Patent Application
20220177762
The present disclosure relates to a composition comprising a refrigerant, use of the composition, a refrigerating machine having the composition, and a method for operating the refrigerating machine.
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 (PTL 1).
A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), 1,3,3,3-tetrafluoropropene (R1234ze), and difluoromethane (R32).
The refrigerant according to the present disclosure has a low GWP.
The present inventors conducted intensive studies to solve the above problems, and consequently found that a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), 2,3,3,3-tetrafluoro-1-propene (R1234yf), trifluoroethylene (HFO-1123), and difluoromethane (R32) 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.
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). Non-fluorocarbon compounds include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), ammonia (R717), and the like.
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, a refrigerant having “WCF lower flammability” means that the most flammable composition (worst case of formulation for flammability: WCF) has a burning velocity of 10 cm/s or less according to the US ANSI/ASHRAE Standard 34-2013. Further, in the present specification, a refrigerant having “ASHRAE lower flammability” means that the burning velocity of WCF is 10 cm/s or less, that the most flammable fraction composition (worst case of fractionation for flammability: WCFF), which is specified by performing a leakage test during storage, shipping, or use based on ANSI/ASHRAE 34-2013 using WCF, has a burning velocity of 10 cm/s or less, and that the flammability classification according to the US ANSI/ASHRAE Standard 34-2013 is determined to be classified as “Class 2L.”
The refrigerant according to the present disclosure comprises trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and difluoromethane (R32). In this specification, this refrigerant is sometimes referred to as “Refrigerant 1.”
The refrigerant according to the present disclosure may further comprise 2,3,3,3-tetrafluoro-1-propene (R1234yf). This refrigerant is sometimes referred to as “Refrigerant 2” in this specification. The refrigerants according to the present disclosure have a low GWP.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132(E), HFO-1123, R1234ze, and R32 based on their sum is respectively represented by x, y, z, and a,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines GG′, G′B, BD, DC, and CG that connect the following 5 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point G′ (0.0314a2−1.8079a+72.0, −0.0199a2+0.0677a+3.8, 100−a−x−y),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y),
point D (0.0, 0.0234a2+0.0647a+86.3, 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GG′, G′B, and DC (excluding point B, point D, point C, and point G);
if 11.1<a≤16.4, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GG′, G′B, BO, and OG that connect the following 4 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point G′ (−1.0566a+67.528, −0.3962a+6.4981, 100−a−x−y),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GG′ and G′B (excluding point B, point O, and point G);
if 16.4<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x),
point A (0.0076a2−1.7a+76.031, 0.0, 100−a−x),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point C, point I, point A, and point B);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (0.00738a2−1.0762a+65.22, 100−a−x, 0.0),
point I (0.00738a2−1.0762a+65.22, 0.0, 100−a−x),
point A (0.00582a2−1.5915a+74.4, 0.0, 100−a−x),
point B (0.0, 0.00328a2−1.3169a+67.421, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point G, point I, point A, and point B); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (−0.45a+51.91, 100−a−x, 0.0),
point I (−0.45a+51.91, 0.0, 100−a−x),
point A (−1.075a+62.985, 0.0, 100−a−x),
point B (0.0, −1.025a+60.895, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point G, point I, point A, and point B). When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A, and further ensures a WCF lower flammability.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132(E), HFO-1123, R1234ze, and R32 based on their sum is respectively represented by x, y, z, and a,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BD, DC, and CJ that connect the following 8 points:
point J (100−a−y, 0.0072a2−0.1704a+52.9, 0.0),
point Q (0.0112a2−1.3048a+62.1, 96.5−a−x, 3.5),
point N (0.0207a2−1.5817a+65.9, −0.0547a2+1.1392a+21.6, 100−a−x-Y),
point M (0.0278a2−1.7325a+64.5, 80.0−a−x, 20.0),
point K (0.0421a2−2.2419a+62.5, 100−a−x-z, −0.0132a2+0.768a+25.1),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y),
point D (0.0, 0.0234a2+0.0647a+86.3, 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B);
if 11.1<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BO, and OJ that connect the following 7 points:
point J (100−a−y, −0.0285a2+0.5371a+49.443, 0.0),
point Q (0.0166a2−1.382a+62.291, 96.5−a−x, 3.5),
point N (0.0183a2−1.5044a+65.339, −0.0395a2+1.4643a+16.116, 100−a−x−y),
point M (0.0145a2−1.4001a+62.448, 80.0−a−x, 20.0),
point K (0.0184a2−1.7325a+59.763, 100−a−x−z, −0.009a2+0.6996a+25.34),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BO, and OJ that connect the following 7 points:
point J (100−a−y, 0.00542a2−1.3598a+75.92, 0.0),
point Q (0.0049a2−0.728a+53.204, 96.5−a−x, 3.5),
point N (0.0075a2−0.971a+58.81, −0.0038a2−0.0303a30.581, 100−a−x−y),
point M (0.0019a2−0.7375a+53.782, 80.0−a−x, 20.0),
point K (0.0086a2−1.2345a+53.442, 100−a−x−z, −0.0045a2+0.4752a+28.157),
