Refrigerant-containing composition, use thereof, refrigerator having same and method of operating said refrigerator

Abstract

The objective is to provide a new low-GWP refrigerant mixture. [Solution] The present invention provides a composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), 1,3,3,3-tetrafluoropropene (R1234ze), and 2,3,3,3-tetrafluoro-1-propene (R1234yf).

Description

Technical Field

[0001] The present disclosure relates to a composition containing a refrigerant, its use, a refrigerator having the same, and a method for operating the refrigerator.

Background Art

[0002] As a working medium for a heat cycle that can replace R410A, a working medium for a heat cycle containing trifluoroethylene (HFO-1123) and 1,2-difluoroethylene (HFO-1132) has been proposed (Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a novel low-GWP mixed refrigerant.

Means for Solving the Problems

[0005] Item 1. A composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), 1,3,3,3 -tetrafluoropropene (R1234ze) and 2,3,3,3-tetrafluoro-1-pro pene (R1234yf). Item 2. In the refrigerant, the mass of HFO-1132(E), R1234ze, and R1234yf, based on the sum of these ​When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) Within the area of ​​the figure enclosed by the line segments AB, BF, FE, and EA connecting the four points, or on the line segments the law of nature, Line segments AB, BF, and EA are straight lines, and A point on line segment FE is (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 (-7.5772x + 194.748) To be made The composition described in item 1. Section 3. In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DF, FE, and EC connecting the four points respectively, or on the line segments the law of nature, Line segments DF and EC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment FE is (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 (-7.5772x + 194.748) To be made The composition described in item 1. Section 4. In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H(2.1, 1.0, 96.9) and Point G(14.4, 84.6, 1.0) Within the area of ​​the figure enclosed by the line segments AB, BH, HG, and GA connecting the four points, or on the line segments the law of nature, Line segments AB, BH, and GA are straight lines. A point on line segment HG is (x, -0.1974x 2 +10.054x-19.242, 0.1974x 2 It is expressed as -11.054x + 119.242, The composition described in item 1. Section 5. In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I (22.6, 76.4, 1.0) within the range of the figure surrounded by the line segments AB, BJ, JI, and IA connecting these four points respectively or on said line segments, and the line segments AB, BJ, and IA are straight lines, and the points on the line segment JI are (x, -0.1609x 2 +12.934x - 133.76, 0.1609x 2 -13.934x + 233.76), the composition according to claim 1. Item 6. In the refrigerant, when the mass percentages of HFO-1132(E), R1234ze, and R1234yf based on their total are x, y, and z respectively, in the three-component composition diagram where the total of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x, y, z) are point A(72.0, 27.0, 1.0), point B(72.0, 1.0, 27.0), point H’(31.3, 1.0, 67.7) and point G’(44.1, 54.9, 1.0) within the range of the figure surrounded by the line segments AB, BH’, H’G’, and G’A connecting these four points respectively or on said line segments, and the line segments AB, BH’, and G’A are straight lines, and the points on the line segment H’G’ are (x, -0.08728x2 + 10.791x - 251.26, 0.08728x -11.791x + 351.26), 2 the composition according to claim 1. Item 7. Item 7. In the refrigerant, when the mass percentages of HFO-1132(E), R1234ze, and R1234yf based on their total are x, y, and z respectively, in the three-component composition diagram where the total of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x, y, z) are point C(38.7, 60.3, 1.0), point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point H(2.1, 1.0, 96.9) and Point G(14.4, 84.6, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DH, HG, and GC connecting the four points respectively, or on the line segments the law of nature, Line segments DH and GC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment HG is (x, -0.1974x 2 +10.054x-19.242, 0.1974x 2 (-11.054x + 119.242) To be made The composition described in item 1. Section 8. In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I (22.6, 76.4, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DJ, JI, and IC connecting the four points respectively, or on the line segments the law of nature, Line segments DJ and IC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment JI is (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 It is expressed as -13.934x + 233.76. The composition described in item 1. Section 9. In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7) Within the range of the figure enclosed by the line segments PD, DH', and H'P connecting the three points respectively, or on the aforementioned straight line the law of nature, The line segment DH' is a straight line, A point on line segment PD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 It is expressed as -0.8166x-35.54) ,and A point on line segment H'P is (x, -0.08728x 2 +10.791x-251.26, 0.08728x 2 It is expressed as -11.791x + 351.26. The composition described in item 1. Section 10. Furthermore, the composition according to any one of claims 1 to 9, further containing refrigerant oil. Section 11. A composition according to any one of items 1 to 10, used as a substitute refrigerant for R404A. Section 12. A refrigerator comprising a composition described in any one of items 1 to 10 as a working fluid. Section 13. The method of operating a refrigerator, A method comprising the step of circulating a composition described in any one of items 1 to 10 as a working fluid in a refrigerator. Section 14. Use of any one of the compositions described in items 1 to 10 as a substitute refrigerant for R410A. [Effects of the Invention]

