8
20.6
22.8
24.2
17.5


temperature glide









Comp.
Comp.



Comp.


Item
Unit
Ex. 177
Ex. 178
Ex. 171
Ex. 172
Ex. 179
Ex. 180
Ex. 181
Ex. 173





HFO-1132a
mass %
6.5
9.0
11.5
1.5
4.0
6.5
9.0
11.5


R32
mass %
17.5
17.5
17.5
20.0
20.0
20.0
20.0
20.0


R1234yf
mass %
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0


R1234ze
mass %
76.0
73.5
71.0
78.5
76.0
73.5
71.0
68.5


GWP

123
123
123
140
140
139
139
139


COP ratio
% (relative to
108.4
106.8
105.2
112.0
110.2
108.6
107.0
105.5



R404A)


Refrigerating
% (relative to
72.1
76.6
81.2
67.0
71.6
76.2
80.9
85.6


capacity ratio
R404A)


Condensation
° C.
20.2
22.1
23.3
13.6
17.0
19.5
21.2
22.3


temperature glide




















Comp.
Comp.
Comp.
Comp.
Comp.



Item
Unit
Ex. 174
Ex. 178
Ex. 176
Ex. 177
Ex. 178







HFO-1132a
mass %
1.5
4.0
6.5
9.0
11.5



R32
mass %
22.5
22.5
22.5
22.5
22.5



R1234yf
mass %
0.0
0.0
0.0
0.0
0.0



R1234ze
mass %
76.0
73.5
71.0
68.5
66.0



GWP

156
156
156
156
156



COP ratio
% (relative to
112.1
110.3
108.7
107.1
105.6




R404A)



Refrigerating
% (relative to
70.8
75.6
80.3
85.1
90.0



capacity ratio
R404A)



Condensation
° C.
13.4
16.5
18.8
20.3
21.3



temperature glide


























TABLE 17










Comp.
Comp.



Comp.
Comp.


Item
Unit
Ex. 182
Ex. 179
Ex. 180
Ex. 183
Ex. 184
Ex. 185
Ex. 181
Ex. 182





HFO-1132a
mass %
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5


R32
mass %
10.0
10.0
10.0
15.0
15.0
15.0
15.0
15.0


R1234yf
mass %
83.5
73.5
63.5
78.5
68.5
58.5
38.5
28.5


R1234ze
mass %
5.0
15.0
25.0
5.0
15.0
25.0
45.0
55.0


GWP

71
71
72
105
105
105
106
106


COP ratio
% (relative to
106.9
107.4
108.0
107.3
107.8
108.3
109.5
110.0



R404A)


Refrigerating
% (relative to
70.9
68.7
66.5
79.2
76.7
74.2
69.1
66.5


capacity ratio
R404A)


Condensation
° C.
8.1
8.5
9.0
8.4
8.9
9.5
10.8
11.5


temperature glide













Comp.
Comp.


Item
Unit
Ex. 186
Ex. 187
Ex. 188
Ex. 189
Ex. 190
Ex. 191
Ex. 183
Ex. 184





HFO-1132a
mass %
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5


R32
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
25.0


R1234yf
mass %
73.5
63.5
53.5
43.5
33.5
23.5
3.5
68.5


R1234ze
mass %
5.0
15.0
25.0
35.0
45.0
55.0
75.0
5.0


GWP

138
138
139
139
139
139
140
172


COP ratio
% (relative to
107.6
108.1
108.7
109.3
109.9
110.5
111.7
107.8



R404A)


Refrigerating
% (relative to
87.4
84.7
81.9
79.1
76.2
73.4
67.9
95.4


capacity ratio
R404A)


Condensation
° C.
8.2
8.8
9.4
10.2
10.9
11.7
13.3
7.6


temperature glide



















Comp.
Comp.
Comp.
Comp.
Comp.
Comp.


Item
Unit
Ex. 185
Ex. 186
Ex. 187
Ex. 188
Ex. 189
Ex. 190





HFO-1132a
mass %
1.5
1.5
1.5
1.5
1.5
1.5


R32
mass %
25.0
25.0
25.0
25.0
25.0
25.0


R1234yf
mass %
58.5
48.5
38.5
28.5
18.5
8.5


R1234ze
mass %
15.0
25.0
35.0
45.0
55.0
65.0


GWP

172
172
172
173
173
173


COP ratio
% (relative to
108.4
109.1
109.7
110.3
111.0
111.6



R404A)


Refrigerating
% (relative to
92.5
89.4
86.3
83.2
80.2
77.2


capacity ratio
R404A)


Condensation
° C.
8.2
9.0
9.8
10.7
11.5
12.4


temperature glide

























TABLE 18










Comp.
Comp.