point B (0.0, 0.00328a2−1.3169a+67.421, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JN, NM, MK, KA, AB, BO, and OJ that connect the following 7 points:
point J (100−a−y, −0.9a+66.22, 0.0),
point N (−0.425a+49.315, −0.3a+8.86, 100−a−x−y),
point M (−0.525a+48.095, 80.0−a−x, 20.0),
point K (15.9, 0.0, 84.1−a),
point A (−1.075a+62.985, 0.0, 100−a−x),
point B (0.0, −1.025a+60.895, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines NM, MK, KA, and AB (excluding point J and point B). When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A, and further ensures an ASHRAE lower flammability.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132(E), HFO-1123, R1234yf, R1234ze, and R32 based on their sum is respectively x, y, z1, z2, and a, the sum of z1 and z2 is z, z1/z is r, and w=−0.00162a2−0.0097a+0.592,
if 0<a≤11.1, and 0<r≤w, coordinates (x, y, z) in a ternary composition diagram whose vertices are a point of (100−a) mass % of HFO-1132(E), a point of (100−a) mass % of HFO-1123, and a point of (100−a) mass % of the sum of R1234yf and R1234ze are within the range of a figure surrounded by straight lines GG′r, G′rBr, BrDr, DrC, and CG that connect the following 5 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point G′r (0.0314a2−1.8079a+72.0, (−0.0708a2+0.9972a−4.8964)r2+(0.0424a2−0.7622a−3.5518)r+(−0.0199a2+0.0677a+3.8), 100−a−x−y),
point Br (0.0, −r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.0603a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471a+86.3), 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GG′r, G′rBr, and DrC (excluding point G, point Br, point Dr, and point C);
if 0<a≤11.1, and w<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrDr, DrC, and CG that connect the following 6 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point I (0.0314a2−1.8079a+72.0, 0.0, 100−a−x),
point Ar ((−0.0031a2+0.0165a−1.6)r2+(0.0095a2−0.2769a−6.0)r+(0.0084a2−1.7237a+76.2), 0.0, 100−a−x),
point Br (0.0, (−a2)r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.0603a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471a+86.3), 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GI, IAr, ArBr, and DrC (excluding point G, point I, point Ar, point Br, point Dr, and point C);
if 11.1<a≤16.4, and 0<r≤w, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GG′r, G′rBr, BrO, and OG that connect the following 4 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point G′, (0.021a2−0.1227a+4.6878, (4.1824a2−114.54a+753.47)r2+(0.0346a2+0.3301a−14.707)r+(−0.0099a2−0.1227a+4.6878), 100−a−x−y),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GG′r and G′rBr (excluding point G and point Br);
if 11.1<a≤16.4, and w<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x),
point Ar ((0.1221a2−4.6027a−34.247)r2+(−0.0564a2+2.0217a−23.397)r+(0.0076a2−1.7a+76.031), 0.0, 100−a−x),
point Br (0.0, (0.0839a2−3.1.38a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br);
if 16.4<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x),
point Ar ((0.1221a2−4.6027a−34.247)r2+(−0.0564a2+2.0217a−23.397)r+(0.0076a2−1.7a+76.031), 0.0, 100−a−x),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.00738a2−1.0762a+65.22, 100−a−x, 0.0),
point I (0.00738a2−1.0762a+65.22, 0.0, 100−a−x),
point Ar ((−0.009465a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.005842a2−1.5915a+74.4), 0.100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (−0.45a+51.91, 100−a−x, 0.0),
point I (−0.45a+51.91, 0.0, 100−a−x),
point Ar ((−1.6r2+(0.05a−12.39)r+(−1.075a+62.985), 0.100−a−x),
point Br (0.0, (3.8a−167.84)r2+(−3.8a+155.94)r+(−1.025a+60.895), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br). When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A, and further ensures a WCF lower flammability.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132(E), HFO-1123, R1234yf, R1234ze, and R32 based on their sum is respectively x, y, z1, z2, and a, the sum of z1 and z2 is z, z1/z is r, and v=−0.0581a+2.5484,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram whose vertices are a point of (100−a) mass % of HFO-1132(E), a point of (100−a) mass % of HFO-1123, and a point of (100−a) mass % of the sum of R1234yf and R1234ze are within the range of a figure surrounded by straight lines JKr, KrBr, BrDr, D2C, and CJ that connect the following 5 points:
point J (−0.0072a2−0.8296a+47.1, 100−a−x, 0.0),
point Kr ((−0.0241a2+0.4296a−2.8)r2+(0.033a2−0.6279a+2.0)r+(0.0421a2−2.2419a+62.5), (0.0142a2−0.3016a+1.4)r2+(−0.0167a2+0.2395a−7.9)r+(−0.0289a2+0.4739a+12.4), 100−a−x−y),
point Br (0.0, r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.0603a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471x+86.3), 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines JKr, KrBr, BrDr, and DrC (excluding point J, point Br, point Dr, and point C);
if 11.1<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points:
point J (0.0285a2−1.5371a+50.557, 100−a−x, 0.0),
point Kr ((0.0556a2−2.057a+14.984)r2+(−0.0217a2+0.7843a−6.9374)r+(0.0184a2−1.7325a+59.763), (0.0567a2−2.162a+16.817)r2+(−0.0298a2+1.0456a−15.236)r+(−0.0094a2+0.0329a+14.897), 100−a−x−y),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 26.6<a≤35.3, and 0<r≤v, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points:
point J (−0.00542a2+0.3598a+24.08, 100−a−x, 0.0),
point Kr ((−0.2299a+5.7149)r2+(0.1379a−5.069)r+(−0.7011x+45.351), (0.069a−2.4345)r2+(−0.1264a−5.1368)r+(−0.4943a+22.247), 100−a−x−y),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 26.6<a≤35.3, and v<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points:
point J (−0.00542a2+0.3598a+24.08, 0.0, 100−a−x),
point Kr ((−0.3218a+8.1609)r2+(1.4023a−38.701)r+(−1.3103a+61.555), 0.0, 100−a−x),