[0006] The refrigerant disclosed herein is low GWP. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic diagram of the apparatus used for the flammability test. [Figure 2] This is a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, and points A to F are shown. [Figure 3] This is a three-component composition diagram in which the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, and points A to D are shown in addition to G to J, G', and H'. [Modes for carrying out the invention]

[0008] In order to solve the above problems, the inventors conducted diligent research and found that a mixed refrigerant containing HFO-1132(E), R1234ze, and R1234yf has the above characteristics.

[0009] This disclosure is the result of further research based on the aforementioned findings. This disclosure includes the following embodiments. <Definition of Terms> In this specification, the term "refrigerant" includes at least a compound that has been assigned a refrigerant number (ASHRAE number) beginning with R, as defined by ISO 817 (International Organization for Standardization), which indicates the type of refrigerant. Furthermore, even if a refrigerant number has not yet been assigned, it includes substances that have equivalent refrigerant properties. Refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds" in terms of their compound structure. "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons. It contains orocarbon (HFC).

[0010] In this specification, the term "composition containing a refrigerant" includes at least (1) the refrigerant itself (including a mixture of refrigerants), (2) a composition further containing other components that can be used to obtain a working fluid for a refrigerator by mixing with at least refrigerant oil, and (3) a working fluid for a refrigerator containing refrigerant oil. In this specification, of these three embodiments, composition (2) is referred to as "refrigerant composition" to distinguish it from the refrigerant itself (including a mixture of refrigerants). Also, working fluid for a refrigerator (3) is referred to as "refrigerant oil-containing working fluid" to distinguish it from "refrigerant composition".

[0011] In this specification, when the term “substitute” is used in the context of “substituting” a first refrigerant with a second refrigerant, the first type means that equipment designed to operate using the first refrigerant can be operated under optimal conditions using the second refrigerant with only minor changes to parts (at least one of the following: refrigerant oil, gaskets, packing, expansion valves, dryers, and other parts) and equipment adjustments as needed. In other words, this type refers to operating the same equipment with a “substitute” refrigerant. The forms of “substitution” in this type are, in order of decreasing degree of change or adjustment required when replacing with the second refrigerant, “drop-in substitution,” and “nealy drop-in substitution.” Possible alternatives include "p in" and "retrofit".

[0012] A second type of "substitution" includes using equipment designed to operate with a second refrigerant, but instead using the second refrigerant for the same existing applications as the first refrigerant. This type refers to providing the same application by "substituting" a refrigerant.

[0013] In this specification, the term "refrigeration unit" refers to any device that removes heat from an object or space to a temperature lower than the surrounding ambient air and maintains that low temperature. In other words, a refrigerator is a conversion device that obtains energy from an external source, performs work, and converts energy in order to transfer heat from a lower temperature to a higher temperature.

[0014] Unless otherwise specified, the pressures described herein are in absolute pressure units.

[0015] In this specification, a refrigerant is considered "WCF (Wide Flammable)" according to the US ANSI / ASHRAE 34-2013 standard. The worst case of formulation for flammability (WCF) is the rate of combustion. This means the temperature is 10 cm / s or less.

