Patent Application
20220145154
The present disclosure relates to a composition containing a refrigerant, use of the composition, a refrigerating machine containing the composition, and a method for operating the refrigerating machine.
R404A is currently used as a refrigerant for refrigeration apparatuses such as freezing and refrigerating equipment for commercial use. R404A is a three-component mixture refrigerant composed of pentafluoroethane (R125) (44%), 1,1,1-trifluoroethane (R143a) (52%), and 1,1,1,2-tetrafluoroethane (R134a) (4%). However, the global warming potential (GWP) of R404A is 3920. Due to growing concerns over global warming, there is demand for refrigerants with a lower GWP. For this reason, various low-GWP mixed refrigerants that can replace R404A have been proposed (PTL 1 to 5).
A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).
The refrigerant according to the present disclosure has a low GWP.
The present inventors conducted intensive research to solve the above problem, and found that a mixed refrigerant containing trans-1,2-difluoroethylene (HFO-1132(E)), 1,3,3,3-tetrafluoropropene (R1234ze), trifluoroethylene (HFO-1123), and difluoromethane (R32) has the above properties.
The present disclosure was completed as a result of further research based on this finding. The present disclosure includes the following embodiments.
In the present disclosure, 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), and ammonia (R717).
In the present disclosure, 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 disclosure, 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 disclosure, 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 achieved 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 disclosure, the term “refrigerating machine” (refrigerator) 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 disclosure, “a refrigerant having WCF lower-flammability” means that a most flammable formulation (worst case of formulation for flammability) in accordance with U.S. ANSI/ASHRAE Standard 34-2013 has a burning velocity of 10 cm/s or less. In the present disclosure, “a refrigerant having an ASHRAE lower-flammability” means that the WCF burning velocity is 10 cm/s or less, and that the most flammable faction formulation (worst case of fractionation for flammability: WCFF) determined by conducting a leakage test in storage, shipping, and use in accordance with ANSI/ASHRAE Standard 34-2013 by using WCF has a burning velocity of 10 cm/s or less, and is classified under the category of “Class 2L” in the flammability classification of U.S. ANSI/ASHRAE Standard 34-2013.
The refrigerant according to the present disclosure contains trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).
The refrigerant according to the present disclosure may contain, as R1234ze, either R1234ze(E) or R1234ze(Z), or both, and preferably contains only R1234ze(E).
The refrigerant according to the present disclosure has a low GWP.
The refrigerant is preferably as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KF, FE, and EI, which connect the following 5 points, or fall on any of line segments IJ, JK, KF, and FE:
point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),
line segments KF and EI are straight lines,
coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),
coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and
coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).
In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 70% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of WCF lower flammability.
The refrigerant is preferably as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KD, DC, and CI, which connect the following 5 points, or fall on any of the line segments:
point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point D (10.7, 21.6, 67.7), and
point C (38.6, 1.0, 60.4),
line segments KD and CI are straight lines,
coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),
coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and
coordinates (x,y,z) of a point on line segment DC are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).
In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 80% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of WCF lower flammability.
The refrigerant is preferably as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments LM, MN, NF, FE, and EL, which connect the following 5 points, or fall on any of the line segments:
point L (34.8, 1.0, 64.2),
point M (20.4, 10.0, 69.6),
point N (17.1, 21.6, 61.3),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),
line segments NF and EL are straight lines,
coordinates (x,y,z) of a point on line segment LM are represented by (x, 0.0399x2−2.8271x+51.071, −0.0399x2+1.8271x+48.929),
coordinates (x,y,z) of a point on line segment MN are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and
coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).
In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 70% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of ASHRAE lower flammability.
The refrigerant is preferably as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments ON, ND, and DO, which connect the following 3 points, or fall on any of line segments ON, ND, and DO:
point O (18.1, 15.8, 66.1),
point N (17.1, 21.6, 61.3), and
point D (10.7, 21.6, 67.7),
line segment ND is a straight line,
coordinates (x,y,z) of a point on line segment ON are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and
coordinates (x,y,z) of a point on line segment DO are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).