point Ar ((−0.00946a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.00584a2−1.5915a+74.4), 0.0, 100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br);
if 35.3<a≤43.8, and 0<r≤v, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points:
point J (−0.00542a2+0.3598a+24.08, 100−a−x, 0.0),
point Kr ((0.2824a−12.367)r2+(0.0235a−1.0306)r+(−0.5529a+40.119), (1.1294a−49.468)r+(−0.5647a+24.734), 100−a−x−y),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 35.3<a≤43.8, and v<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points:
point J (−0.00542a2+0.3598a+24.08, 100−a−x, 0.0),
point Kr ((0.2588a−12.336)r2+(−0.5294a+29.488)r+(0.0706a+12.808), 0.0, 100−a−x)),
point Ar ((−0.00946a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.00584a2−1.5915a+74.4), 0.0, 100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points:
point J (−0.1a+33.78, 100−a−x, 0.0),
point Kr (−r2+(−0.2a+15.06)r+15.9, 0.0, 100−a−x),
point Ar (−1.6r2+(0.05a−12.39)r+(−1.075a+62.985), 0.0, 100−a−x),
point Br (0.0, (3.8a−167.84)r2+(−3.8a+155.94)r+(−1.025a+60.895), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br). When the requirements above are satisfied, the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A, and further ensures an ASHRAE lower flammability.
Refrigerant 1 according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), HFO-1123, R1234ze, and R32 as long as the above properties and effects are not impaired. In this respect, the refrigerant according to the present disclosure preferably comprises HFO-1132(E), HFO-1123, R1234ze, and R32 in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, and even more preferably 99.9 mass % or more, based on the entire refrigerant.
Further, Refrigerant 2 according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), HFO-1123, R1234ze, R1234yf, and R32 as long as the above properties and effects are not impaired. In this respect, the refrigerant according to the present disclosure preferably comprises HFO-1132(E), HFO-1123, R1234ze, R1234yf, and R32 in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, and even more preferably 99.9 mass % or more, based on the entire refrigerant.
Such additional refrigerants are not limited, and can be selected from a wide range of refrigerants. The mixed refrigerant may comprise a single additional refrigerant, or two or more additional refrigerants.
The refrigerant according to the present disclosure can be preferably used as a working fluid in a refrigerating machine.
The composition according to the present disclosure is suitable for use as an alternative refrigerant for R410A.
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 %.
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.
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 tracers.
The refrigerant composition according to the present disclosure may contain one or more tracers at a total concentration of about 10 parts per million by weight (ppm) to about 1000 ppm based on the entire refrigerant composition. The refrigerant composition according to the present disclosure may preferably contain one or more tracers at a total concentration of about 30 ppm to about 500 ppm, and more preferably about 50 ppm to about 300 ppm, based on the entire refrigerant composition.
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.
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-pentaflucropropylamine 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.
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.
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.
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, are 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.
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.
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 trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), 1,3,3,3-tetrafluoropropene (R1234ze), and difluoromethane (R32).
Item 2.
The composition according to Item 1,
wherein
when the mass % of HFO-1132(E), HFO-1123, R1234ze, and R32 based on their sum in the refrigerant is respectively represented by x, y, z, and a,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines GG′, G′B, BD, DC, and CC that connect the following 5 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point G′ (0.0314a2−1.8079a+72.0, −0.0199a2+0.0677a+3.8, 100−a−x−y),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y),
point D (0.0, 0.0234a2+0.0647a+86.3, 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GG′, G′B, and DC (excluding point B, point D, point C, and point G);
if 11.1<a≤16.4, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GG′, G′B, BO, and OG that connect the following 4 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point G′ (−1.0566a+67.528, −0.3962a+6.4981, 100−a−x−y),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GG′ and G′B (excluding point B, point O, and point G);
if 16.4<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x),
point A (0.0076a2−1.7a+76.031, 0.0, 100−a−x),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O(0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point G, point I, point A, and point B);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (0.00738a2−1.0762a+65.22, 100−a−x, 0.0),
point I (0.00738a2−1.0762a+65.22, 0.0, 100−a−x),
point A (0.00582a2−1.5915a+74.4, 0.0, 100−a−x),
point B (0.0, 0.00328a2−1.3169a+67.421, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point G, point I, point A, and point B); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (−0.45a+51.91, 100−a−x, 0.0),
point I (−0.45a+51.91, 0.0, 100−a−x),
point A (−1.075a+62.985, 0.0, 100−a−x),
point B (0.0, −1.025a+60.895, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point G, point I, point A, and point B).
Item 3.