[0016] Furthermore, in this specification, when a refrigerant is referred to as ASHRAE low-flammability (WCF & WCFF low-flammability), it means that the combustion rate of WCF is... The temperature is 10 cm / s or less, and storage, transport, and use are based on ANSI / ASHRAE 34-2013 using WCF. This means that the worst case of fractionation for flammability (WCFF), identified through leakage testing, has a burning rate of 10 cm / s or less, and is classified as "2L class" according to the US ANSI / ASHRAE 34-2013 standard for flammability.

[0017] 1. refrigerant The refrigerants of this disclosure include HFO-1132(E), R1234ze, and R1234yf.

[0018] The refrigerant in this disclosure is a low GWP mixed refrigerant.

[0019] The refrigerant of this disclosure preferably satisfies the following requirements. In this case, the refrigerant of this disclosure is WCF It becomes a low-flammability gas, and the refrigeration capacity ratio based on R404A is 70% or higher. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) Within the area of ​​the figure enclosed by the line segments AB, BF, FE, and EA connecting the four points, or on the line segments the law of nature, Line segments AB, BF, and EA are straight lines, and A point on line segment FE is (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 (-7.5772x + 194.748) To be made to do something.

[0020] The refrigerant of this disclosure preferably satisfies the following requirements. In this case, the refrigerant of this disclosure is ASHRAE low-flammability (WCF & WCFF low-flammability) and has a refrigeration capacity ratio of 70% or more based on R404A. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts in percent are x, y, and z respectively, the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass. In the three-component composition diagram, the coordinates (x,y,z) are: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DF, FE, and EC connecting the four points respectively, or on the line segments the law of nature, Line segments DF and EC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment FE is (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 (-7.5772x + 194.748) To be made to do something.

[0021] The refrigerant of this disclosure preferably satisfies the following requirements. In this case, the refrigerant of this disclosure is WCF It becomes slightly flammable, and the refrigeration capacity ratio based on R134a is 100% or more. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H(2.1, 1.0, 96.9) and Point G(14.4, 84.6, 1.0) Within the area of ​​the figure enclosed by the line segments AB, BH, HG, and GA connecting the four points, or on the line segments the law of nature, Line segments AB, BH, and GA are straight lines. A point on line segment HG is (x, -0.1974x 2 +10.054x-19.242, 0.1974x 2 It can be expressed as (-11.054x + 119.242).

[0022] The refrigerant of this disclosure preferably satisfies the following requirements. In this case, the refrigerant of this disclosure is WCF It becomes a weak flame and its boiling point drops below -40°C. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I (22.6, 76.4, 1.0) Within the area of ​​the figure enclosed by the line segments AB, BJ, JI, and IA connecting the four points, or on the line segments the law of nature, Line segments AB, BJ, and IA are straight lines, and A point on line segment JI is (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 It can be expressed as (-13.934x + 233.76).

[0023] The refrigerant of this disclosure preferably satisfies the following requirements. In this case, the refrigerant of this disclosure is ASHRAE low-flammability (WCF & WCFF low-flammability) and has a refrigeration capacity ratio of 150% or more relative to R134a. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts in percent are x, y, and z respectively, the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass. In the three-component composition diagram, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H'(31.3, 1.0, 67.7) and Point G'(44.1, 54.9, 1.0) The area within the figure enclosed by the line segments AB, BH', H'G', and G'A connecting the four points, or the aforementioned line It is on the ground, Line segments AB, BH', and G'A are straight lines, and The point on line segment H'G' is (x, -0.08728x² + 10.791x - 251.26, 0.08728x 2 It is expressed as -11.791x + 351.26).

[0024] The refrigerant of this disclosure preferably satisfies the following requirements. In this case, the refrigerant of this disclosure is ASHRAE low-flammability (WCF & WCFF low-flammability) and has a refrigeration capacity ratio of 100% or more relative to R134a. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point H(2.1, 1.0, 96.9) and Point G(14.4, 84.6, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DH, HG, and GC connecting the four points respectively, or on the line segments the law of nature, Line segments DH and GC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment HG is (x, -0.1974x 2 +10.054x-19.242, 0.1974x 2 (-11.054x + 119.242) To be made to do something.