Comp.
Comp.


Item
Unit
Ex. 192
Ex. 191
Ex. 192
Ex.193
Ex.194
Ex.195
Ex. 193
Ex. 194





HFO-1132a
mass %
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9


R32
mass %
10.0
10.0
10.0
15.0
15.0
15.0
15.0
15.0


R1234yf
mass %
83.1
73.1
63.1
78.1
68.1
58.1
38.1
28.1


R1234ze
mass %
5.0
15.0
25.0
5.0
15.0
25.0
45.0
55.0


GWP

71
71
72
105
105
105
105
106


COP ratio
% (relative to
106.8
107.3
107.8
107.1
107.6
108.2
109.3
109.8



R404A)


Refrigerating
% (relative to
71.5
69.4
67.2
79.9
77.4
74.9
69.7
67.1


capacity ratio
R404A)


Condensation
° C.
8.4
8.9
9.4
8.7
9.3
9.9
11.3
12.1


temperature glide













Comp.
Comp.


Item
Unit
Ex. 196
Ex. 197
Ex. 198
Ex. 199
Ex. 200
Ex. 201
Ex. 195
Ex. 196





HFO-1132a
mass %
1.9
1.9
1.9
1.9
1.9
1.9
1.9
1.9


R32
mass %
20.0
20.0
20.0
20.0
20.0
20.0
20.0
25.0


R1234yf
mass %
73.1
63.1
53.1
43.1
33.1
23.1
3.1
68.1


R1234ze
mass %
5.0
15.0
25.0
35.0
45.0
55.0
75.0
5.0


GWP

138
138
139
139
139
139
140
172


COP ratio
% (relative to
107.4
108.0
108.5
109.1
109.7
110.3
111.5
107.7



R404A)


Refrigerating
% (relative to
88.1
85.4
82.6
79.7
76.9
74.1
68.5
96.2


capacity ratio
R404A)


Condensation
° C.
8.4
9.0
9.8
10.5
11.3
12.2
13.9
7.8


temperature glide



















Comp.
Comp.
Comp.
Comp.
Comp.
Comp.


Item
Unit
Ex. 197
Ex. 198
Ex. 199
Ex. 200
Ex. 201
Ex. 202





HFO-1132a
mass %
1.9
1.9
1.9
1.9
1.9
1.9


R32
mass %
25.0
25.0
25.0
25.0
25.0
25.0


R1234yf
mass %
58.1
48.1
38.1
28.1
18.1
8.1


R1234ze
mass %
15.0
25.0
35.0
45.0
55.0
65.0


GWP

172
172
172
173
173
173


COP ratio
% (relative to
108.3
108.9
109.5
110.1
110.7
111.4



R404A)


Refrigerating
% (relative to
93.2
90.1
87.0
83.9
80.9
77.9


capacity ratio
R404A)


Condensation
° C.
8.5
9.3
10.2
11.0
12.0
12.9


temperature glide

























TABLE 19












Comp.
Comp.





Item
Unit
Ex. 202
Ex. 203
Ex. 204
Ex. 203
Ex. 204
Ex. 205
Ex. 206
Ex. 207





HFO-1132a
mass %
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0


R32
mass %
10.0
10.0
10.0
10.0
10.0
15.0
15.0
15.0


R1234yf
mass %
79.0
69.0
59.0
39.0
29.0
74.0
64.0
54.0


R1234ze
mass %
5.0
15.0
25.0
45.0
55.0
5.0
15.0
25.0


GWP

71
71
71
72
72
105
105
105


COP ratio
% (relative to
105.6
105.9
106.2
106.9
107.2
105.8
106.1
106.5



R410A)


Refrigerating
% (relative to
78.5
76.2
73.8
68.9
66.5
87.2
84.6
81.9


capacity ratio
R410A)


Condensation
° C.
11.6
12.4
13.3
15.6
17.0
11.3
12.2
13.1


temperature glide










Comp.






