Patent Application
20230174836
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)), trifluoroiodomethane (CF3I), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and difluoromethane (R32).
The refrigerant of the present disclosure has a low GWP.
The present inventors conducted intensive studies to solve the above problem, and consequently found that a mixed refrigerant comprising HFO-1132(E), CF3I, and R1234yf, as well as 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.
The refrigerant of the present disclosure comprises HFO-1132(E), CF3I, R1234yf, and R32.
The refrigerant of the present disclosure is a low-GWP mixed refrigerant.
The refrigerant of the present disclosure preferably satisfies the following requirements. In this case, the refrigerant of the present disclosure has a refrigerating capacity ratio of 75% or more relative to that of R410A.
When the mass % of HFO-1132 (E), CF3I, R1234yf, and R32 based on their sum is respectively represented by x, y, z, and a, provided that 0<a≤29.2,
if 0<a≤7.0, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), CF3I, and R1234yf is (100−a) mass % are within the range of a figure surrounded by straight lines AS, SB, BO, and OA that connect the following 4 points:
point A (−0.0167a2−2.6115a+52.1, 0.0167a2+1.6115a+47.9, 0.0),
point S (0.0042a2−2.2866a+48.3, 0.0023a2+0.8408a+26.0, −0.0065a2+0.4458a+25.7),
point B (0.0088a2−1.8471a+48.5, 0.0, −0.0088a2+0.8471a+51.5), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B);
if 7.0<a≤17.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AS, SB, BO, and OA that connect the following 4 points:
point A (−0.0423a2−2.1749a+50.299, 0.0423a2+1.1749a+49.701, 0.0),
point S (0.007a2−2.3257a+48.437, −0.0029a2+0.9539a+25.465, −0.0041a2+0.3718a+26.098),
point B (0.0129a2−1.857a+48.367, 0.0, −0.0129a2+0.857a+51.633), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B); or
if 17.3<a≤29.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines PA, AS, SB, BO, and OP that connect the following 5 points:
point P (0.0, 100.0−a, 0.0),
point A (0.0, 0.2556a2−17.615a+310.95, −0.2556a2+16.615a−210.95),
point S (0.0034a2−0.8211a+23.493, 0.1285a2−8.8263a+155.32, −0.1319a2+8.6474a−78.813),
point B (0.0113a2-1.8198a+48.199, 0.0, −0.0113a2+0.8198a+51.801), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B).
The refrigerant of the present disclosure more preferably satisfies the following requirements. In this case, the refrigerant of the present disclosure has a refrigerating capacity ratio of 90% or more relative to that of R410A.
Requirements
When the mass % of HFO-1132 (E), CF3I, R1234yf, and R32 based on their sum in the refrigerant is respectively represented by x, y, z, and a, provided that 0<a≤29.2, if 0<a≤17.3, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), CF3I, and R1234yf is (100−a) mass % are within the range of a figure surrounded by straight lines CW, WD, DO, and OC that connect the following 4 points:
point C (−0.0027a2−2.3528a+82.9, 0.0027a2+1.3528a+17.1, 0.0),
point W (0.0045a2−2.2743a+81.5, 0.0033a2+0.7052a+8.9, −0.0078a2+0.5692a+9.6),
point D (0.0151a2−2.1344a+80.8, 0.0. −0.0151a2+1.1344a+19.2), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CW and WD (excluding the points C and D);
if 17.3<a≤33.1, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, and OC that connect the following 4 points:
point C (−0.0136a2−1.9352a+78.947, 0.0136a2+0.9352a+21.053, 0.0),
point W (0.0045a2−2.2651a+81.337, 0.0009a2+0.765a+8.598, −0.0054a2+0.5001a+10.065),
point D (0.0094a2−1.923a+78.855, 0.0. −0.0094a2+0.923a+21.145), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CW and WD (excluding the points C and D);
if 33.1<a≤33.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point W (0.5a−5.25, −5.0a+200.4, 3.5a−95.15),
point D (−1.5a+75.15, 0.0. 0.5a+24.85),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CW and WD (excluding the points C and D); or
if 33.3<a≤51.6, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, OP, and PC that connect the following 5 points:
point C (0.0, 0.0795a2−9.8365a+304.81, −0.0795a2+8.8365a−204.81),
point W (−0.00783a2+0.1576a+14.848, 0.05178a2−6.0017a+176.35, −0.04392a2+4.8441a−91.2),
point D (0.00837a2−1.8518a+77.595, 0.0. −0.00837a2+0.8518a+22.405),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CW and WD (excluding the points C and D).
In the above refrigerant, in terms of preventing disproportionation and in terms of refrigerating capacity, x is preferably 10 wt. % or more and 70 wt. % or less, more preferably 15 wt. % or more and 60 wt. % or less, and even more preferably 17.5 wt. % or more and 50 wt. % or less.
In the above refrigerant, in terms of preventing the deterioration of the refrigeration oil and in terms of low GWP, y is preferably 10 wt. % or more and 60 wt. % or less, more preferably 15 wt. % or more and 50 wt. % or less, and even more preferably 20 wt. % or more and 40 wt. % or less.
In the above refrigerant, in terms of low GWP and refrigerating capacity, a is preferably 2.5 wt. % or more and 29.2 wt. % or less (GWP: 200 or less), more preferably 5.0 wt. % or more and 25.5 wt. % or less (GWP: 175 or less), and even more preferably 7.5 wt. % or more and 21.8 wt. % or less (GWP: 150).
The refrigerant of the present disclosure may further comprise trifluoroethylene (HFO-1123).
When the refrigerant of the present disclosure further comprises HFO-1123, it preferably satisfies the following requirements. In this case, the refrigerant of the present disclosure has a refrigerating capacity ratio of 75% or more relative to that of R410A.
