Patent Application
20220380649
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).
The present inventors performed independent examination, and conceived of the idea that no prior art had developed refrigerant compositions having two types of performance, i.e., a coefficient of performance (COP) that is equivalent to that of R410A and a sufficiently low GWP. An object of the present disclosure is to solve this unique problem.
A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and difluoromethane (R32), wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments IK, KB′, B′H, HR, RG, and GI that connect the following 6 points:
the line segment IK is represented by coordinates (0.025z2−1.7429 z+72.00, −0.025z2+0.7429z+28.0, z),
the line segment HR is represented by coordinates (−0.6198z2+9.8223z−16.772, 0.6198z2−10.8223 z+116.772, z),
the line segment RG is represented by coordinates (−0.072z2−1.1998 z+38.5, 0.072z2+0.1998z+61.5, z), and
the line segments KB′, B′H and GI are straight lines.
A composition comprising a refrigerant, the refrigerant comprising HFO-1132 (E), HFO-1123, and R32, wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments IJ, JR, RG, and GI that connect the following 4 points:
the line segment IJ is represented by coordinates (0.025z2−1.7429z+72.0, −0.025z2+0.7429z+28.0, z),
the line segment RG is represented by coordinates (−0.072z2−1.1998z+38.5, 0.072z2+0.1998z+61.5, z), and
the line segments JR and GI are straight lines.
A composition comprising a refrigerant, the refrigerant comprising HFO-1132 (E), HFO-1123, and R32, wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments MP, PB′, B′H, HR, RG, and GM that connect the following 6 points:
the line segment MP is represented by coordinates (0.0083z2−0.984z+47.1, −0.0083z2−0.016z+52.9, z),
the line segment HR is represented by coordinates (−0.6198z2+9.8223z−16.772, 0.6198z2−10.8223z+116.772, z),
the line segment RG is represented by coordinates (−0.072z2−1.1998z+38.5, 0.072z2+0.1998z+61.5, z), and
the line segments PB′, B′H and GM are straight lines.
A composition comprising a refrigerant, the refrigerant comprising HFO-1132 (E), HFO-1123, and R32, wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments MN, NR, RG, and GM that connect the following 4 points:
the line segment MN is represented by coordinates (0.0083z2−0.984 z+47.1, −0.0083z2−0.016z+52.9, z),
the line segment RG is represented by coordinates (−0.072z2−1.1998z+38.5, 0.072z2+0.1998z+61.5, z), and
the line segments NR and GM are straight lines.
A composition comprising a refrigerant, the refrigerant comprising HFO-1132 (E), HFO-1123, and R32, wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments PS, ST, and TP that connect the following 3 points:
the line segment ST is represented by coordinates (−0.0632z2−0.2026z+50.03, 0.0632z2−0.7974z+49.97, z),
the line segment TP is represented by coordinates (0.0083z2−0.984z+47.1, −0.0083z2−0.016z+52.9, z), and
the line segment PS is a straight line.
A composition comprising a refrigerant, the refrigerant comprising HFO-1132 (E), HFO-1123, and R32, wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments C′L, LB″, B″D, DU, and UC′ that connect the following 5 points:
the line segment C′L is represented by coordinates (0.0098z2−1.238z+67.852, −0.0098z2+0.238z+32.148, z),
the line segment DU is represented by coordinates (−1.3777z2+78.306z−1083.8, 1.3777z2−79.306z+1183.8, z),
the line segment UC′ is represented by coordinates (−0.0656z2+1.1139z+50.472, 0.0656z2−2.1139z+49.528, z), and
the line segments LB″ and B″D are straight lines.
A composition comprising a refrigerant, the refrigerant comprising HFO-1132 (E), HFO-1123, and R32, wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments QB″, B″D, DU, and UQ that connect the following 4 points:
the line segment DU is represented by coordinates (−1.3777z2+78.306z−1083.8, 1.3777z2−79.306z+1183.8, z),
the line segment UQ is represented by coordinates (0.0192z2−1.1891z+47.168, −0.0192z2+0.1891z+52.832, z), and
the line segments QB″ and B″D are straight lines.
A composition comprising a refrigerant, the refrigerant comprising HFO-1132 (E), HFO-1123, and R32, wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments Oc′, c′d′, d′e′, e′ a′, and a′O that connect the following 5 points:
or on the line segments c′d′, d′e′, and e′ a′ (excluding the points c′ and a′);
the line segment c′d′ is represented by coordinates (−0.0297z2−0.1915z+56.7, 0.0297z2−0.8085z+43.3, z),
the line segment d′e′ is represented by coordinates (−0.0535z2+0.3229z+53.957, 0.0535z2−1.3229z+46.043, z), and
the line segments Oc′, e′ a′, and a′O are straight lines.