In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 80% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of ASHRAE lower flammability.
The refrigerant according to the present disclosure may further contain 2,3,3,3-tetrafluoropropene (R1234yf).
The refrigerant is preferably as follows: when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,
in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,
when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:
point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),
when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of the straight lines:
point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Br (1.0, 0.1885r2+0.0694+21.543, −0.1885r2−0.0694+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).
In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 70% or more relative to R404A, and is classified under the category of WCF lower flammability.
The refrigerant is preferably as follows: when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,
in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,
when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines LrI′r, L′rMr, MrM′r, M′rNr, NrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:
point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),
when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of the straight lines:
point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Br (1.0, 0.1885r2+0.0694r+21.543, −0.1885r2−0.0694r+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).
In this case, the refrigerant according to the present disclosure has a refrigerating capacity of 70% or more relative to R404A, and is classified under the category of ASHRAE lower flammability.
The refrigerant according to the present disclosure may further contain other additional refrigerants in addition to HFO-1132(E), R32, R1234ze, and R1234yf, as long as the above properties and effects are not impaired. In this respect, the refrigerant according to the present disclosure contains HFO-1132(E), R32, and R1234ze in a total amount of preferably 99.5 mass % or more, more preferably 99.75 mass % or more, and still more preferably 99.9 mass % or more based on the entire refrigerant. In another embodiment, the refrigerant according to the present disclosure contains HFO-1132(E), R32, R1234ze, and R1234yf in a total amount of preferably 99.5 mass % or more, more preferably 99.75 mass % or more, and still 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 contain 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 R404A.
The refrigerant composition according to the present disclosure contains 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 contains at least one other component in addition to the refrigerant according to the present disclosure. The refrigerant composition according to the present disclosure may contain 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 contain 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 contain 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 (NH2O). The tracer is particularly preferably a hydrofluorocarbon, hydrochlorofluorocarbon, chlorofluorocarbon, hydrochlorocarbon, fluorocarbon, or fluoroether.
The following compounds are preferable as the tracer.
FC-14 (tetrafluoromethane, CF4)
HCC-40 (chloromethane, CH3Cl)
HFC-23 (trifluoromethane, CHF3)
HFC-41 (fluoromethane, CH3Cl)
HFC-125 (pentafluoroethane, CF3CHF2)
HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F)
HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2)
HFC-143a (1,1,1-trifluoroethane, CF3CH3)
HFC-143 (1,1, 2-trifluoroethane, CHF2CH2F)
HFC-152a (1, 1-difluoroethane, CHF2CH3)
HFC-152 (1,2-difluoroethane, CH2FCH2F)
HFC-161 (fluoroethane, CH3CH2F)
HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2)
HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3)
HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2)
HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3)
HCFC-22 (chlorodifluoromethane, CHClF2)
HCFC-31 (chlorofluoromethane, 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 according to the present disclosure may contain a 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 according to the present disclosure may contain a 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 contain 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 contain 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 nitrobenzene and nitrostyrene.
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 contain 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 contains at least the refrigerant or refrigerant composition according to the present disclosure and a refrigeration oil, and is used 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 contains 10 to 50 mass % of refrigeration oil.
The composition according to the present disclosure may contain 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 the compatibilizing agents described below.
The refrigeration oil-containing working fluid according to the present disclosure may contain 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 includes 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.
A composition comprising a refrigerant, the refrigerant comprising trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), and 1,3,3,3-tetrafluoropropene (R1234ze).
The composition according to Item 1,
wherein
when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KF, FE, and EI, which connect the following 5 points, or fall on any of the line segments:
point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),
line segments KF and EI are straight lines,
coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),
coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and
coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).