When the total mass % of HFO-1123 and HFO-1132(E) is represented by x, the mass % of CF3I is represented by y, the mass % of R1234yf is represented by z, and the mass % of R32 is represented by a, provided that 0<a≤29.2, based on the sum of HFO-1123, HFO-1132(E), CF3I, R1234yf, and R32, and r=HFO-1123/(HFO-1123+HFO-1132(E)), provided that 0<r<1,
if 0<a≤7.0, coordinates (x,y,z) in a ternary composition diagram having the sum of HFO-1123 and HFO-1132(E) as a first vertex, CF3I as a second vertex, and R1234yf as a third vertex are within the range of a figure surrounded by straight lines ArSr, SrBr, BrO, and OA that connect the following 4 points:
point Ar ((0.0192a2−0.3057a+8.8)r2+(0.0178a2+0.7898a−29.4)r+(−0.0167a2−2.6115a+52.1), (−0.0192a2+0.3057a−8.8)r2−(0.0178a2−+0.7898a−29.4)r+(0.0167a2+1.6115a+47.9), 0.0),
point Sr ((0.022a2−0.4968a+6.6)r2+(−0.0059a2+0.8981a−19.9)r+(0.0042a2−2.2866a+48.3)), (−0.0105a2+0.2166a−3.4)r2+(−0.0123a2−0.414a+13.9)r+(0.0023a2+0.8408a+26.0), (−0.0115a2+0.2803a−3.2)r2+(0.0181a2−0.4841a+6.0) r+(−0.0066a2+0.4459a+25.7)),
point Br ((−0.0021a2−0.3567a+6.2)r2+(0.0013a2+0.6624a−11.7)r+(0.0088a2−1.8471a+48.5), 0.0, (0.0021a2+0.3567a−6.2)r2−(0.0013a2+0.6624a−11.7)r+(−0.0088a2+0.8471a+51.5)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br);
if 7.0<a≤17.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines ArSr, SrBr, BrO, and OA that connect the following 4 points:
point Ar ((−0.0774a2+1.142a+3.3965)r2+(0.1316a2−0.965a−22.694)r+(−0.0423a2−2.1749a+50.299), (0.0774a2−1.142a−3.3965)r2−(0.1316a2−0.965a−22.694)r+(0.0423a2+1.1749a+49.701), 0.0),
point Sr (((0.0219a2−0.901a+10.434)r2+(−0.0265a2+1.7025a−26.018)r+(0.0136a2−2.5337a+50.071), (−0.0157a2+0.4991a−5.1221)r2+(0.012a2−0.9332a+16.343)r+(−0.0029a2+0.9539a+25.465), (0.007a2−0.014a−2.0437)r2+(−0.0052a2−0.1454a+4.7729)r+(−0.0041a2+0.3719a+26.099)),
point Br ((0.0114a2−0.5683a+7.0195)r2+(−0.0183a2+0.9587a−12.815)r+(0.0129a2−1.857a+48.367), 0.0, (−0.0114a2+0.5683a−7.0195)r2+(0.0183a2−0.9587a+12.815)r+(−0.0129a2+0.857a+51.633)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br); or
if 17.3<a≤29.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines PAr, ArSr, SrBr, BrO, and OP that connect the following 5 points:
point P (0.0, 100.0−a, 0.0),
point Ar (0.0, 0.2556a2−17.615a+310.95, −0.2556a2+16.615a−210.95),
point Sr ((0.0141a2−0.7748a+10.574)r2+(−0.036a2+2.0515a−29.22)r+(0.0034a2−0.8211a+23.493), (−0.0104a2+0.5843a−8.1967)r2−(0.0289a2−1.6641a+23.933)r+(0.1285a2−8.8263a+155.32), (−0.0037a2+0.1905a−2.3774)r2+(0.0071a2−0.3874a−5.2871)r+(−0.1319a2+8.6474a−78.814)),
point Br ((−0.0008a2−0.0129a+1.0643)r2+(−0.0077a2+0.5019a−8.0723)r+(0.0113a2−1.8198a+48.199), 0.0, (0.0008a2+0.0129a−1.0643)r2+(0.0077a2−0.5019a+8.0723)r+(−0.0113a2+0.8198a+51.801)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br).
When the refrigerant of the present disclosure further comprises HFO-1123, it more preferably satisfies the following requirements. In this case, the refrigerant of the present disclosure has a refrigerating capacity ratio of 90% or more relative to that of R410A.