A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and difluoromethane (R32), wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments Oc, cd, de, ea′, and a′O that connect the following 5 points:
the line segment cde is represented by coordinates (−0.017z2+0.0148z+77.684, 0.017z2−1.0148z+22.316, z), and
the line segments Oc, ea′, and a′O are straight lines.
A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and difluoromethane (R32), wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments Oc′, c′d′, d′ a, and aO that connect the following 4 points:
the line segment c′d′ is represented by coordinates (−0.0297z2−0.1915z+56.7, 0.0297z2−0.8085z+43.3, z), and
the line segments Oc′, d′ a, and aO are straight lines.
A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and difluoromethane (R32), wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum in the refrigerant is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments Oc, cd, da, and aO that connect the following 4 points:
the line segment cd is represented by coordinates (−0.017z2+0.0148z+77.684, 0.017z2−1.0148z+22.316, z), and the line segments Oc, da, and aO are straight lines.
The composition according to any one of Items 1 to 11, for use as a working fluid for a refrigerating machine, wherein the composition further comprises a refrigeration oil.
The composition according to any one of Items 1 to 12, for use as an alternative refrigerant for R410A.
Use of the composition according to any one of Items 1 to 12 as an alternative refrigerant for R410A.
A refrigerating machine comprising the composition according to any one of claims 1 to 12 as a working fluid.
A method for operating a refrigerating machine, comprising the step of circulating the composition according to any one of claims 1 to 12 as a working fluid in a refrigerating machine.
The refrigerant according to the present disclosure has two types of performance, i.e., a coefficient of performance that is equivalent to that of R410A and a sufficiently low GWP.
The present inventors conducted intensive studies to solve the above problem, and consequently found that a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), trifluoroethylene (HFO-1123), and difluoromethane (HFC-32 or R32) has the properties described above.
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 is a mixed refrigerant comprising trans-1,2-difluoroethylene (HFO-1132 (E)), trifluoroethylene (HFO-1123), and difluoromethane (R32).
The refrigerant according to the present disclosure has various properties that are desirable as an R410A-alternative refrigerant, i.e., a coefficient of performance equivalent to that of R410A and a sufficiently low GWP.
The refrigerant according to the present disclosure is preferably a refrigerant wherein when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments IK, KB′, B′H, HR, RG, and GI that connect the following 6 points:
the line segment IK is represented by coordinates (0.025z2−1.7429z+72.00, −0.025z2+0.7429z+28.0, z),
the line segment HR is represented by coordinates (−0.6198z2+9.8223z−16.772, 0.6198z2−10.8223z+116.772, z),
the line segment RG is represented by coordinates (−0.072z2−1.1998z+38.5, 0.072z2+0.1998z+61.5, z), and
the line segments KB′, B′H and GI are straight lines.
When the requirements above are satisfied, the refrigerant according to the present disclosure has WCF lower flammability, a COP ratio of 93% or more relative to that of R410A, and a GWP of 125 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments IJ, JR, RG, and GI that connect the following 4 points:
the line segment IJ is represented by coordinates (0.025z2−1.7429 z+72.0, −0.025z2+0.7429z+28.0, z),
the line segment RG is represented by coordinates (−0.072z2−1.1998 z+38.5, 0.072z2+0.1998z+61.5, z), and
the line segments JR and GI are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has WCF lower flammability, a COP ratio of 93% or more relative to that of R410A, and a GWP of 65 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments MP, PB′, B′H, HR, RG, and GM that connect the following 6 points:
the line segment MP is represented by coordinates (0.0083z2−0.984 z+47.1, −0.0083z2−0.016 z+52.9, z),
the line segment HR is represented by coordinates (−0.6198z2+9.8223z−16.772, 0.6198z2−10.8223 z+116.772, z),
the line segment RG is represented by coordinates (−0.072z2−1.1998 z+38.5, 0.072z2+0.1998z+61.5, z), and
the line segments PB′, B′H and GM are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has ASHRAE lower flammability, a COP ratio of 93% or more relative to that of R410A, and a GWP of 125 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments MN, NR, RG, and GM that connect the following 4 points:
the line segment MN is represented by coordinates (0.0083z2−0.984 z+47.1, −0.0083z2−0.016 z+52.9, z),
the line segment RG is represented by coordinates (−0.072z2−1.1998 z+38.5, 0.072z2+0.1998z+61.5, z), and
the line segments NR and GM are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has ASHRAE lower flammability, a COP ratio of 93% or more relative to that of R410A, and a GWP of 65 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments PS, ST, and TP that connect the following 3 points:
the line segment ST is represented by coordinates (−0.0632z2−0.2026 z+50.03, 0.0632z2−0.7974 z+49.97, z),
the line segment TP is represented by coordinates (0.0083z2-0.984 z+47.1, −0.0083z2−0.016 z+52.9, z), and
the line segment PS is a straight line. When the requirements above are satisfied, the refrigerant according to the present disclosure has ASHRAE lower flammability, a COP ratio of 94.5% or more relative to that of R410A, and a GWP of 125 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments C′L, LB″, B″D, DU, and UC″ that connect the following 5 points:
the line segment C′L is represented by coordinates (0.0098z2−1.238 z+67.852, −0.0098z2+0.238z+32.148, z),
the line segment DU is represented by coordinates (−1.3777z2+78.306z−1083.8, 1.3777z2−79.306 z+1183.8, z),
the line segment UC′ is represented by coordinates (−0.0656z2+1.1139z+50.472, 0.0656z2−2.1139 z+49.528, z), and
the line segments LB″ and B″D are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has WCF lower flammability, a COP ratio of 96% or more relative to that of R410A, and a GWP of 250 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments QB″, B″D, DU, and UQ that connect the following 4 points:
the line segment DU is represented by coordinates (−1.3777z2+78.306z−1083.8, 1.3777z2−79.306 z+1183.8, z),
the line segment UQ is represented by coordinates (0.0192z2−1.1891 z+47.168, −0.0192z2+0.1891z+52.832, z), and
the line segments QB″ and B″D are straight lines.