The composition according to Item 1,
wherein
when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KD, DC, and CI, which connect the following 5 points, or fall on any of line segments IJ, JK, KD, and DC:
point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point D (10.7, 21.6, 67.7), and
point C (38.6, 1.0, 60.4),
line segments KD and CI are straight lines,
coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),
coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and
coordinates (x,y,z) of a point on line segment DC are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).
The composition according to Item 1,
wherein
when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments LM, MN, NF, FE, and EL, which connect the following 5 points, or fall on any of line segments LM, MN, NF, and FE:
point L (34.8, 1.0, 64.2),
point M (20.4, 10.0, 69.6),
point N (17.1, 21.6, 61.3),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),
line segments NF and EL are straight lines,
coordinates (x,y,z) of a point on line segment LM are represented by (x, 0.0399x2−2.8271x+51.071, −0.0399x2+1.8271x+48.929),
coordinates (x,y,z) of a point on line segment MN are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and
coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).
The composition according to Item 1,
wherein
when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments ON, ND, and DO, which connect the following 3 points, or fall on any of line segments ON, ND, and DO:
point O (18.1, 15.8, 66.1),
point N (17.1, 21.6, 61.3), and
point D (10.7, 21.6, 67.7),
line segment ND is a straight line,
coordinates (x,y,z) of a point on line segment ON are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and
coordinates (x,y,z) of a point on line segment DO are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).
The composition according to any one of Items 1 to 5, wherein the refrigerant further comprises 2,3,3,3-tetrafluoropropene (R1234yf).
The composition according to Item 6,
wherein
when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,
in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,
when 0.103≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, and E′rEr:
point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),
when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrBr, BrE′r, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrBr, BrFr, FrEr′, and Er′Er:
point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Br (1.0, 0.1885r2+0.0694+21.543, −0.1885r2−0.0694r+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).
The composition according to Item 6,
wherein
when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the refrigerant,
in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,
when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines LrI′r, L′rMr, MrM′r, M′rNr, NrBr, FrEr, E′rEr, and ErIr, which connect the following 8 points, or fall on any of straight lines LrI′r, L′rMr, MrM′r, M′rNr, NrFr, FrEr, and Erer:
point Lr (−5.5999r2+20.0r+34.8, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),
when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, and E′rEr:
point Lr (−5.5999r2+20.0r+34.8, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Br (1.0, 0.1885r2+0.0694r+21.543, −0.1885r2−0.0694r+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).
The composition according to any one of Items 1 to 8, which is for use as a working fluid for a refrigerating machine, the composition further comprising a refrigeration oil.
The composition according to any one of Items 1 to 9, which is for use as an alternative refrigerant for R404A.
Use of the composition of any one of Items 1 to 9 as an alternative refrigerant for R404A.
A refrigerating machine comprising the composition of any one of Items 1 to 9 as a working fluid.
A method for operating a refrigerating machine, comprising circulating the composition of any one of Items 1 to 9 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), R32, and R1234ze in mass % shown in Table 1 based on their sum.
The GWP of R404A (R125=44%/R143A=52%/R134A=4%) and the mixed refrigerants was evaluated based on the values stated in the Intergovernmental Panel on Climate Change (IPCC), fourth assessment 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 R404A and the 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.
The COP and refrigerating capacity of these mixed refrigerants relative to those of R404A were determined. The computational conditions were as follows.
Evaporating temperature: −40° C.
Condensation temperature: 40° C.
Superheating temperature: 20 K
Subcooling temperature: 0 K
Compressor efficiency: 70%
Tables 1 to 3 show these values together with the GWP of each mixed refrigerant. The COP and refrigerating capacity are percentages relative to R410A.
The coefficient of performance (COP) was determined by the following formula.
COP=(refrigerating capacity or heating capacity)/power consumption
A leak was simulated with the formulation of each mixture as WCF, under the conditions of equipment, storage, shipping, leak, and recharge based on ASHRAE Standard 34-2013, by using the NIST Standard Reference Database Refleak Version 4.0, and the most flammable fraction was determined to be WCFF.