The composition according to Item 1,
wherein
when the mass % of HFO-1132(E), HFO-1123, R1234ze, and R32 based on their sum in the refrigerant is respectively represented by x, y, z, and a,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BD, DC, and CJ that connect the following 8 points:
point J (100−a−y, 0.0072a2−0.1704a+52.9, 0.0),
point Q (0.0112a2−1.3048a+62.1, 96.5−a−x, 3.5),
point N (0.0207a2−1.5817a+65.9, −0.0547a2+1.1392a+21.6, 100−a−x−y),
point M (0.0278a2−1.7325a+64.5, 80.0−a−x, 20.0),
point K (0.0421a2−2.2419a+62.5, 100−a−x−z, −0.0132a2+0.768a+25.1),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y),
point D (0.0, 0.0234a2+0.0647a+86.3, 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B);
if 11.1<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BO, and OJ that connect the following 7 points:
point J (100−a−y, −0.0285a2+0.5371a+49.443, 0.0),
point Q (0.0166a2−1.382a+62.291, 96.5−a−x, 3.5),
point N (0.0183a2−1.5044a+65.339, −0.0395a2+1.4643a+16.116, 100−a−x−y),
point M (0.0145a2−1.4001a+62.448, 80.0−a−x, 20.0),
point K (0.0184a2−1.7325a+59.763, 100−a−x−z, −0.009a2+0.6996a+25.34),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BO, and OJ that connect the following 7 points:
point J (100−a−y, 0.00542a2−1.3598a+75.92, 0.0),
point Q (0.0049a2−0.728a+53.204, 96.5−a−x, 3.5),
point N (0.0075a2−0.971a+58.81, −0.0038a2−0.0303a+30.581, 100−a−x−y)
point M (0.0019a2−0.7375a+53.782, 80.0−a−x, 20.0),
point K (0.0086a2−1.2345a+53.442, 100−a−x−z, −0.0045a2+0.4752a+28.157),
point B (0.0, 0.00328a2−1.3169a+67.421, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JN, NM, MK, KA, AB, BO, and OJ that connect the following 7 points:
point J (100−a−y, −0.9a+66.22, 0.0),
point N (−0.425a+49.315, −0.3a+8.86, 100−a−x−y),
point M (−0.525a+48.095, 80.0−a−x, 20.0),
point K (15.9, 0.0, 84.1−a),
point A (−1.075a+62.985, 0.0, 100−a−x),
point B (0.0, −1.025a+60.895, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines NM, MK, KA, and AB (excluding point J and point B).
Item 4.
The composition according to Item 1,
wherein the refrigerant further comprises 2,3,3,3-tetrafluoro-1-propene (R1234yf).
Item 5.
The composition according to Item 4,
wherein
when the mass % of HFO-1132(E), HFO-1123, R1234yf, R1234ze, and R32 based on their sum in the refrigerant is respectively x, y, z1, z2, and a, the sum of z1 and z2 is z, z1/z is r, and w=−0.00162a2−0.0097a+0.592,
if 0<a≤11.1, and 0<r≤w, coordinates (x, y, z) in a ternary composition diagram whose vertices are a point of (100−a) mass % of HFO-1132(E), a point of (100−a) mass % of HFO-1123, and a point of (100−a) mass % of the sum of R1234yf and R1234ze are within the range of a figure surrounded by straight lines GG′r, G′rBr, BrDr, DrC, and CC that connect the following 5 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point G′r (0.0314a2 1.8079a+72.0, (−0.0708a2+0.9972a−4.8964)r2+(0.0424a2−0.7622a−3.5518)r+(−0.0199a2+0.0677a+3.8), 100−a−x−y),
point Br (0.0, −r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.06 03a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471a+86.3), 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GG′r, G′rBr, and DrC (excluding point G, point Br, point Dr, and point C);
if 0<a≤11.1, and w<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrDr, DrC, and CG that connect the following 6 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point I (0.0314a2−1.8079a+72.0, 0.0, 100−a−x),
point Ar ((−0.0031a2+0.0165a−1.6)r2+(0.0095a2−0.2769a−6.0)r+(0.0084a2−1.7237a+76.2), 0.0, 100−a−x),
point Br (0.0, (−a2)r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.0603a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471a+86.3), 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GI, IAr, ArBr, and DrC (excluding point G, point I, point Ar, point Br, point Dr, and point C);
if 11.1<a≤16.4, and 0<r≤w, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GG′r, G′rBr, BrO, and OG that connect the following 4 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point G′r (0.021a2−0.1227a+4.6878, (4.1824a2−114.54a+753.47)r2+(0.0346a2+0.3301a−14.707)r+(−0.0099a2−0.1227a+4.6878), 100−a−x−y),
point Br (0.0, (0.0839a2−3.1.38a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GG′r and G′rBr (excluding point G and point Br);
if 11.1<a≤16.4, and w<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x),
point Ar ((0.1221a2−4.6027a−34.247)r2+(−0.0564a2+2.0217a−23.397)r+(0.0076a2−1.7a+76.031), 0.0, 100−a−x),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a41.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br);
if 16.4<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x),
point Ar ((0.1221a2−4.6027a−34.247)r2+(−0.0564a42.0217a−23.397)r+(0.0076a2−1.7a4−76.031), 0.0, 100−a−x),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a41.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.00738a2−1.0762a+65.22, 100−a−x, 0.0),
point I (0.00738a2−1.0762a+65.22, 0.0, 100−a−x),
point Ar ((−0.009465a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.005842a2−1.5915a+74.4), 0.100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br); and
if 43.8<a47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (−0.45a+51.91, 100−a−x, 0.0),
point I (−0.45a+51.91, 0.0, 100−a−x),
point Ar ((−1.6r2+(0.05a−12.39)r+(−1.075a+62.985), 0.100−a−x),
point Br (0.0, (3.8a−167.84)r2+(−3.8a+155.94)r+(−1.025a+60.895), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br).