When the requirements above are satisfied, the refrigerant according to the present disclosure has ASHRAE lower flammability, a COP ratio of 96% or more relative to that of R410A, and a GWP of 250 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments Oc′, c′d′, d′e′, e′ a′, and a′O that connect the following 5 points:
the line segment c′d′ is represented by coordinates (−0.0297z2−0.1915 z+56.7, 0.0297z2−0.8085 z+43.3, z),
the line segment d′e′ is represented by coordinates (−0.0535z2+0.3229z+53.957, 0.0535z2−1.3229 z+46.043, z), and
the line segments Oc′, e′ a′, and a′O are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a COP ratio of 92.5% or more relative to that of R410A, and a GWP of 125 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments Oc, cd, de, ea′, and a′O that connect the following 5 points:
the line segment cde is represented by coordinates (−0.017z2+0.0148z+77.684, 0.017z2−1.0148 z+22.316, z), and
the line segments Oc, ea′, and a′O are straight lines.
When the requirements above are satisfied, the refrigerant according to the present disclosure has a COP ratio of 95% or more relative to that of R410A, and a GWP of 125 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments Oc′, c′d′, d′ a, and aO that connect the following 4 points:
the line segment c′d′ is represented by coordinates (−0.0297z2−0.1915 z+56.7, 0.0297z2−0.8085 z+43.3, z), and
the line segments Oc′, d′ a, and aO are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a COP ratio of 93.5% or more relative to that of R410A, and a GWP of 65 or less.
The refrigerant according to the present disclosure is preferably a refrigerant wherein
when the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass % are within the range of a figure surrounded by line segments Oc, cd, da, and aO that connect the following 4 points:
the line segments Oc, da, and aO are are straight lines. When the requirements above are satisfied, the refrigerant according to the present disclosure has a COP ratio of 95% or more relative to that of R410A, and a GWP of 65 or less.
The refrigerant according to the present disclosure may further comprise other additional refrigerants in addition to HFO-1132 (E), HFO-1123, 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, 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 the tracer.
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-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.
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, and R32 at mass % based on their sum shown in Tables 1 and 2.
The composition of each mixture was defined as WCF. A leak simulation was performed using National Institute of Science and Technology (NIST) Standard Reference Data Base Refleak Version 4.0 under the conditions for equipment, storage, shipping, leak, and recharge according to the ASHRAE Standard 34-2013. The most flammable fraction was defined as WCFF.
For each mixed refrigerant, the burning velocity was measured according to the ANSI/ASHRAE Standard 34-2013. When the burning velocities of the WCF composition and the WCFF composition are 10 cm/s or less, the flammability of such a refrigerant is classified as Class 2L (lower flammability) in the ASHRAE flammability classification.
A burning velocity test was performed using the apparatus shown in
Tables 1 and 2 show the results.
The results in Table 1 indicate that in a ternary composition diagram of a mixed refrigerant of HFO-1132 (E), HFO-1123, and R32 in which their sum is 100 mass %, a line segment connecting a point (0.0, 100.0, 0.0) and a point (0.0, 0.0, 100.0) is the base, the point (0.0, 100.0, 0.0) is on the left side, and the point (0.0, 0.0, 100.0) is on the right side, when coordinates (x,y,z) are on or below line segments IK and KL that connect the following 3 points:
For the points on the line segment IK, an approximate curve (x=0.025z2−1.7429 z+72.00) was determined from three points, i.e., I (72.0, 28,0, 0.0), J (57.7, 32.8, 9.5), and K (48.4, 33.2, 18.4) by using the least-square method to determine coordinates
(x=0.025z2−1.7429 z+72.00, y=100-z-x=−0.025z2+0.7429z+28.00, z).