For the flammability, the burning velocity was measured according to ANSI/ASHRAE Standard 34-2013. Compositions having a burning velocity of 10 cm/s or less in both WCF and WCFF were determined to be “Class 2L (lower flammability).”
A burning velocity test was performed using the apparatus shown in
Su=Sb*ρu/ρb
ρu: adiabatic flame temperature (unburned)
ρb: adiabatic flame temperature (burned)
ρu was calculated from a measurement temperature, and ρb was calculated from the combustion and isobaric specific heat of combustion gas.
Table 2 shows the results.
From these results, it is understood that a mixed refrigerant has a refrigerating capacity of 70% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of WCF lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the mixed refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KF, FE, and EI, which connect the following 5 points, or fall on any of the line segments:
point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),
line segments KF and EI are straight lines,
coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),
coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and
coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).
It is also understood that a mixed refrigerant has a refrigerating capacity of 80% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of WCF lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the mixed refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments IJ, JK, KD, DC, and CI, which connect the following 5 points, or fall on any of the line segments:
point I (70.3, 1.0, 28.7),
point J (57.1, 10.0, 32.9),
point K (45.4, 21.8, 32.8),
point D (10.7, 21.6, 67.7), and
point C (38.6, 1.0, 60.4),
line segments KD and CI are straight lines,
coordinates (x,y,z) of a point on line segment IJ are represented by (x, 0.00991x2−1.945x+88.734, −0.00991x2+0.945x+11.266),
coordinates (x,y,z) of a point on line segment JK are represented by (x, 0.01605x2−2.6528x+109.17, −0.01605x2+1.6528x−9.17), and
coordinates (x,y,z) of a point on line segment DC are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).
It is also understood that a mixed refrigerant has a refrigerating capacity of 70% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of ASHRAE lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the mixed refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments LM, MN, NF, FE, and EL, which connect the following 5 points, or fall on any of the line segments:
point L (34.8, 1.0, 64.2),
point M (20.4, 10.0, 69.6),
point N (17.1, 21.6, 61.3),
point F (2.8, 21.6, 75.6), and
point E (30.2, 1.0, 68.8),
line segments NF and EL are straight lines,
coordinates (x,y,z) of a point on line segment LM are represented by (x, 0.0399x2−2.8271x+51.071, −0.0399x2+1.8271x+48.929),
coordinates (x,y,z) of a point on line segment MN are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and
coordinates (x,y,z) of a point on line segment FE are represented by (x, 0.0017x2−0.8094x+23.852, −0.0017x2−0.1906x+76.148).
It is also understood that a mixed refrigerant has a refrigerating capacity of 80% or more relative to R404A and has a GWP of 150 or less, and is classified under the category of ASHRAE lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E), R32, and R1234ze based on their sum in the mixed refrigerant is respectively x, y, and z, coordinates (x,y,z) in a ternary composition diagram in which the sum of HFO-1132(E), R32, and R1234ze is 100 mass % fall within a figure surrounded by line segments ON, ND, and DO, which connect the following 3 points, or fall on any of line segments ON, ND, and DO:
point O (18.1, 15.8, 66.1),
point N (17.1, 21.6, 61.3), and
point D (10.7, 21.6, 67.7),
line segment ND is a straight line,
coordinates (x,y,z) of a point on line segment ON are represented by (x, 0.9452x2−38.959x+411.42, −0.9452x2+37.959x−311.42), and
coordinates (x,y,z) of a point on line segment DO are represented by (x, 0.00195x2−0.8346x+30.307, −0.00195x2−0.1654x+69.693).
The approximate expressions that represent line segments connecting the points were each determined in the following manner.