[0025] The refrigerant of this disclosure preferably satisfies the following requirements. In this case, the refrigerant of this disclosure is ASHRAE slightly flammable (WCF & WCFF slightly flammable) and has a boiling point of -40°C or lower. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I (22.6, 76.4, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DJ, JI, and IC connecting the four points respectively, or on the line segments the law of nature, Line segments DJ and IC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment JI is (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2It can be expressed as (-13.934x + 233.76).

[0026] The refrigerant of this disclosure preferably satisfies the following requirements. In this case, the refrigerant of this disclosure is ASHRAE low-flammability (WCF & WCFF low-flammability) and has a refrigeration capacity ratio of 150% or more relative to R134a. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7) Within the range of the figure enclosed by the line segments PD, DH', and H'P connecting the three points respectively, or on the aforementioned straight line the law of nature, The line segment DH' is a straight line, A point on line segment PD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 It is expressed as -0.8166x-35.54) ,and A point on line segment H'P is (x, -0.08728x 2 +10.791x-251.26, 0.08728x 2 It is expressed as -11.791x + 351.26).

[0027] The refrigerants of this disclosure may contain additional refrigerants in addition to HFO-1132(E), R1234ze, and R1234yf, to the extent that they do not impair the above-mentioned properties and effects. In this regard, in some embodiments... In this case, the refrigerant disclosed herein contains a total of HFO-1132(E), R1234ze, and R1234yf relative to the total refrigerant. Preferably, it contains 99.5% by mass or more, more preferably 99.75% by mass or more, and 99.9% by mass. It is more preferable to contain % by amount or more, even more preferable to contain 99.999% by mass, and most preferable to contain 99.9999% by mass or more. The refrigerant of this disclosure may consist substantially of only HFO-1132(E), R1234ze and R1234yf, in which case the refrigerant of this disclosure may consist only of HFO-1132(E), R1234ze and R1234y, and unavoidable impurities. The refrigerant may consist only of HFO-1132(E), R1234ze, and R1234yf.

[0028] The additional refrigerant is not particularly limited and can be broadly selected. The mixed refrigerant may contain one additional refrigerant alone or two or more additional refrigerants. Examples of additional refrigerants include acetylene, HFO-1132a, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, HFC-152a, HFC-161, and 3,3,3-trifluoropropyne. The total amount of additional refrigerants is preferably 0.5% by mass or less, and more preferably 0.25% by mass or less, relative to the total amount of refrigerant. It is more preferably 0.1% by mass or less, and most preferably 0.01% by mass or less. stomach.

[0029] 2. Refrigerant composition The refrigerant compositions of this disclosure contain at least the refrigerant of this disclosure and can be used for the same purposes as the refrigerant of this disclosure. Furthermore, the refrigerant compositions of this disclosure can be used to obtain a working fluid for a refrigeration system by further mixing them with at least refrigerant oil. The refrigerant compositions of this disclosure contain, in addition to the refrigerant of this disclosure, at least one other component. The refrigerant compositions of this disclosure may optionally contain at least one of the following other components. As described above, when the refrigerant compositions of this disclosure are used as working fluids in a refrigerator, they are usually used in mixture with at least refrigerant oil. Therefore, the refrigerant compositions of this disclosure preferably contain substantially no refrigerant oil. Specifically, the refrigerant composition of this disclosure preferably contains 1% by mass or less of refrigerant oil relative to the total refrigerant composition. It is below, and more preferably 0.1% by mass or less.

[0030] 2.1 water The refrigerant composition of this disclosure may contain trace amounts of water. Preferably, the water content in the refrigerant composition is 0.1% by mass or less relative to the total refrigerant. As a result, the intramolecular double bonds of unsaturated fluorocarbon compounds that may be contained in the refrigerant are stabilized, and oxidation of unsaturated fluorocarbon compounds is also less likely to occur, thus cooling The stability of the medium composition is improved.

[0031] 2.2 tracer The tracer is added to the refrigerant composition of the Disclosure at a detectable concentration so that any changes to the refrigerant composition of the Disclosure can be tracked if it is diluted, contaminated, or otherwise altered.

[0032] The refrigerant composition of this disclosure may contain one tracer alone or two or more tracers.

[0033] The tracer is not particularly limited and can be appropriately selected from among commonly used tracers.