Likewise, for the points on the line segment KL, an approximate curve was determined from three points, i.e., K (48.4, 33.2, 18.4), Example 10 (41.1, 31.2,27.7), and L (35.5, 27.5, 37.0) by using the least-square method to determine coordinates, in the same manner as for the points on the line segment IK.
The results in Table 2 indicate that in a ternary composition diagram of a mixed refrigerant of HFO-1132 (E), HFO-1123, and R32 in which their sum is 100 mass %, a line segment connecting a point (0.0, 100.0, 0.0) and a point (0.0, 0.0, 100.0) is the base, the point (0.0, 100.0, 0.0) is on the left side, and the point (0.0, 0.0, 100.0) is on the right side, when coordinates (x,y,z) are on or below line segments MP and PQ that connect the following 3 points:
In the above, the line segment MP is represented by coordinates (0.0083z2-0.984 z+47.1, −0.0083z2−0.016 z+52.9, z), and the line segment PQ is represented by coordinates (0.0192z2−1.189 z+47.168, −0.0192z2+0.189z+52.832, z).
For the points on the line segment MP, an approximate curve was determined from three points, i.e., points M, N, and P, by using the least-square method to determine coordinates. For the points on the line segment PQ, an approximate curve was determined from three points, i.e., points P. U, and Q, by using the least-square method to determine coordinates, in the same manner as for the points on the line segment IK.
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 (which may be referred to as “cooling capacity” or “capacity”) ratio relative to those of R410 of the mixed refrigerants were determined. The conditions for calculation were as described below.
Evaporating temperature: 5° C.
Condensation temperature: 45° C.
Degree of superheating: 5K
Degree of subcooling: 5K
Compressor efficiency: 70%
Tables 3 to 23 show these values together with the GWP of each mixed refrigerant.
The above results indicate that under the condition that the mass % of HFO-1132 (E), HFO-1123, and R32 based on their sum is respectively represented by x, y, and z, when coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132 (E), HFO-1123, and R32 is 100 mass %, a line segment connecting a point (0.0, 100.0, 0.0) and a point (0.0, 0.0, 100.0) is the base, and the point (0.0, 100.0, 0.0) is on the left side are within the range of a figure surrounded by line segments that connect the following 4 points:
The results also indicate that when coordinates (x,y,z) are within the range of a figure surrounded by line segments that connect the following 4 points:
The results also indicate that when coordinates (x,y,z) are within the range of a figure surrounded by line segments that connect the following 4 points:
The results also indicate that when coordinates (x,y,z) are on the left side of line segments that connect the following 3 points:
In the above, the line segment CU is represented by coordinates (−0.0656z2+1.1139z+50.472, 0.0656z2-2.1139 z+49.528, z), and the line segment UD is represented by coordinates (−1.3777z2+78.306z−1083.8, 1.3777z2−79.306 z+1183.8, z).
The points on the line segment CU are determined from three points, i.e., point C, Example 2, and point U, by using the least-square method.
The points on the line segment UD are determined from three points, i.e., point U, Example 4, and point D, by using the least-square method.
The results also indicate that when coordinates (x,y,z) are on the left side of line segments that connect the following 3 points:
In the above, the line segment ES is represented by coordinates (−0.0632z2−0.2026 z+50.03, 0.0632z2−0.7974 z+49.97, z).
The points on the line segment ES are determined from three points, i.e., points E, T, and S, by using the least-square method.
The results also indicate that when coordinates (x,y,z) are on the left side of line segments that connect the following 3 points:
In the above, the line segment RG is represented by coordinates (−0.072z2−1.1998 z+38.5, 0.072z2+0.1998z+61.5, z), and
The points on the line segment RG are determined from three points, i.e., point G, Example 7, and point R, by using the least-square method.
The points on the line segment HR are determined from three points, i.e., point R, Example 9, and point H, by using the least-square method.
In contrast, as shown in, for example, Comparative Examples 8, 13, 15, and 18, when R32 is not contained, the concentrations of HFO-1132(E) and HFO-1123, which have a double bond, become relatively high; this undesirably leads to deterioration, such as decomposition, or polymerization in the refrigerant compound.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-242186 | Dec 2017 | JP | national |
| PCT/JP2018/038747 | Oct 2018 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16913648 | Jun 2020 | US |
| Child | 17880237 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16772589 | Jun 2020 | US |
| Child | 16913648 | US |