When the total mass % of HFO-1123 and HFO-1132(E) is represented by x, the mass % of CF3I is represented by y, the mass % of R1234yf is represented by z, and the mass % of R32 is represented by a, provided that 0<a≤29.2, based on the sum of HFO-1123, HFO-1132(E), CF3I, R1234yf, and R32 in the refrigerant, and r=HFO-1123/(HFO-1123+HFO-1132(E)), provided that 0<r<1,
if 0<a≤17.3, coordinates (x,y,z) in a ternary composition diagram having the sum of HFO-1123 and HFO-1132(E) as a first vertex, CF3I as a second vertex, and R1234yf as a third vertex are within the range of a figure surrounded by straight lines CrWr, WrDr, DrO, and OCr that connect the following 4 points:
point Cr ((−0.0031a2−0.2355a+13.0)r2+(0.0213a2+0.5511a−41.9)r+(−0.0027a2−2.3528a+82.9), (0.0031a2+0.2355a−13.0)r2+(−0.0213a2−0.5511a+41.9)r+(0.0027a2+1.3528a+17.1), 0.0),
point Wr ((0.0184a2−0.7005a+14.2)r2+(−0.009a2+1.0629a−37.3)r+(0.0045a2−2.2743a+81.5), (−0.0536a2+0.6606a−6.0)r2+(0.0421a2−0.7805a+22.2)r+(0.0033a2+0.7052a+8.9), (0.0351a2+0.0399a−8.2)r2+(−0.0331a2−0.2824a+15.1)r+(−0.0078a2+0.5692a+9.6)),
point Dr ((0.0154a2−0.8793a+16.2)r2+(−0.0191a2+1.3765a−30.1)r+(0.0151a2−2.1344a+80.8), 0.0. (−0.0154a2+0.8793a−16.2)r2+(0.0191a2−1.3765a+30.1)r+(−0.01529a2+1.1344a+19.2)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CrWr and WrDr (excluding the points Cr and Dr);
if 17.3<a≤33.1, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CrWr, WrDr, DrO, and OCr that connect the following 4 points:
point Cr ((−0.01728a2+0.3644a+6.8668)r2+(0.0335a2−0.0444a−35.267)r+(−0.0136a2−1.9352a+78.947), (0.01728a2−0.3644a−6.8668)r2+(−0.0335a2+0.0444a+35.267)r+(0.0136a2+0.9352a+21.053), 0.0),
point Wr ((0.02317a2−1.5719a+27.864)r2+(−0.0219a2+2.1686a−52.553)r+(0.0045a2−2.2651a+81.337), (−0.0963a2+5.4972a−76.891)r2+(0.0922a2−5.8047a+94.129)r+(0.0009a2+0.765a+8.598), (0.07312a2−3.9253a+49.027)r2+(−0.0703a2+3.6361a−41.576)r+(−0.0054a2+0.5001a+10.065)),
point Dr ((0.01078a2−0.8205a+16.576)r+(−0.0156a2+1.3436a−30.573)r+(0.0094a2−1.923a+78.855), 0.0. (−0.01078a2+0.8205a−16.576) r2+(0.0156a2−1.3436a+30.573)r+(−0.0094a2+0.923a+21.145)), and
point O (100.0−a, 0.0, 0.0), or on the straight lines CrWr and WrDr (excluding the points Cr and Dr);
if 33.1<a≤33.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CWr, WrDr, DrO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point Wr ((6.0a−197.4)r2+(−6.0a+193.8)r+(0.5a−5.25), (−20.0a+661.6)r2+(20.0a−659.0)r+(−5.0a+200.4), (14.0a−464.2)r2+(−14.0a+465.2)r+(3.5a−95.15)),
point Dr ((−a+34.3)r2+(1.5a−52.85)r+(−1.5a+75.15), 0.0, (a−34.3)r2+(−1.5a+52.85)r+(0.5a+24.85)),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CWr and WrDr (excluding the points C and Dr); or
if 33.3<a≤51.6, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CWr, WrDr, DrO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point Wr (0.0073a2−0.7541a+19.376)r2+(−0.0183a2+1.8853a−48.44)r+(−0.00784a2+0.1576a+14.848), (−0.02246a2+2.1482a−51.018)r2+(0.03082−3.0a+72.712)r+(0.05178a2−6.0017a+176.35), (0.01513a2−1.3941a+31.642)r2+(−0.0125a2+1.1146a−24.273)r+(−0.04392a2+4.8441a−91.2)),
point Dr ((0.0002a2−0.0706a+3.143)r2+(−0.005a2+0.5806a−16.671)r+(0.00836a2−1.8518a+77.595), 0.0, (−0.0002a2+0.0706a−3.143)r2+(0.005a2−0.5806a+16.671)r+(−0.00836a2+0.8518a+22.405)),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CWr and WrDr (excluding the points C and Dr).
In the above refrigerant, in terms of preventing disproportionation, x is preferably 70 wt. % or less, more preferably 60 wt. % or less, and even more preferably 50 wt. % or less.
In the above refrigerant, in terms of refrigerating capacity, x is preferably 10 wt. % or more, more preferably 15 wt. % or more, and even more preferably 17.5 wt. % or more.
In the above refrigerant, in terms of preventing the deterioration of the refrigeration oil, y is preferably 60 wt. % or less, more preferably 50 wt. % or less, and even more preferably 40 wt. % or less.
In the above refrigerant, in terms of low GWP, y is preferably 10 wt. % or more, more preferably 15 wt. % or more, and even more preferably 20 wt. % or more.
In the above refrigerant, in terms of low GWP, a is preferably 29.2 wt. % or less (GWP: 200 or less), more preferably 25.5 wt. % or less (GWP: 175), and even more preferably 21.8 wt. % or less (GWP: 150).
In the above refrigerant, in terms of refrigerating capacity, x is preferably 2.5 wt. % or more, more preferably 5.0 wt. % or more, and even more preferably 7.5 wt. % or more.
The refrigerant of the present disclosure may further comprise other additional refrigerants in addition to HFO-1132(E), CF3I, R1234yf, and R32, as long as the above properties and effects are not impaired. In this respect, in an embodiment, the refrigerant of the present disclosure preferably comprises HFO-1132(E), CF3I, R1234yf, and R32 in a total amount of 99.5 mass % or more, more preferably 99.75 mass % or more, even more preferably 99.9 mass; or more, still even more preferably 99.99 mass % or more, and most preferably 99.999 mass % or more, based on the entire refrigerant. In another embodiment, the refrigerant of the present disclosure preferably comprises HFO-1123, HFO-1132(E), CF3I, and R1234yf in a total amount of 99.5 mass, or more, more preferably 99.75 mass % or more, even more preferably 99.9 mass % or more, still even more 99.99 mass % or more, and most preferably 99.999 mass % or more, based on the entire refrigerant. Further, the refrigerant of the present disclosure may essentially consist of HFO-1132(E), CF3I, R1234yf, and R32, or may consist of HFO-1132(E), CF3T, R1234yf, and R32. When the refrigerant of the present disclosure essentially consists of HFO-1132 (E), CF3I, R1234yf, and R32, it may further contain, in addition to these compounds, only impurities inevitably mixed in the production process of these compounds.
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 the tracer.