Item 6.
The composition according to item 4,
wherein
when the mass % of HFO-1132(E), HFO-1123, R1234yf, R1234ze, and R32 based on their sum in the refrigerant is respectively x, y, z1, z2, and a, the sum of z1 and z2 is z, z1/z is r, and v=−0.0581a+2.5484,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram whose vertices are a point of (100−a) mass % of HFO-1132(E), a point of (100−a) mass % of HFO-1123, and a point of (100−a) mass % of the sum of R1234yf and R1234ze are within the range of a figure surrounded by straight lines JKr, KrBr, BrDr, DrC, and CJ that connect the following 5 points:
point J (−0.0072a2−0.8296a+47.1, 100−a−x, 0.0),
point Kr ((−0.0241a2+0.4296a−2.8)r2+(0.033a2−0.6279a+2.0)r+(0.0421a2−2.2419a+62.5), (0.0142a2−0.3016a+1.4)r2+(−0.0167a2+0.2395a−7.9)r+(−0.0289a2+0.4739a+12.4), 100−a−x−y),
point Br (0.0, r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.0603a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471x+86.3), 100−a−y),
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines JKr, KrBr, BrDr, and DrC (excluding point J, point Br, point Dr, and point C);
if 11.1<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points:
point J (0.0285a2−1.5371a+50.557, 100−a−x, 0.0),
point Kr ((0.0556a2−2.057a+14.984)r2+(−0.0217a2+0.7843a−6.9374)r+(0.0184a2−1.7325a+59.763), (0.0567a2−2.162a+16.817)r2+(−0.0298a2+1.0456a−15.236)r+(−0.0094a2+0.0329a+14.897), 100−a−x−y),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a41.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 26.6<a≤35.3, and 0<r≤v, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points:
point J (−0.00542a2+0.3598a+24 .08, 100−a−x, 0.0),
point Kr ((−0.2299a+5.7149)r2+(0.1379a−5.069)r+(−0.7011x+45.351), (0.069a−2.4345)r2+(−0.1264a−5.1368)r+(−0.4943a+22.247), 100−a−x−y),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 26.6<≤a35.3, and v<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points:
point J (−0.00542a2+0.3598a+24.08, 0.0, 100−a−x),
point Kr ((−0.3218a+8.1609)r2+(1.4023a−38.701)r+(−1.3103a+61.555), 0.0, 100−a−x),
point Ar ((−0.00946a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.00584a2−1.5915a+74.4), 0.0, 100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br);
if 35.3<a≤43.8, and 0<r≤v, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points:
point J (−0.00542a2+0.3598a+24.08, 100−a−x, 0.0),
point Kr ((0.2824a−12.367)r2+(0.0235a−1.0306)r+(−0.5529a+40.119), (1.1294a−49.468)r+(−0.5647a+24.734), 100−a−x−y),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 35.3<a≤43.8, and v<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points:
point J (−0.00542a2+0.3598a+24.08, 100−a−x, 0.0),
point Kr ((0.2588a−12.336)r2+(−0.5294a+29.488)r+(0.0706a+12.808), 0.0, 100−a−x)),
point Ar ((−0.00946a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.00584a2−1.5915a+74.4), 0.0, 100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points:
point J (−0.1a+33.78, 100−a−x, 0.0),
point Kr (−r2+(−0.2a+15.06)r+15.9, 0.0, 100−a−x),
point Ar (−1.6r2+(0.05a−12.39)r+(−1.075a+62.985), 0.0, 100−a−x),
point Br (0.0, (3.8a−167.84)r2+(−3.8a+155.94)r+(−1.025a+60.895), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br).
Item 7.
The composition according to any one of Items 1 to 6, for use as a working fluid for a refrigerating machine, wherein the composition further comprises a refrigeration oil.
Item 8.
The composition according to any one of Items 1 to 7, for use as an alternative refrigerant for R410A.
Item 9.
Use of the composition according to any one of Items 1 to 7 as an alternative refrigerant for R410A.
Item 10.
A refrigerating machine comprising the composition according to any one of Items 1 to 7 as a working fluid.
Item 11.
A method for operating a refrigerating machine, comprising the step of circulating the composition according to any one of Items 1 to 7 as a working fluid in a refrigerating machine.
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-1132(E), HFO-1123, R1234ze, and R32 at a mass % based on their sum as shown in Tables 1 to 11.
The GWP of compositions each comprising a mixture of R410A (R32=50%/R125=50%) was evaluated based on the values stated in the intergovernmental Panel on Climate Change (IPCC), fourth report. The GWP of HFO-1132(E), which was not stated therein, was assumed to be 1 from HFO-1132a (GWP=1 or less) and HFO-1123 (GWP=0.3, described in PTL 1). The refrigerating capacity of compositions each comprising R410A and a mixture of HFO-1132(E) and HFO-1123 was determined by performing theoretical refrigeration cycle calculations for the mixed refrigerants using the National Institute of Science and Technology (NIST) and Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.