[0034] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodized compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). Fluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers are particularly preferred.

[0035] The following compounds are preferred as tracers. 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, CH2ClF) CFC-1113 (chlorotrifluoroethylene, CF2=CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2) HFE-134a (tri Fluoromethyl-fluoromethyl ether (CF3OCH2F)HFE-143a (trifluoromethyl-methyl ether, CF3OCH3) HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3) HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)

[0036] The refrigerant composition of this disclosure may contain tracers in total at about 10 parts by weight per million (ppm) or more relative to the entire refrigerant composition. Alternatively, the refrigerant composition of this disclosure may contain tracers in total at about 1000 ppm or less relative to the entire refrigerant composition. The refrigerant composition of this disclosure may preferably contain tracers in total at about 30 ppm or more, more preferably at about 50 ppm or more, relative to the entire refrigerant composition. The refrigerant composition of this disclosure may contain tracers The total amount of - may preferably be about 500 ppm or less, and may also be about 300 ppm or less, relative to the entire refrigerant composition.

[0037] 2.3 UV fluorescent dyes The refrigerant composition of this disclosure may contain one ultraviolet fluorescent dye alone, or it may contain two or more ultraviolet fluorescent dyes.

[0038] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0039] Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, as well as their derivatives. Naphthalimide and coumarin, or either or both, are particularly preferred as ultraviolet fluorescent dyes.

[0040] 2.4 Stabilizer The refrigerant composition of this disclosure may contain one stabilizer alone or two or more stabilizers.

[0041] The stabilizer is not particularly limited and can be appropriately selected from among commonly used stabilizers.

[0042] Examples of stabilizers include nitro compounds, ethers, and amines.

[0043] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0044] Examples of ethers include 1,4-dioxane.

[0045] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0046] Other examples include butylhydroxyxylene and benzotriazole.

[0047] The stabilizer content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total refrigerant. It is preferable to keep it below % and more preferably below 2% by mass.

[0048] 2.5 Polymerization inhibitors The refrigerant composition of this disclosure may contain one polymerization inhibitor alone or two or more polymerization inhibitors.

[0049] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0050] Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, and hydroquinone. Examples include methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0051] The polymerization inhibitor content is preferably 0.01% by mass or more relative to the total refrigerant. It is more preferable that the amount be 0.05% by mass or more. The content of the polymerization inhibitor is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total amount of refrigerant.

[0052] 3. Working fluid containing refrigeration oil The refrigerant oil-containing working fluid of this disclosure comprises at least the refrigerant or refrigerant composition of this disclosure and refrigerant oil, and is used as a working fluid in a refrigerator. Specifically, the refrigerant oil-containing working fluid of this disclosure is obtained by mixing refrigerant oil used in the compressor of a refrigerator with the refrigerant or refrigerant composition. The refrigerant oil-containing working fluid generally contains 10% by mass or more of refrigerant oil. The refrigerant oil-containing working fluid generally contains 50% by mass or less of refrigerant oil.

[0053] 3.1 Refrigerating machine oil The composition of this disclosure may contain one type of refrigeration oil alone, or it may contain two or more types.

[0054] The refrigeration oil is not particularly limited and can be appropriately selected from commonly used refrigeration oils. In that case, compatibility with the mixture and A refrigerating oil that is superior in terms of improving the stability of the aforementioned mixture can be appropriately selected.

[0055] Examples of base oils for refrigeration oils include polyalkylene glycol (PAG) and polyols. At least one selected from the group consisting of sterl (POE) and polyvinyl ether (PVE) is preferred.

[0056] Refrigerant oil may contain additives in addition to the base oil. The additives may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents, and defoaming agents.

[0057] For refrigeration oil, a kinematic viscosity of 5 cSt or higher at 40°C is preferable from a lubrication standpoint. Furthermore, for refrigeration oil, a kinematic viscosity of 400 cSt or lower at 40°C is preferable from a lubrication standpoint.

[0058] The refrigerant oil-containing working fluid of this disclosure may optionally further contain at least one additive. Examples of additives include the following compatibilizers.