FC-14 (tetrafluoromethane, CF4)
HCC-40 (chloromethane, CH3Cl)
HFC-23 (trifluoromethane, CHF3)
HFC-41 (fluoromethane, CH3Cl)
HFC-125 (pentafluoroethane, CF3CHF2)
HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)
HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)
HFC-143a (1,1,1-trifluoroethane, CF3CH3)
HFC-143 (1,1,2-trifluoroethane, CHF2CH2F)
HFC-152a (1,1-difluoroethane, CHF2CHF)
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 (trifluoromethyl-fluoromethyl ether, CF3OCH2F)
HFE-143a (trifluoromethyl-methyl ether, CF3OCH3)
HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3)
HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3)
The refrigerant composition of the present disclosure may contain the tracer in a total amount of about 10 parts per million by weight (ppm) to about 1000 ppm based on the entire refrigerant composition. The refrigerant composition of the present disclosure may contain the tracer in a total amount of preferably about 30 ppm to about 500 ppm, and more preferably about 50 ppm to about 300 ppm, based on the entire refrigerant composition.
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-pentafluoropropylamine and diphenylamine.
Examples of stabilizers also include butylhydroxyxylene and benzotriazole.
The content of the stabilizer is not limited. Generally, the content of the stabilizer is preferably 0.01 to 5 mass %, and more preferably 0.05 to 2 mass %, based on the entire refrigerant.
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)), trifluoroiodomethane (CF3I), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and difluoromethane (R32).
Item 2.
The composition according to Item 1, wherein
when the mass % of HFO-1132 (E), CF3I, R1234yf, and R32 based on their sum in the refrigerant is respectively represented by x, y, z, and a, provided that 0<a≤29.2,
if 0<a≤7.0, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), CF3I, and R1234yf is (100−a) mass % are within the range of a figure surrounded by straight lines AS, SB, BO, and OA that connect the following 4 points:
point A (−0.0167a2−2.6115a+52.1, 0.0167a2+1.6115a+47.9, 0.0),
point S (0.0042a2−2.2866a+48.3, 0.0023a2+0.8408a+26.0, −0.0065a2+0.4458a+25.7),
point B (0.0088a2−1.8471a+48.5, 0.0, −0.0088a2+0.8471a+51.5), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B);
if 7.0<a≤17.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AS, SB, BO, and OA that connect the following 4 points:
point A (−0.0423a2−2.1749a+50.299, 0.0423a2+1.1749a+49.701, 0.0),
point S (0.007a2−2.3257a+48.437, −0.0029a2+0.9539a+25.465, −0.0041a2+0.3718a+26.098),
point B (0.0129a2−1.857a+48.367, 0.0, −0.0129a2+0.857a+51.633), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B); or
if 17.3<a≤29.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines PA, AS, SB, BO, and OP that connect the following 5 points:
point P (0.0, 100.0−a, 0.0),
point A (0.0, 0.2556a2−17.615a+310.95, −0.2556a2+16.615a−210.95),
point S (0.0034a2−0.8211a+23.493, 0.1285a2−8.8263a+155.32, −0.1319a2+8.6474a−78.813),
point B (0.0113a2−1.8198a+48.199, 0.0, −0.0113a2+0.8198a+51.801), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B).
Item 3.
The composition according to Item 1,
wherein
when the mass % of HFO-1132(E), CF3I, R1234yf, and R32 based on their sum in the refrigerant is respectively represented by x, y, z, and a, provided that 0<a≤29.2,
if 0<a≤17.3, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), CF3I, and R1234yf is (100−a) mass % are within the range of a figure surrounded by straight lines CW, WD, DO, and OC that connect the following 4 points:
point C (−0.0027a2−2.3528a+82.9, 0.0027a2+1.3528a+17.1, 0.0),
point W (0.0045a2−2.2743a+81.5, 0.0033a2+0.7052a+8.9, −0.0078a2+0.5692a−9.6),
point D (0.0151a2−2.1344a+80.8, 0.0. −0.0151a2+1.1344a+19.2), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CW and WD (excluding the points C and D);
if 17.3<a≤33.1, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, and OC that connect the following 4 points:
point C (−0.0136a2−1.9352a+78.947, 0.0136a2+0.9352a+21.053, 0.0),
point W (0.0045a2−2.2651a+81.337, 0.0009a2+0.765a+8.598, −0.0054a2+0.5001a+10.065),
point D (0.0094a2−1.923a+78.855, 0.0. −0.0094a2+0.923a+21.145), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CW and WD (excluding the points C and D);
if 33.1<a≤33.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point W (0.5a−5.25, −5.0a+200.4, 3.5a−95.15),
point D (−1.5a+75.15, 0.0. 0.5a+24.85),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CW and WD (excluding the points C and D); or
if 33.3<a≤51.6, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, OP, and PC that connect the following 5 points:
point C (0.0, 0.0795a2−9.8365a+304.81, −0.0795a2+8.8365a−204.81),
point W (−0.00783a2+0.1576a+14.848, 0.05178a2−6.0017a+176.35, −0.04392a2+4.8441a−91.2),
point D (0.00837a2−1.8518a+77.595, 0.0. −0.00837a2+0.8518a+22.405),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CW and WD (excluding the points C and D).
Item 4.
The composition according to any one of Items 1 to 3, wherein the refrigerant further comprises trifluoroethylene (HFO-1123).
Item 5.