Item
Unit
Ex. 208
Ex. 209
Ex. 210
Ex. 205
Ex. 211
Ex. 212
Ex. 213
Ex. 214





HFO-1132a
mass %
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0


R32
mass %
15.0
15.0
15.0
15.0
20.0
20.0
20.0
20.0


R1234yf
mass %
44.0
34.0
24.0
4.0
69.0
59.0
49.0
39.0


R1234ze
mass %
35.0
45.0
55.0
75.0
5.0
15.0
25.0
35.0


GWP

105
105
106
106
138
138
139
139


COP ratio
% (relative to
106.9
107.2
107.6
108.4
106.0
106.4
106.8
107.2



R410A)


Refrigerating
% (relative to
79.1
76.4
73.6
68.3
95.7
92.9
89.9
86.8


capacity ratio
R410A)


Condensation
° C.
14.3
15.5
16.8
19.7
10.6
11.5
12.6
13.7


temperature glide










Comp.
Comp.
Comp.
Comp.
Comp.


Item
Unit
Ex. 215
Ex. 216
Ex. 217
Ex. 206
Ex. 207
Ex. 208
Ex. 209
Ex. 210





HFO-1132a
mass %
6.0
6.0
6.0
6.0
6.0
6.0
6.0
6.0


R32
mass %
20.0
20.0
20.0
25.0
25.0
25.0
25.0
25.0


R1234yf
mass %
29.0
19.0
9.0
64.0
54.0
44.0
34.0
24.0


R1234ze
mass %
45.0
55.0
65.0
5.0
15.0
25.0
35.0
45.0


GWP

139
139
139
172
172
172
172
172


COP ratio
% (relative to
107.6
108.1
108.5
106.2
106.6
107.0
107.5
108.0



R410A)


Refrigerating
% (relative to
83.8
80.8
77.9
104.0
100.8
97.6
94.3
91.0


capacity ratio
R410A)


Condensation
° C.
15.0
16.3
17.7
9.7
10.7
11.8
13.0
14.3


temperature glide

















Comp.
Comp.



Item
Unit
Ex. 211
Ex. 212







HFO-1132a
mass %
6.0
6.0



R32
mass %
25.0
25.0



R1234yf
mass %
14.0
4.0



R1234ze
mass %
55.0
65.0



GWF

173
173



COP ratio
% (relative to
108.5
108.9




R410A)



Refrigerating
% (relative to
87.8
84.7



capacity ratio




R410A)



Condensation
° C.
15.6
17.1



temperature glide


























TABLE 20












Comp.
Comp.





Item
Unit
Ex. 218
Ex. 219
Ex. 220
Ex. 213
Ex. 214
Ex. 221
Ex. 222
Ex. 223





HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
5.0
5.0
5.0
5.0
5.0
10.0
10.0
10.0


R1234yf
mass %
80.0
70.0
60.0
40.0
30.0
75.0
65.0
55.0


R1234ze
mass %
5.0
15.0
25.0
45.0
55.0
5.0
15.0
25.0


GWP

37
38
38
38
38
71
71
71


COP ratio
% (relative to
104.3
104.4
104.4
104.6
104.8
104.4
104.5
104.6



R410A)


Refrigerating
% (relative to
76.5
74.4
72.2
67.6
65.2
85.6
83.1
80.6


capacity ratio
R410A)


Condensation
° C.
13.8
14.9
16.2
19.2
20.9
13.8
14.8
16.0


temperature glide










Comp.


Item
Unit
Ex. 224
Ex. 225
Ex. 226
Ex. 215
Ex. 227
Ex. 228
Ex. 229
Ex. 230





HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
10.0
10.0
10.0
10.0
15.0
15.0
15.0
15.0


R1234yf
mass %
45.0
35.0
25.0
5.0
70.0
60.0
50.0
40.0


R1234ze
mass %
35.0
45.0
55.0
75.0
5.0
15.0
25.0
35.0


GWP

72
72
72
72
104
105
105
105


COP ratio
% (relative to
104.7
104.9
105.1
105.5
104.5
104.7
104.8
105.0



R410A)


Refrigerating
% (relative to
77.9
75.2
72.5
67.3
94.6
91.9
89.0
86.0


capacity ratio
R410A)


Condensation
° C.
17.4
18.9
20.6
24.4
13.1
14.2
15.4
16.7


temperature glide





Item
Unit
Ex. 231
Ex. 232
Ex. 233
Ex. 234
Ex. 235
Ex. 236
Ex. 237
Ex. 238





HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
15.0
15.0
15.0
20.0
20.0
20.0
20.0
20.0


R1234yf
mass %
30.0
20.0
10.0
65.0
55.0
45.0
35.0
25.0


R1234ze
mass %
45.0
55.0
65.0
5.0
15.0
25.0
35.0
45.0


GWP

105
105
106
138
138
138
139
139


COP ratio
% (relative to
105.3
105.5
105.7
104.6
104.8
105.1
105.3
105.6



R410A)


Refrigerating
% (relative to
83.0
80.0
77.1
103.4
100.4
97.2
93.9
90.7


capacity ratio
R410A)


Condensation
° C.
18.2
19.9
21.6
12.1
13.2
14.5
15.8
17.3


temperature glide









Comp.
Comp.
Comp.
Comp.
Comp.
Comp.