[0059] 3.2 Compatibilizer The refrigerant oil-containing working fluid of this disclosure may contain one type of compatibilizer alone, or it may contain two or more types of compatibilizers.

[0060] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0061] Examples of compatibilizers include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. Polyoxyalkylene glycol ethers are particularly preferred as compatibilizers.

[0062] 4. How to operate a refrigerator The method for operating the refrigerator described herein is a method for operating the refrigerator using the refrigerant described herein.

[0063] Specifically, the method for operating the refrigerator of this disclosure includes a step of circulating the refrigerant of this disclosure in the refrigerator.

[0064] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0065] The following provides further details with reference to examples. However, this disclosure is not limited to these examples.

[0066] HFO-1132(E), R1234ze, and R1234yf are shown in Table 1, based on their sum. A mixed refrigerant was prepared by mixing it in the specified mass percentage. The global warming capacity (GWP) of R410A (R32=50% / R125=50%) and the above mixed refrigerant was evaluated based on the values ​​from the IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report. The GWP of HFO-1132(E) was assumed to be 1. The refrigeration capacity of R410A and the above mixed refrigerant was determined by performing theoretical calculations of the refrigeration cycle of the mixed refrigerant under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0).

[0067] For each of these refrigerant mixtures, the COP ratio and refrigeration capacity ratio were determined relative to R410A. The calculation conditions were as follows: Evaporation temperature: -50°C (Table 1) and (Table 5), -10°C (Table 2) and (Table 6) Condensation temperature: 45℃ Superheat degree: 5K Supercooling degree: 5K Compressor efficiency: 70% These values, along with the GWP for each refrigerant mixture, are shown in Table 1. Note that the specific COP and specific refrigeration capacity are expressed as percentages of R410A or R134a.

[0068] The coefficient of performance (COP) was calculated using the following formula. COP = (Refrigeration capacity or heating capacity) / Power consumption

[0069] The combustion rate test was performed using the apparatus shown in Figure 1, as follows. First, the mixed refrigerant used was made 99.5% or higher in purity and degassed by repeating a cycle of freezing, pumping, and thawing until no trace of air was visible on the vacuum gauge. The combustion rate was measured using the closed method. The initial temperature was the ambient temperature. Ignition was performed by generating an electrical spark between electrodes at the center of the sample cell. The discharge duration was 1.0 to 9.9 ms, and the ignition energy was typically about 0.1 to 1.0 J. The flame propagation was visualized using the Schlieren method. We tried a cylindrical container (inner diameter: 155mm, length: 198mm) with two light-transmitting acrylic windows. A xenon lamp was used as the light source for the sieve cell. The Schlieren image of the flame was recorded with a high-speed digital video camera at a framing speed of 600fps and saved to a PC.

[0070] The combustion rate (Su (cm / s)) is expressed as the volume of unburned gas consumed per unit time by a unit area of ​​the flame surface, and is calculated using the following formula. Su = Sb * ρu / ρb Sb; Flame propagation speed (cm / s) ρu; adiabatic flame temperature (unburned) ρb; adiabatic flame temperature (already combusted) Here, Sb was obtained from the Schlieren video image, ρu was the measured temperature, and ρb was calculated from the heat of combustion and specific heat at constant pressure of the combustion gas.

[0071] [Table 1]

[0072] [Table 2]

[0073] Based on these results, the refrigerant of this disclosure is a WCF-free refrigerant when it satisfies the following requirements. It is clear that it becomes a fuel, and the refrigeration capacity ratio based on R404A is 70% or more. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) Within the area of ​​the figure enclosed by the line segments AB, BF, FE, and EA connecting the four points, or on the line segments the law of nature, Line segments AB, BF, and EA are straight lines, and A point on line segment FE is (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 (-7.5772x + 194.748) To be made to do something.

[0074] These results show that, when the refrigerant of this disclosure satisfies the following requirements, the refrigerant of this disclosure becomes WCFF slightly flammable and has a refrigeration capacity ratio of 70% or more relative to R404A. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DF, FE, and EC connecting the four points respectively, or on the line segments the law of nature, Line segments DF and EC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment FE is (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 (-7.5772x + 194.748) To be made to do something.