The composition according to Item 4,
wherein
when the total mass; of HFO-1123 and HFO-1132(E) is represented by x, the mass % of CF3I is represented by y, the mass % of R1234yf is represented by z, and the mass % of R32 is represented by a, provided that 0<a≤29.2, based on the sum of HFO-1123, HFO-1132(E), CF3I, R1234yf, and R32 in the refrigerant, and r=HFO-1123/(HFO-1123+HFO-1132(E)), provided that 0<r<1,
if 0<a≤7.0, coordinates (x,y,z) in a ternary composition diagram having the sum of HFO-1123 and HFO-1132(E) as a first vertex, CF3I as a second vertex, and R1234yf as a third vertex are within the range of a figure surrounded by straight lines ArSr, SrBr, BrO, and OA that connect the following 4 points:
point Ar ((0.0192a2−0.3057a+8.8)r2+(0.0178a2+0.7898a−29.4)r+(−0.0167a2−2.6115a−52.1), (−0.0192a2+0.3057a−8.8)r2−(0.0178a2+0.7898a−29.4)r+(0.0167a2+1.6115a+47.9), 0.0),
point Sr ((0.022a2−0.4968a+6.6)r2+(−0.0059a2+0.8981a−19.9)r+(0.0042a2−2.2866a+48.3)), (−0.0105a2+0.2166a−3.4)r2+(−0.0123a2−0.414a+13.9)r+(0.0023a2+0.8408a+26.0), (−0.0115a2+0.2803a−3.2)r2+(0.0181a2−0.4841a+6.0)r+(−0.0066a2+0.4459a+25.7)),
point Br ((−0.0021a2−0.3567a+6.2)r2+(0.0013a2+0.6624a−11.7)r+(0.0088a2−1.8471a+48.5), 0.0, (0.0021a2+0.3567a−6.2)r2−(0.0013a2+0.6624a−11.7)r+(−0.0088a2+0.8471a+51.5)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br);
if 7.0<a≤17.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines ArSr, SrBr, BrO, and OA that connect the following 4 points:
point Ar ((−0.0774a2+1.142a+3.3965)r2+(0.1316a2−0.965a−22.694)r+(−0.0423a2−2.1749a−50.299), (0.0774a2−1.142a−3.3965)r2−(0.1316a2−0.965a−22.694)r+(0.0423a2+1.1749a+49.701), 0.0),
point Sr ((0.0219a2−0.901a+10.434)r2+(−0.0265a2+1.7025a−26.018)r+(0.0136a2−2.5337a+50.071), (−0.0157a2+0.4991a−5.1221)r2+(0.012a2−0.9332a+16.343)r+(−0.0029a2+0.9539a+25.465), (0.007a2−0.014a−2.0437)r2+(−0.0052a2−0.1454a+4.7729)r+(−0.0041a2+0.3719a+26.099)),
point Br ((0.0114a2−0.5683a+7.0195)r2+(−0.0183a2+0.9587a−12.815)r+(0.0129a2−1.857a+48.367), 0.0, (−0.0114a2+0.5683a−7.0195)r2−(0.0183a2−0.9587a+12.815)r+(−0.0129a2+0.857a+51.633)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br); or
if 17.3<a≤29.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines PAr, ArSr, SrBr, BrO, and OP that connect the following 5 points:
point P (0.0, 100.0−a, 0.0),
point Ar (0.0, 0.2556a2−17.615a+310.95, −0.2556a2+16.615a−210.95),
point Sr ((0.0141a2−0.7748a+10.574)r2+(−0.036a2+2.0515a−29.22)r+(0.0034a2−0.8211a+23.493), (−0.0104a2+0.5843a−8.1967)r2+(0.0289a2−1.6641a+23.933)r+(0.1285a2−8.8263a+155.32), (−0.0037a2+0.1905a−2.3774)r2+(0.0071a2−0.3874a+5.2871)r+(−0.1319a2+8.6474a−78.814)),
point Br ((−0.0008a2−0.0129a+1.0643)r2+(−0.0077a2+0.5019a−8.0723)r+(0.0113a2−1.8198a+48.199), 0.0, (0.0008a2+−0.0129a−1.0643)r2+(0.0077a2−0.5019a+8.0723)r+(−0.0113a2+0.8198a+51.801)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br).
Item 6.
The composition according to Item 4,
wherein
when the total mass' of HFO-1123 and HFO-1132(E) is represented by x, the mass % of CF3I is represented by y, the mass % of R1234yf is represented by z, and the mass % of R32 is represented by a, provided that 0<a≤29.2, based on the sum of HFO-1123, HFO-1132(E), CF3I, R1234yf, and R32 in the refrigerant, and r=HFO-1123/(HFO-1123+HFO-1132(E)), provided that 0<r<1,
if 0<a≤17.3, coordinates (x,y,z) in a ternary composition diagram having the sum of HFO-1123 and HFO-1132(E) as a first vertex, CF3I as a second vertex, and R1234yf as a third vertex are within the range of a figure surrounded by straight lines CrWr, WrDr, DrO, and OCr that connect the following 4 points:
point Cr ((−0.0031a2−0.2355a+13.0)r2+(0.0213a2+0.5511a−41.9)r+(−0.0027a2−2.3528a+82.9), (0.0031a2+0.2355a−13.0)r2+(−0.0213a2−0.5511a+41.9)r+(0.0027a2+1.3528a+17.1), 0.0),
point Wr ((0.0184a2−0.7005a+14.2)r2+(−0.009a2+1.0629a−37.3)r+(0.0045a2−2.2743a+81.5), (−0.0536a2+0.6606a−6.0) r2+(0.0421a2−0.7805a+22.2)r+(0.0033a2+0.7052a+8.9), (0.0351a2+0.0399a−8.2)r2+(−0.0331a2−0.2824a+15.1)r+(−0.0078a2+0.5692a+9.6)),
point Dr ((0.0154a2−0.8793a+16.2)r2+(−0.0191a2+1.3765a−30.1)r+(0.0151a2−2.1344a+80.8), 0.0. (−0.0154a2+0.8793a−16.2)r2+(0.0191a2−1.3765a+30.1)r+(−0.01529a2−+1.1344a+19.2)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CrWr and WrDr (excluding the points Cr and Dr);
if 17.3<a≤33.1, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CrWr, WrDr, DrO, and OCr that connect the following 4 points:
point Cr ((−0.01728a2−+0.3644a+6.8668)r2+(0.0335a2−0.0444a−35.267)r+(−0.0136a2−1.9352a+78.947), (0.01728a2−0.3644a−6.8668)r2+(−0.0335a2+0.0444a+35.267)r+(0.0136a2+0.9352a+21.053), 0.0),