The COP ratio and the refrigerating capacity ratio of the mixed refrigerants relative to those of R410 were determined. The calculation conditions were as follows.
Evaporating temperature: 5° C.
Condensation temperature: 45° C.
Degree of superheating: 5 K
Degree of subcooling: 5 K
Compressor efficiency: 70%
Tables 1 to 11 show 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
The composition of each mixture was defined as WCF. A leak simulation was performed using NIST Standard Reference Data Base Refleak Version 4.0 under the conditions of Equipment, Storage, Shipping, Leak, and Recharge according to the ASHRAE Standard 34-2013. The most flammable fraction was defined as WCFF.
For the flammability, the burning velocity was measured according to the ANSI/ASHRAE Standard 34-2013. Both WCF and WCFF having a burning velocity of 10 cm/s or less were determined to be “Class 2L (lower flammability).”
A burning velocity test was performed using the apparatus shown in
The flame propagation velocity Sb (cm/sec) was measured using the video image. The burning velocity (Su) is the volume of unburned gas in which the flame surface of the unit area is consumed in the unit time, and was calculated according to the following equation.
Su=Sb*ρu/ρb
ρu: Adiabatic flame temperature (unburned)
ρb: Adiabatic flame temperature (already burned)
ρu was the measured temperature, and ρb was calculated from the heat of the combustion of the combustion gas and the specific heat of constant pressure.
Tables 12 to 19 show the results.
These results indicate that a mixed refrigerant has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A, and further ensures a WCF lower flammability when the following requirements are satisfied. Specifically, when the mass % of HFO-1132(E), HFO-1123, R1234ze, and R32 based on their sum in the mixed refrigerant is respectively represented by x, y, z, and a,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines GG′, G′B, BD, DC, and CG that connect the following 5 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point G′ (0.0314a2−1.8079a+72.0, −0.0199a2+0.0677a+3.8, 100−a−x−y)
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y),
point D (0.0, 0.0234a2+0.0647a+86.3, 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GG′, G′B, and DC (excluding point B, point D, point C, and point G);
if 11.1<a≤16.4, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GG′, G′B, BO, and OG that connect the following 4 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point G′ (−1.0566a+67.528, −0.3962a+6.4981, 100−a−x−y),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GG′ and G′B (excluding point B, point O, and point G);
if 16.4<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x),
point A (0.0076a2−1.7a+76.031, 0.0, 100−a−x),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point G, point I, point A, and point B);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (0.00738a2−1.0762a+65.22, 100−a−x, 0.0),
point I (0.00738a2−1.0762a+65.22, 0.0, 100−a−x),
point A (0.00582a2−1.5915a+74.4, 0.0, 100−a−x),
point B (0.0, 0.00328a2−1.3169a+67.421, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point G, point I, point A, and point B); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IA, AB, BO, and OG that connect the following 5 points:
point G (−0.45a+51.91, 100−a−x, 0.0),
point I (−0.45a+51.91, 0.0, 100−a−x),
point A (−1.075a+62.985, 0.0, 100−a−x),
point B (0.0, −1.025a+60.895, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI and AB (excluding point G, point I, point A, and point B).
The results also indicate that a mixed refrigerant has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A, and further ensures an ASHRAE lower flammability when the following requirements are satisfied. Specifically, when the mass % of HFO-1132(E), HFO-1123, R1234ze, and R32 based on their sum in the mixed refrigerant is respectively represented by x, y, z, and a,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram in which the sum of HFO-1132(E), HFO-1123, and R1234ze is (100−a) mass % are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BD, DC, and CJ that connect the following 8 points:
point J (100−a−y, 0.0072a2−0.1704a+52.9, 0.0),
point Q (0.0112a2−1.3048a+62.1, 96.5−a−x, 3.5),
point N (0.0207a2−1.5817a+65.9, −0.0547a2+1.1392a+21.6, 100−a−x−y),
point M (0.0278a2−1.7325a+64.5, 80.0−a−x, 20.0),
point K (0.0421a2−2.2419a+62.5, 100−a−x−z, −0.0132a2+0.768a+25.1),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y),
point D (0.0, 0.0234a2+0.0647a+86.3, 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B);
if 11.1<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BO, and OJ that connect the following 7 points:
point J (100−a−y, −0.0285a2+0.5371a+49.443, 0.0),
point Q (0.0166a2−1.382a+62.291, 96.5−a−x, 3.5),
point N (0.0183a2−1.5044a+65.339, −0.0395a2+1.4643a+16.116, 100−a−x−y),
point M (0.0145a2−1.4001a+62.448, 80.0−a−x, 20.0),
point K (0.0184a2−1.7325a+59.763, 100−a−x−z, −0.009a2+0.6996a+25.34),
point B (0.0, 0.0057a2−1.4197a+68.462, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JQ, QN, NM, MK, KB, BO, and OJ that connect the following 7 points:
point J (100−a−y, 0.00542a2−1.3598a+75.92, 0.0),
point Q (0.0049a2−0.728a+53.204, 96.5−a−x, 3.5),
point N (0.0075a2−0.971a+58.81, −0.0038a2−0.0303a+30.581, 100−a−x−y),
point M (0.0019a2−0.7375a+53.782, 80.0−a−x, 20.0),
point K (0.0086a2−1.2345a+53.442, 100−a−x−z, −0.0045a2+0.4752a+28.157),
point B (0.0, 0.00328a2−1.3169a+67.421, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JQ, QN, NM, MK, and KB (excluding point J and point B); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JN, NM, MK, KA, AB, BO, and OJ that connect the following 7 points:
point J (100−a−y, −0.9a+66.22, 0.0),
point N (−0.425a+49.315, −0.3a+8.86, 100−a−x−y),
point M (−0.525a+48.095, 80.0−a−x, 20.0),
point K (15.9, 0.0, 84.1−a),
point A (−1.075a+62.985, 0.0, 100−a−x),
point B (0.0, −1.025a+60.895, 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines NM, MK, KA, and AB (excluding point J and point B).