[0075] Based on these results, the refrigerant of this disclosure is a WCF-free refrigerant when it satisfies the following requirements. It is found that it becomes combustible, and the refrigeration capacity ratio based on R134a is 100% or more. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H(2.1, 1.0, 96.9) and Point G(14.4, 84.6, 1.0) Within the area of ​​the figure enclosed by the line segments AB, BH, HG, and GA connecting the four points, or on the line segments the law of nature, Line segments AB, BH, and GA are straight lines. A point on line segment HG is (x, -0.1974x 2 +10.054x-19.242, 0.1974x 2 It can be expressed as (-11.054x + 119.242).

[0076] Based on these results, the refrigerant of this disclosure is a WCF-free refrigerant when it satisfies the following requirements. It is found that it burns and its boiling point is below -40°C. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point J(12.3, 1.0, 86.7) and Point I (22.6, 76.4, 1.0) Within the area of ​​the figure enclosed by the line segments AB, BJ, JI, and IA connecting the four points, or on the line segments the law of nature, Line segments AB, BJ, and IA are straight lines, and A point on line segment JI is (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 It can be expressed as (-13.934x + 233.76).

[0077] Based on these results, the refrigerant of this disclosure is a WCF-free refrigerant when it satisfies the following requirements. It is found that it becomes combustible, and the refrigeration capacity ratio based on R134a is 150% or more. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point A(72.0, 27.0, 1.0), Point B(72.0, 1.0, 27.0), Point H'(31.3, 1.0, 67.7) and Point G'(44.1, 54.9, 1.0) The area within the figure enclosed by the line segments AB, BH', H'G', and G'A connecting the four points, or the aforementioned line It is on the ground, Line segments AB, BH', and G'A are straight lines, and The point on line segment H'G' is (x, -0.08728x² + 10.791x - 251.26, 0.08728x 2 It is expressed as -11.791x + 351.26).

[0078] These results show that, when the refrigerant of this disclosure satisfies the following requirements, the refrigerant of this disclosure becomes WCFF slightly flammable and has a refrigeration capacity ratio of 100% or more relative to R134a. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts in percent are x, y, and z respectively, the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass. In the three-component composition diagram, the coordinates (x,y,z) are: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point H(2.1, 1.0, 96.9) and Point G(14.4, 84.6, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DH, HG, and GC connecting the four points respectively, or on the line segments the law of nature, Line segments DH and GC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment HG is (x, -0.1974x 2 +10.054x-19.242, 0.1974x 2 (-11.054x + 119.242) To be made to do something.

[0079] These results show that the refrigerant of this disclosure becomes WCFF slightly flammable and has a boiling point of -40°C or lower when it satisfies the following requirements. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point J(12.3, 1.0, 86.7) and Point I (22.6, 76.4, 1.0) Within the area of ​​the figure enclosed by the line segments CD, DJ, JI, and IC connecting the four points respectively, or on the line segments the law of nature, Line segments DJ and IC are straight lines, and The point on line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 (-0.8166x-35.54) and A point on line segment JI is (x, -0.1609x2 +12.934x-133.76, 0.1609x 2 It can be expressed as (-13.934x + 233.76).

[0080] These results show that, when the refrigerant of this disclosure satisfies the following requirements, the refrigerant of this disclosure becomes WCFF slightly flammable and has a refrigeration capacity ratio of 150% or more relative to R134a. <Requirements> In the aforementioned refrigerants, the quality of HFO-1132(E), R1234ze, and R1234yf is based on the sum of these. When the amounts (%) are x, y, and z respectively, in a three-component composition diagram where the sum of HFO-1132(E), R1234ze, and R1234y is 100% by mass, the coordinates (x,y,z) are: Point P(41.95, 47.8, 10.25), Point D(52.4, 1.0, 46.6) and Point H'(31.3, 1.0, 67.7) Within the range of the figure enclosed by the line segments PD, DH', and H'P connecting the three points respectively, or on the aforementioned straight line the law of nature, The line segment DH' is a straight line, A point on line segment PD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 It is expressed as ±0.8166x-35.54), and A point on line segment H'P is (x, -0.08728x 2 +10.791x-251.26, 0.08728x 2 It is expressed as -11.791x + 351.26).