point Wr ((0.02317a2−1.5719a+27.864)r2+(−0.0219a2+2.1686a−52.553)r+(0.0045a2−2.2651a+81.337), (−0.0963a2+5.4972a−76.891)r2+(0.0922a2−5.8047a+94.129)r+(0.0009a2+0.765a+8.598), (0.07312a2−3.9253a+49.027)r2+(−0.0703a2+3.6361a−41.576)r+(−0.0054a2+0.5001a+10.065)),
point Dr ((0.01078a2−0.8205a+16.576)r2+(−0.0156a2+1.3436a−30.573)r+(0.0094a2−1.923a+78.855), 0.0. (−0.01078a2+0.8205a−16.576)r2+(0.0156a2−1.3436a+30.573)r+(−0.0094a2+0.923a+21.145)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CrWr and WrDr (excluding the points Cr and Dr);
if 33.1<a≤33.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CWr, WrDr, DrO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point Wr ((6.0a−197.4)r2+(−6.0a+193.8)r+(0.5a−5.25), (−20.0a+661.6)r2+(20.0a−659.0)r+(−5.0a+200.4), (14.0a−464.2)r2+(−14.0a+465.2)r+(3.5a−95.15)),
point Dr ((−a+34.3)r2+(1.5a−52.85)r+(−1.5a+75.15), 0.0, (a−34.3)r2+(−1.5a+52.85)r+(0.5a+24.85)),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CWr and WrDr (excluding the points C and Dr); or
if 33.3<a≤51.6, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CWr, WrDr, DrO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point Wr (0.0073a2−0.7541a+19.376)r2+(−0.0183a2+1.8853a−48.44)r+(−0.00784a2+0.1576a+14.848), (−0.02246a2+2.1482a−51.018)r2+(0.03082−3.0a+72.712)r+(0.05178a2−6.0017a+176.35), (0.01513a2−1.3941a+31.642)r2+(−0.0125a2+1.1146a−24.273)r+(−0.04392a2+4.8441a−91.2)),
point Dr ((0.0002a2−0.0706a+3.143)r2+(−0.005a2+(0.5806a−16.671)r+(0.00836a2−1.8518a−77.595), 0.0, (−0.0002a2+0.0706a−3.143)r2+(0.005a2−0.5806a+16.671)r+(−0.00836a2+0.8518a+22.405)),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CWr and WrDr (excluding the points C and Dr).
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 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), CF3I, R1234yf, and R32 at mass % shown in Table 1 based on their sum.
The GWP of R410A (R32=50%/R125=50%) and the above mixed refrigerants 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 R410A and the above mixed refrigerants 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.
For each of these mixed refrigerants, the COP ratio and refrigerating capacity ratio relative to those of R410A were determined. The calculation conditions were as follows:
Evaporating temperature: 5° C.
Condensation temperature: 45° C.
Superheating temperature: 5 K
Subcooling temperature: 5 K
Compressor efficiency: 70%
Table 1 shows these values together with the GWP of each mixed refrigerant. The COP and refrigerating capacity are ratios relative to R410A.
The coefficient of performance (COP) was determined by the following formula.
COP=(refrigerating capacity or heating capacity)/power consumption
Approximate expressions indicating the coordinates of each point were obtained by determining approximate expressions for the curves connecting three points, as shown in Tables 2 and 3.
These results demonstrate that the mixed refrigerants have a refrigerating capacity ratio of 75% or more relative to that of R410A when they satisfy the following requirements.
When the mass % of HFO-1132 (E), CF3I, R1234yf, and R32 based on their sum in the refrigerant is respectively represented by x, y, z, and a, provided that 0<a≤29.2,
if 0<a≤7.0, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), CF3I, and R1234yf is (100−a) mass % are within the range of a figure surrounded by straight lines AS, SB, BO, and OA that connect the following 4 points:
point A (−0.0167a2−2.6115a+52.1, 0.0167a2+1.6115a+47.9, 0.0),
point S (0.0042a2−2.2866a+48.3, 0.0023a2+0.8408a+26.0, −0.0065a2+0.4458a+25.7),
point B (0.0088a2−1.8471a+48.5, 0.0, −0.0088a2+0.8471a+51.5), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B);
if 7.0<a≤17.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines AS, SB, BO, and OA that connect the following 4 points:
point A (−0.0423a2−2.1749a+50.299, 0.0423a2+1.1749a+49.701, 0.0),
point S (0.007a2−2.3257a+48.437, −0.0029a2+0.9539a+25.465, −0.0041a2+0.3718a+26.098),
point B (0.0129a2−1.857a+48.367, 0.0, −0.0129a2+0.857a+51.633), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B); or
if 17.3<a≤29.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines PA, AS, SB, BO, and OP that connect the following 5 points:
point P (0.0, 100.0−a, 0.0),
point A (0.0, 0.2556a2−17.615a+310.95, −0.2556a2+16.615a−210.95),
point S (0.0034a2−0.8211a+23.493, 0.1285a2−8.8263a+155.32, −0.1319a2+8.6474a−78.813),
point B (0.0113a2−1.8198a+48.199, 0.0, −0.0113a2+0.8198a+51.801), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines AS and SB (excluding the points A and B).
These results demonstrate that the mixed refrigerants have a refrigerating capacity ratio of 90% or more relative to that of R410A when they satisfy the following requirements.