Mixed refrigerants were prepared such that the mass % of HFO-1132(E), the mass % of R32, and the total mass % of R1234ze and R1234yf were as shown in Tables 4 and 5 based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and evaluated in the same manner as in Example A. Tables 4 and 5 show the results. The alphabetical letter “r” represents R1234yf/(R1234ze+R1234yf).
The coordinates of each point were determined by using an approximate expression in the following manner.
Nr)
From these results, it is understood that a mixed refrigerant has a refrigerating capacity of 70% or more relative to R404A and is classified under the category of WCF lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the mixed refrigerant,
in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,
when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:
point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),
when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines IrI′r, I′rJr, JrJ′r, J′rKr, KrBr, BrFr, FrE′r, E′rEr and ErIr, which connect the following 9 points, or fall on any of the straight lines:
point Ir (70.3, 1.0, 28.7),
point I′r (63.8, 5.0, 31.2),
point Jr (57.1, 10.0, 32.9),
point J′r (51.6, 15.0, 33.4),
point Kr (45.4, 21.8, 32.8),
point Br (1.0, 0.1885r2+0.0694+21.543, −0.1885r2−0.0694+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).
It is also understood that a mixed refrigerant has a refrigerating capacity of 70% or more relative to R404A and is classified under the category of ASHRAE lower flammability when the mixed refrigerant is represented as follows: when the mass % of HFO-1132(E) is x, the mass % of R32 is y, and the total mass % of R1234ze and R1234yf is z based on the sum of HFO-1132(E), R32,
R1234ze, and R1234yf, and r=R1234yf/(R1234ze+R1234yf) in the mixed refrigerant,
in a ternary composition diagram having HFO-1132(E) as a first vertex, R32 as a second vertex, and the sum of 1234ze and R1234yf as a third vertex,
when 0.1030≥r>0, coordinates (x,y,z) fall within a figure surrounded by straight LrI′r, L′rMr, MrM′r, M′rNr, NrFr, FrE′r, E′rEr, and ErIr, which connect the following 8 points, or fall on any of the straight lines:
point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Fr (−17.476r+2.8, 21.6, 17.476r+75.6),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78),
when 1.0>r>0.103, coordinates (x,y,z) fall within a figure surrounded by straight lines LrL′r, L′rMr, MrM′r, M′rNr, NrBr, BrFr, FrE′r, E′rEr, and ErIr, which connect the following 9 points, or fall on any of the straight lines:
point Lr (−5.5999r2+20.0r+34.87, 1.0, 5.5999r2−20.0r+64.2),
point L′r (−4.5644r2+18.673r+25.41, 5.0, 4.5644r2−18.673r+69.59),
point Mr (−3.8003r2+15.899r+20.401, 10.0, 3.8003r2−15.899r+69.599),
point M′r (−3.0027r2+13.693r+18.309, 15.0, 3.0027r2−13.693r+66.691),
point Nr (−1.7082r2+11.022r+17.134, 0.3345r+21.594, 1.7082r2−11.3565r+61.272),
point Br (1.0, 0.1885r2+0.0694r+21.543, −0.1885r2−0.0694r+77.457)
point Fr (1.0, 1.6787r2−15.118r+23.139, −1.6787r2+15.118r+75.861),
point E′r (−0.3615r2−17.002r+17.781, 10.0, 0.3615r2+17.002r+72.219), and
point Er (0.3938r2−17.016r+30.22, 1.0, −0.3938r2+17.016r+68.78).
Mixed refrigerants were prepared such that the mass % of HFO-1132(E), the mass % of R32, and the total mass % of R1234ze and R1234yf were as shown in Tables 8 to 11 based on the sum of HFO-1132(E), R32, R1234ze, and R1234yf, and evaluated in the same manner as in Example A. Tables 8 to 11 show the results. The alphabetical letter “r” represents R1234yf/(R1234ze+R1234yf).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-114161 | Jun 2019 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2020/024180 | Jun 2020 | US |
| Child | 17551822 | US |