[0081] The approximate formulas showing the coordinates of points on each line segment were obtained by deriving the approximate formula for the curve connecting the three points using the least squares method, as shown in Tables 3 and 4.

[0082] [Table 3]

[0083] [Table 4]

[0084] Furthermore, Table 5 shows the results of comparing the performance of the mixed refrigerants listed therein with that of R404A.

[0085] [Table 5]

[0086] Furthermore, the results of comparing the performance of the mixed refrigerants shown in Table 6 with that of R134a are also shown in the same table.

[0087] [Table 6]

Claims

1. A composition comprising a refrigerant, The composition contains 0.1% by mass or less of water based on the total amount of the refrigerant, The refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), 1,3,3,3-tetrafluoropropene (R1234ze), and 2,3,3,3-tetrafluoro-1-propene (R1234yf) in a total amount of 99.5 mass% or more based on the total amount of the refrigerant, In the refrigerant, when the mass percentages of HFO-1132(E), R1234ze, and R1234yf based on the sum of these are x, y, and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R1234ze, and R1234yf is 100 mass%, the coordinates (x, y, z) are as follows: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point F(17.0, 1.0, 82.0) and Point E(34.1, 64.9, 1.0) The area is within the shape enclosed by the line segments CD, DF, FE, and EC connecting the four points above, or on the line segments above, The line segments DF and EC are straight lines, and The point on the line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and The point on the line segment FE is (x, -0.0556x 2 +6.5772x-94.748, 0.0556x 2 -7.5772x+194.748).

2. A composition comprising a refrigerant, The composition contains 0.1% by mass or less of water based on the total amount of the refrigerant, The refrigerant contains HFO-1132(E), R1234ze, and R1234yf in a total amount of 99.5% by mass or more based on the total amount of the refrigerant, In the refrigerant, when the mass percentages of HFO-1132(E), R1234ze, and R1234yf based on the sum of these are x, y, and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R1234ze, and R1234yf is 100 mass%, the coordinates (x, y, z) are as follows: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point H(2.1, 1.0, 96.9) and Point G(14.4, 84.6, 1.0) The area is within the shape enclosed by the line segments CD, DH, HG, and GC connecting the four points above, or on said line segments, The line segments DH and GC are straight lines, and The point on the line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and The point on the line segment HG is (x, -0.1974x 2 +10.054x-19.242, 0.1974x 2 -11.054x+119.242), a composition.

3. A composition comprising a refrigerant, The composition contains 0.1% by mass or less of water based on the total amount of the refrigerant, The refrigerant contains HFO-1132(E), R1234ze, and R1234yf in a total amount of 99.5% by mass or more based on the total amount of the refrigerant, In the refrigerant, when the mass percentages of HFO-1132(E), R1234ze, and R1234yf based on the sum of these are x, y, and z, respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R1234ze, and R1234yf is 100 mass%, the coordinates (x, y, z) are as follows: Point C(38.7, 60.3, 1.0), Point D(52.4, 1.0, 46.6), Point J (12.3, 1.0, 86.7) and Point I (22.6, 76.4, 1.0) It is within the range of the figure enclosed by the line segments CD, DJ, JI, and IC connecting the four points above, or on said line segments, The line segments DJ and IC are straight lines, and The point on the line segment CD is (x, -0.0455x 2 -0.1834x+135.54, 0.0455x 2 -0.8166x-35.54), and The point on the line segment JI is (x, -0.1609x 2 +12.934x-133.76, 0.1609x 2 -13.934x+233.76).

4. The composition according to any one of claims 1 to 3, further comprising a refrigerating machine oil.

5. The composition according to any one of claims 1 to 4, which is used as an alternative refrigerant to R404A.

6. A refrigerator comprising the composition according to any one of claims 1 to 4 as a working fluid.

7. A method for operating a refrigerator, comprising: A method comprising circulating the composition of any one of claims 1 to 4 as a working fluid in a refrigerator.

8. Use of the composition according to any one of claims 1 to 4 as an alternative refrigerant to R410A.

Images