When the mass % of HFO-1132 (E), CF3I, R1234yf, and R32 based on their sum in the refrigerant is respectively represented by x, y, z, and a, provided that 0<a≤29.2,
if 0<a≤17.3, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), CF3I, and R1234yf is (100−a) mass % are within the range of a figure surrounded by straight lines CW, WD, DO, and OC that connect the following 4 points:
point C (−0.0027a2−2.3528a+82.9, 0.0027a2+1.3528a+17.1, 0.0),
point W (0.0045a2−2.2743a+81.5, 0.0033a2+0.7052a+8.9, −0.0078a2+0.5692a+9.6),
point D (0.0151a2−2.1344a+80.8, 0.0. −0.0151a2+1.1344a+19.2), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CW and WD (excluding the points C and D);
if 17.3<a≤33.1, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, and OC that connect the following 4 points:
point C (−0.0136a2−1.9352a+78.947, 0.0136a2+0.9352a+21.053, 0.0),
point W (0.0045a2−2.2651a+81.337, 0.0009a2+0.765a+8.598, −0.0054a2+0.5001a+10.065),
point D (0.0094a2−1.923a+78.855, 0.0. −0.0094a2+0.923a+21.145), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CW and WD (excluding the points C and D);
if 33.1<a≤33.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point W (0.5a−5.25, −5.0a+200.4, 3.5a−95.15),
point D (−1.5a+75.15, 0.0. 0.5a+24.85),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CW and WD (excluding the points C and D); or
if 33.3<a≤51.6, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CW, WD, DO, OP, and PC that connect the following 5 points:
point C (0.0, 0.0795a2−9.8365a+304.81, −0.0795a2+8.8365a−204.81),
point W (−0.00783a2+0.1576a+14.848, 0.05178a2−6.0017a+176.35, −0.04392a2−+4.8441a−91.2),
point D (0.00837a2−1.8518a+77.595, 0.0. −0.00837a2+0.8518a+22.405),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CW and WD (excluding the points C and D).
Mixed refrigerants further comprising HFO-1123 in addition to HFO-1132(E), CF3I, R1234yf, and R32 were evaluated in the same manner as described above. Table 4 shows the results.
indicates data missing or illegible when filed
Approximate expressions indicating the coordinates of each point were obtained by determining approximate expressions for the curves connecting three points, as shown in Tables 5 to 7.
The mixed refrigerants further comprising HFO-1123 in addition to HFO-1132 (E), CF3I, R1234yf, and R32 have a refrigerating capacity ratio of 75′, or more relative to that of R410A, because they satisfy the following requirements.
When the total mass % of HFO-1123 and HFO-1132(E) is represented by x, the mass % of CF3I is represented by y, the mass % of R1234yf is represented by z, and the mass % of R32 is represented by a, provided that 0<a≤29.2, based on the sum of HFO-1123, HFO-1132 (E), CF3I, R1234yf, and R32 in the refrigerant, and r=HFO-1123/(HFO-1123+HFO-1132 (E)), provided that 0<r<1,
if 0<a≤7.0, coordinates (x,y,z) in a ternary composition diagram having the sum of HFO-1123 and HFO-1132(E) as a first vertex, CF3I as a second vertex, and R1234yf as a third vertex are within the range of a figure surrounded by straight lines ArSr, SrBr, BrO, and OA that connect the following 4 points:
point Ar ((0.0192a2−0.3057a+8.8)r2+(0.0178a2+0.7898a−29.4)r+(−0.0167a2−2.6115a+52.1), (−0.0192a2+0.3057a−8.8)r2−(0.0178a2+0.7898a−29.4)r+(0.0167a2+1.6115a+47.9), 0.0),
point Sr ((0.022a2−0.4968a+6.6)r2+(−0.0059a2+0.8981a−19.9)r+(0.0042a2−2.2866a+48.3)), (−0.0105a2+0.2166a−3.4)r2+(−0.0123a2−0.414a+13.9)r+(0.0023a2+0.8408a+26.0), (−0.0115a2+0.2803a−3.2)r2+(0.0181a2−0.4841a+6.0)r+(−0.0066a2+0.4459a+25.7)),
point Br ((−0.0021a2−0.3567a+6.2)r2+(0.0013a2+0.6624a−11.7)r+(0.0088a2−1.8471a+48.5), 0.0, (0.0021a2+0.3567a−6.2)r2−(0.0013a2−+0.6624a−11.7)r+(−0.0088a2+0.8471a+51.5)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br);
if 7.0<a≤17.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines ArSr, SrBr, BrO, and OA that connect the following 4 points:
point Ar ((−0.0774a2+1.142a+3.3965)r2+(0.1316a2-0.965a−22.694)r+(−0.0423a2−2.1749a+50.299), (0.0774a2−1.142a−3.3965)r2−(0.1316a2-0.965a−22.694)r+(0.0423a2+1.1749a+49.701), 0.0),
point Sr ((0.0219a2−0.901a+10.434)r2+(−0.0265a2+1.7025a−26.018)r+(0.0136a2−2.5337a+50.071), (−0.0157a2+0.4991a−5.1221)r2+(0.012a2−0.9332a+16.343)r+(−0.0029a2+0.9539a+25.465), (0.007a2−0.014a−2.0437)r2+(−0.0052a2−0.1454a+4.7729)r+(−0.0041a2+0.3719a+26.099)),
point Br ((0.0114a2−0.5683a+7.0195)r2+(−0.0183a2+0.9587a−12.815)r+(0.0129a2−1.857a+48.367), 0.0, (−0.0114a2+0.5683a−7.0195)r2+(0.0183a2−0.9587a+12.815)r+(−0.0129a2+0.857a+51.633)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br); or
if 17.3<a≤29.2, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines PAr, ArSr, SrBr, BrO, and OP that connect the following 5 points:
point P (0.0, 100.0−a, 0.0),
point Ar (0.0, 0.2556a2−17.615a+310.95, −0.2556a2+16.615a−210.95),
point Sr ((0.0141a2−0.7748a+10.574)r2+(−0.036a2+2.0515a−29.22)r+(0.0034a2−0.8211a+23.493), (−0.0104a2+0.5843a−8.1967)r2+(0.0289a2−1.6641a+23.933)r+(0.1285a2−8.8263a+155.32), (−0.0037a2+0.1905a−2.3774)r2+(0.0071a2−0.3874a+5.2871)r+(−0.1319a2+8.6474a−78.814)),
point Br ((−0.0008a2−0.0129a+1.0643)r2+(−0.0077a2+0.5019a−8.0723)r+(0.0113a2−1.8198a+48.199), 0.0, (0.0008a2+0.0129a−1.0643)r2+(0.0077a2−0.5019a+8.0723)r+(−0.0113a2+0.8198a+51.801)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines ArSr and SrBr (excluding the points Ar and Br).