The approximate expressions representing the coordinates of each point were obtained as shown below.
Next, mixed refrigerants were prepared by mixing HFO-1132(E), HFO-1123, R1234ze, R1234yf, and R32 at a mass % based on their sum as shown in Tables 32 to 40. In the following, the ratio of R1234yf to the sum of R1234ze and R1234yf is defined as r.
R410A)
R410A)
indicates data missing or illegible when filed
R410A)
R410A)
indicates data missing or illegible when filed
R410A)
R410A)
indicates data missing or illegible when filed
R410A)
R410A)
R410A)
R410A)
R410A)
R410A)
indicates data missing or illegible when filed
R410A)
R410A)
R410A)
R410A)
R410A)
R410A)
Tables 41 to 47 show the results obtained by evaluating the flammability of the mixed refrigerants in the same manner as stated above.
indicates data missing or illegible when filed
These results indicate that the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A, and further ensures a WCF lower flammability when the following requirements are satisfied. Specifically, when the mass % of HFO-1132(E), HFO-1123, R1234yf, R1234ze, and R32 based on their sum in the mixed refrigerant is respectively x, y, z1, z2, and a, the sum of z1 and z2 is z, z1/z is r, and w=−0.00162a2−0.0097a+0.592,
if 0<a≤11.1, and 0<r≤w, coordinates (x, y, z) in a ternary composition diagram whose vertices are a point of (100−a) mass % of HFO-1132(E), a point of (100−a) mass % of HFO-1123, and a point of (100−a) mass % of the sum of R1234yf and R1234ze are within the range of a figure surrounded by straight lines GG′r, G′rBr, BrDr, DrC, and CG that connect the following 5 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point G′r (0.0314a2−1.8079a+72.0, (−0.0708a2+0.9972a−4.8964)r2+(0.0424a2−0.7622a−3.5518)r+(−0.0199a2+0.0677a+3.8), 100−a−x−y),
point Br (0.0, −r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.0603a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471a+86.3), 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GG′r, G′rBr, and DrC (excluding point G, point Br, point Dr, and point C);
if 0<a≤11.1, and w<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrDr, DrC, and CG that connect the following 6 points:
point G (0.0314a2−1.8079a+72.0, 100−a−x, 0.0),
point I (0.0314a2−1.8079a+72.0, 0.0, 100−a−x),
point Ar ((−0.0031a2+0.0165a−1.6)r2+(0.0095a2−0.2769a−6.0)r+(0.0084a2−1.7237a+76.2), 0.0, 100−a−x),
point Br (0.0, (−a2)r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.0603a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471a+86.3), 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines GI, IAr, ArBr, and DrC (excluding point G, point I, point Ar, point Br, point Dr, and point C);
if 11.1<a≤16.4, and 0<r≤w, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GG′r, G′rBr, BrO, and OG that connect the following 4 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point G′r (0.021a2−0.1227a+4.6878, (4.1824a2−114.54a+753.47)r2+(0.0346a2+0.3301a−14.707)r+(−0.0099a2−0.1227a+4.6878), 100−a−x−y),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GG′r and G′rBr (excluding point G and point Br);
if 11.1<a≤16.4, and w<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x),
point Ar ((0.1221a2−4.6027a−34.247)r2+(−0.0564a2+2.0217a−23.397)r+(0.0076a2−1.7a+76.031), 0.0, 100−a−x),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br);
if 16.4<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.015a2−1.4701a+70.266, 100−a−x, 0.0),
point I (0.015a2−1.4701a+70.266, 0.0, 100−a−x), point A, ((0.1221a2−4.6027a−34.247)r2+(−0.0564a2+2.0217a−23.397)r+(0.0076a2−1.7a+76.031), 0.0, 100−a−x),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br);
if 26.6<a≤43.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (0.00738a2−1.0762a+65.22, 100−a−x, 0.0),
point I (0.00738a2−1.0762a+65.22, 0.0, 100−a−x),
point Ar ((−0.009465a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.005842a2−1.5915a+74.4), 0.100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines GI, IAr, ArBr, BrO, and OG that connect the following 5 points:
point G (−0.45a+51.91, 100−a−x, 0.0),
point I (−0.45a+51.91, 0.0, 100−a−x),
point Ar ((−1.6r2+(0.05a−12.39)r+(−1.075a+62.985), 0.100−a−x),
point Br (0.0, (3.8a−167.84)r2+(−3.8a+155.94)r+(−1.025a+60.895), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines GI, IAr, and ArBr (excluding point G, point I, point Ar, and point Br).