Item
Unit
Ex. 239
Ex. 240
Ex. 216
Ex. 217
Ex. 218
Ex. 219
Ex. 220
Ex. 221





HFO-1132a
mass %
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0


R32
mass %
20.0
20.0
25.0
25.0
25.0
25.0
25.0
25.0


R1234yf
mass %
15.0
5.0
60.0
50.0
40.0
30.0
20.0
10.0


R1234ze
mass %
55.0
65.0
5.0
15.0
25.0
35.0
45.0
55.0


GWP

139
139
172
172
172
172
172
173


COP ratio
% (relative to
105.9
106.2
104.7
105.0
105.3
105.6
105.9
106.3



R410A)


Refrigerating
% (relative to
87.5
84.3
111.9
108.5
105.0
101.5
98.1
94.6


capacity ratio
R410A)


Condensation
° C.
19.0
20.7
11.0
12.2
13.5
14.9
16.4
18.0


temperature glide








Claims
  • 1-23. (canceled)
  • 24. A composition comprising a refrigerant, the refrigerant comprising 1,1-difluoroethylene (HFO-1132a), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze) in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines IB, BE, EF, and FI that connect the following four points:point I (10.0, 74.0, 16.0),point B (1.5, 73.9, 24.6),point E (1.5, 56.2, 42.3), andpoint F (10.0, 37.7, 52.3),or on the straight lines.
  • 25. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, and R1234ze in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines G′B, BG, and GG′ that connect the following three points:point G′ (8.6, 73.9, 17.5),point B (1.5, 73.9, 24.6), andpoint G (1.5, 65.9, 32.6),or on the straight lines.
  • 26. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, and R1234ze in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of HFO-1132a, R32, and R1234ze based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132a, R32, and R1234ze is 100 mass % are within the range of a figure surrounded by straight lines JB′, B′E, EF, and FJ that connect the following four points:point J (10.0, 59.0, 31.0),point B′ (1.5, 58.9, 39.6),point E (1.5, 56.2, 42.3), andpoint F (10.0, 37.7, 52.3),or on the straight lines.
  • 27. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, R1234ze, and 2,3,3,3-tetrafluoro-1-propene (R1234yf) in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BC, CD, and DA that connect the following four points:point A (74.0, −a+26.0, 0.0),point B (73.9, 0.0, −a+26.1),point D (0.0098a2−2.1856a+39.064, 0.0, −0.0098a2+1.1856a+60.936), andpoint C (0.0138a2−1.6252a+26.785, −0.0138a2+0.6252a+73.215, 0.0),or on the straight lines AB and CD (excluding the points A, B, C, and D).
  • 28. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, R1234ze, and R1234yf in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BF, FE, and EA that connect the following four points:point A (74.0, −a+26.0, 0.0),point B (73.9, 0.0, −a+26.1),point F (0.0102a2−2.2922a+59.604, 0.0, −0.0102a2+1.2922a+40.396), andpoint E (0.0208a2−2.0723a+47.748, −0.0208a2+1.0723a+52.252, 0.0),or on the straight lines AB and FE (excluding the points A, B, F, and E).
  • 29. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, R1234ze, and R1234yf in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,if 5.0≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines AB, BH, HG, and GA that connect the following four points:point A (74.0, −a+26.0, 0.0),point B (73.9, 0.0, −a+26.1),point H (−0.1143a2+2.3143a+62.686, 0.0, 0.1143a2−3.3143a+37.314),andpoint G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),or on the straight lines AB and HG (excluding the points A, B, H, and G); if 7.5≥x>5.0, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AB, BH, HG, and GA that connect the following four points:point A (74.0, −a+26.0, 0.0),point B (73.9, 0.0, −a+26.1),point H (−0.072a2+1.9a+63.7, 0.0, 0.072a2−2.9a+36.3), andpoint G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),or on the straight lines AB and HG (excluding the points A, B, H, and G); or if 10.0≥x>7.5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AR, RG, and GA that connect the following three points:point A (74.0, −a+26.0, 0.0),point R (73.9, 1.12a−8.4, −2.12a+34.5), andpoint G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),or on the straight lines AR and RG (excluding the points A and G).