The mixed refrigerants further comprising HFO-1123 in addition to HFO-1132(E), CF3I, R1234yf, and R32 have a refrigerating capacity ratio of 90% or more relative to that of R410A, because they satisfy the following requirements.
When the total mass % of HFO-1123 and HFO-1132(E) is represented by x, the mass % of CF3I is represented by y, the mass % of R1234yf is represented by z, and the mass % of R32 is represented by a, provided that 0<a≤29.2, based on the sum of HFO-1123, HFO-1132 (E), CF3I, R1234yf, and R32 in the refrigerant, and r=HFO-1123/(HFO-1123+HFO-1132(E)), provided that 0<r<1,
if 0<a≤17.3, coordinates (x,y,z) in a ternary composition diagram having the sum of HFO-1123 and HFO-1132(E) as a first vertex, CF3I as a second vertex, and R1234yf as a third vertex are within the range of a figure surrounded by straight lines CrWr, WrDr, DrO, and OCr that connect the following 4 points:
point Cr ((−0.0031a2−0.2355a+13.0)r2+(0.0213a2+0.5511a−41.9)r+(−0.0027a2−2.3528a+82.9), (0.0031a2+0.2355a−13.0)r2+(−0.0213a2−0.5511a+41.9)r+(0.0027a2+1.3528a+17.1), 0.0),
point Wr (((0.0184a2−0.7005a+14.2)r2+(−0.009a2+1.0629a−37.3)r+(0.0045a2−2.2743a+81.5), (−0.0536a2+0.6606a−6.0)r2+(0.0421a2−0.7805a+22.2)r+(0.0033a2+0.7052a+8.9), (0.0351a2+0.0399a−8.2)r2+(−0.0331a2−0.2824a+15.1)r+(−0.0078a2+0.5692a+9.6)),
point Dr ((0.0154a2−0.8793a+16.2)r2+(−0.0191a2+1.3765a−30.1)r+(0.0151a2−2.1344a+80.8), 0.0. (−0.0154a2+0.8793a−16.2)r2+(0.0191a2−1.3765a+30.1)r+(−0.01529a2+1.1344a+19.2)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CrWr and WrDr (excluding the points Cr and Dr);
if 17.3<a≤33.1, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CrWr, WrDr, DrO, and OCr that connect the following 4 points:
point Cr((−0.01728a2+0.3644a+6.8668)r2+(0.0335a2−0.0444a−35.267)r+(−0.0136a2−1.9352a−78.947), (0.01728a2−0.3644a−6.8668)r2+(−0.0335a2+0.0444a+35.267)r+(0.0136a2+0.9352a+21.053), 0.0),
point Wr (((0.02317a2−1.5719a+27.864)r2+(−0.0219a2+2.1686a−52.553)r+(0.0045a2−2.2651a+81.337), (−0.0963a2+5.4972a−76.891)r2+(0.0922a2−5.8047a+94.129)r+(0.0009a2−+0.765a+8.598), (0.07312a2−3.9253a+49.027)r2+(−0.0703a2+3.6361a−41.576)r+(−0.0054a2+0.5001a+10.065)),
point Dr ((0.01078a2−0.8205a+16.576)r2+(−0.0156a2+1.3436a−30.573)r+(0.0094a2−1.923a+78.855), 0.0. (−0.01078a2+0.8205a−16.576)r2+(0.0156a2−1.3436a+30.573)r+(−0.0094a2+0.923a+21.145)), and
point O (100.0−a, 0.0, 0.0),
or on the straight lines CrWr and WrDr (excluding the points Cr and Dr);
if 33.1<a≤33.3, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CWr, WrDr, DrO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point Wr ((6.0a−197.4)r2+(−6.0a+193.8)r+(0.5a−5.25), (−20.0a+661.6)r2+(20.0a−659.0)r+(−5.0a+200.4), (14.0a−464.2)r2+(−14.0a+465.2)r+(3.5a−95.15)),
point Dr ((−a+34.3)r2+(1.5a−52.85)r+(−1.5a+75.15), 0.0, (a−34.3)r2+(−1.5a+52.85)r+(0.5a+24.85)),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)), or on the straight lines CWr and WrDr (excluding the points C and Dr); or
if 33.3<a≤51.6, coordinates (x,y,z) in the ternary composition diagram are within the range of a figure surrounded by straight lines CWr, WrDr, DrO, OP, and PC that connect the following 5 points:
point C (0.0, −7.5a+315.15.053, 6.5a−215.15),
point Wr (0.0073a2−0.7541a+19.376)r2+(−0.0183a2+1.8853a−48.44)r+(−0.00784a2+0.1576a+14.848), (−0.02246a2+2.1482a−51.018)r2+(0.03082−3.0a+72.712)r+(0.05178a2−6.0017a+176.35), (0.01513a2−1.3941a+31.642)r2+((−0.0125a2+1.1146a−24.273)r+(−0.04392a2+4.8441a−91.2)),
point Dr ((0.0002a2−0.0706a+3.143)r2+(−0.005a2+0.5806a−16.671)r+(0.00836a2−1.8518a+77.595), 0.0, (−0.0002a2+0.0706a−3.143)r2+(0.005a2−0.5806a+16.671)r+(−0.00836a2+0.8518a+22.405)),
point O (100.0−a, 0.0, 0.0), and
point P (0.0, 100.0, 0.0)),
or on the straight lines CWr and WrDr (excluding the points C and Dr).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-131982 | Aug 2020 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2021/028835 | Aug 2021 | US |
| Child | 18102324 | US |