The results also indicate that the refrigerant according to the present disclosure has a refrigerating capacity ratio of 85% or more relative to that of R410A, and a COP ratio of 92.5% or more relative to that of R410A, and further ensures an ASHRAE lower flammability when the following requirements are satisfied. Specifically, when the mass % of HFO-1132(E), HFO-1123, R1234yf, R1234ze, and R32 based on their sum in the mixed refrigerant is respectively x, y, z1, z2, and a, the sum of z1 and z2 is z, z1/z is r, and v=−0.0581a+2.5484,
if 0<a≤11.1, coordinates (x, y, z) in a ternary composition diagram whose vertices are a point of (100−a) mass % of HFO-1132(E), a point of (100−a) mass % of HFO-1123, and a point of (100−a) mass % of the sum of R1234yf and R1234ze are within the range of a figure surrounded by straight lines JKr, KrBr, BrDr, D2C, and CJ that connect the following 5 points:
point J (−0.0072a2−0.8296a+47.1, 100−a−x, 0.0),
point Kr ((−0.0241a2+0.4296a−2.8)r2+(0.033a2−0.6279a+2.0)r+(0.0421a2−2.2419a+62.5), (0.0142a2−0.3016a+1.4)r2+(−0.0167a2+0.2395a−7.9)r+(−0.0289a2+0.4739a+12.4), 100−a−x−y),
point Br (0.0, r2+(0.004a2−0.1343a−9.1)r+(0.008a2−1.4765a+68.8), 100−a−y),
point Dr (0.0, (−0.0603a2+0.8857a−2.4)r2+(0.1143a2−0.9267a−3.8)r+(0.0079a2+0.1471x+86.3), 100−a−y), and
point C (−0.189a2−0.8664a+32.9, 100−a−x, 0.0),
or on the straight lines JKr, KrBr, BrDr, and DrC (excluding point J, point Br, point Dr, and point C);
if 11.1<a≤26.6, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points;
point J (0.0285a2−1.5371a+50.557, 100−a−x, 0.0),
point Kr ((0.0556a2−2.057a+14.984)r2+(−0.0217a40.7843a−6.9374)r+(0.0184a2−1.7325a+59.763), (0.0567a2−2.162a+16.817)r2+(−0.0298a2+1.0456a−15.236)r+(−0.0094a2+0.0329a+14.897), 100−a−x−y),
point Br (0.0, (0.0839a2−3.138a+23.492)r2+(−0.0396a2+1.4292a−21.082)r+(0.0057a2−1.4197a+68.462), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 26.6<a≤35.3, and 0<r≤v, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points;
point J (−0.00542a2+0.3598a+24.08, 100−a−x, 0.0),
point Kr ((−0.2299a+5.7149)(0.1379a−5.069)r+(−0.7011x+45.351), (0.069a−2.4345)r2+(−0.1264a−5.1368)r+(−0.4943a+22.247), 100−a−x−y),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 26.6<a≤35.3, and v<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points;
point J (−0.00542a2+0.3598a+24.08, 0.0, 100−a−x),
point Kr ((−0.3218a+8.1609)r2+(1.4023a−38.701)r+(−1.3103a+61.555), 0.0, 100−a−x),
point Ar ((−0.00946a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.00584a2−1.5915a+74.4), 0.0, 100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br);
if 35.3<a≤43.8, and 0<r≤v, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrBr, BrO, and OJ that connect the following 4 points;
point J (−0.00542a2+0.3598a+24.08, 100−a−x, 0.0),
point Kr ((0.2824a−12.367)r2+(0.0235a−1.0306)r+(−0.5529a+40.119), (1.1294a−49.468)r+(−0.5647a+24.734), 100−a−x−y),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr and KrBr (excluding point J and point Br);
if 35.3<a≤43.8, and v<r≤1, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points;
point J (−0.00542a2+0.3598a+24.08, 100−a−x, 0.0),
point Kr ((0.2588a−12.336)r2+(−0.5294a+29.488)r+(0.0706a+12.808), 0.0, 100−a−x)),
point Ar ((−0.00946a2+0.6769a−13.119)r2+(0.01143a2−0.846a+4.9102)r+(0.00584a2−1.5915a+74.4), 0.0, 100−a−x),
point Br (0.0, (−0.00279a2+0.1483a−2.5871)r2+(0.00277a2−0.1588a−8.822)r+(0.00327a2−1.3169a+67.421), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br); and
if 43.8<a≤47.8, coordinates (x, y, z) in the ternary composition diagram are within the range of a figure surrounded by straight lines JKr, KrAr, ArBr, BrO, and OJ that connect the following 5 points;
point J (−0.1a+33.78, 100−a−x, 0.0),
point Kr (−r2+(−0.2a+15.06)r+15.9, 0.0, 100−a−x),
point Ar (1.6r2+(0.05a−12.39)r+(−1.075a+62.985), 0.0, 100−a−x),
point Br (0.0, (3.8a−167.84)r2+(−3.8a+155.94)r+(−1.025a+60.895), 100−a−y), and
point O (0.0, 100−a, 0.0),
or on the straight lines JKr, KrAr, and ArBr (excluding point J, point Ar, and point Br).
The approximate expressions representing the coordinates of each point were obtained as shown below.
1: Sample cell
2: High-speed camera
3: Xenon lamp
4: Collimating lens
5: Collimating lens
6: Ring filter
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-114158 | Jun 2019 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2020/024215 | Jun 2020 | US |
| Child | 17549392 | US |