  • 30. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, R1234ze, and R1234yf in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′B′, B′D, DC, and CA′ that connect the following four points:point A′ (59.0, −a+41.0, 0),point B′ (58.9, 0.0, −a+41.1),point D (0.0098a2−2.1856a+39.064, 0.0, −0.0098a2+1.1856a+60.936), andpoint C (0.0138a2−1.6252a+26.785, −0.0138a2+0.6252a+73.215, 0.0),or on the straight lines A′B′ and DC (excluding the points A′, B′, D, and C).
  • 31. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, R1234ze, and R1234yf in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′B′, B′F, FE, and EA′ that connect the following four points:point A′ (59.0, −a+41.0, 0.0),point B′ (58.9, 0.0, −a+41.1),point F (0.0102a2−2.2922a+59.604, 0.0, −0.0102a2+1.2922a+40.396), andpoint E (0.0208a2−2.0723a+47.748, −0.0208a2+1.0723a+52.252, 0.0),or on the straight lines A′B′ and FE (excluding the points A′, B′, F, and E).
  • 32. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, R1234ze, and R1234yf in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,if 5.0≥x≥1.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A′P, PG, and GA′ that connect the following three points:point A′ (59.0, −a+41.0, 0.0),point P (−0.019a2+0.1524a+58.714, −0.2571a2+4.1571a+9.5429, 0.2761a2−5.3095a+31.7431), andpoint G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),or on the straight lines A′P and PG (excluding the points A′ and G); or if 10.0≥x>5, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines A′P, PG, and GA′ that connect the following three points:point A′ (59.0, −a+41.0, 0.0),point P (59.0, −0.136a2+2.94a+12.6, 0.136a2−3.94a+28.4), andpoint G (−0.0505a2+2.6396a+34.049, 0.0505a2−3.6396a+65.951, 0.0),or on the straight lines A′P and PG (excluding the points A′ and G).
  • 33. The composition according to claim 24, which is for use as an alternative refrigerant for R410A.
  • 34. A composition comprising a refrigerant, the refrigerant comprising HFO-1132a, R32, R1234ze, and R1234yf in a total amount of 99.5 mass % or more based on the entire refrigerant, wherein when the mass % of R32 is represented by x, the mass % of R1234yf is represented by y, the mass % of R1234ze is represented by z, and the mass % of HFO-1132a is represented by a, based on the sum of R32, R1234yf, R1234ze, and HFO-1132a in the refrigerant,if 1.9?x21.5, coordinates (x,y,z) in a ternary composition diagram in which the sum of R32, R1234yf, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines A″T, TM, and MA″ that connect the following three points:point A″ (21.8, −a+78.2, 0.0),point T (21.5, −15.0a+28.5, 14.0a+50.0), andpoint M (0.0035a2−0.9809a+10.358, −0.0035a2−0.0191a+89.642, 0.0),or on the straight lines A″T and TM (excluding the points A″ and M); or if 10.0≥x>1.9, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines A″B″, B″L, LM, and MA″ that connect the following four points:point A″ (21.8, −a+78.2, 0.0),point B″ (0.0108a+21.473, 0.0, −1.0108a+78.527),point L (0.0098a2−1.2237a+23.804, 0.0, −0.0098a2+0.2237a+76.196), andpoint M (0.0035a2−0.9809a+10.358, −0.0035a2−0.0191a+89.642, 0.0),or on the straight lines A″B″ and LM (excluding the points A″, B″, L, and M).
  • 35. The composition according to claim 34, which is for use as an alternative refrigerant for R404A.
  • 36. The composition according to claim 24, which is for use as a working fluid for a refrigerating machine, the composition further comprising a refrigeration oil.
  • 37. A refrigerating machine comprising the composition according to claim 24 as a working fluid.
  • 38. A method for operating a refrigerating machine, comprising circulating the composition according to claim 24 as a working fluid in a refrigerating machine.
  • 39. Use of the composition according to claim 24 as an alternative refrigerant for R410A.
  • 40. Use of the composition according to claim 34 as an alternative refrigerant for R404A.
Priority Claims (1)
Number Date Country Kind
2020-206857 Dec 2020 JP national
Continuations (1)
Number Date Country
Parent PCT/JP2021/046094 Dec 2021 US
Child 18209046 US