HEAT TRANSFER COMPOSITIONS, METHODS, AND SYSTEMS

Abstract

The present invention relates to refrigerant compositions comprising at least about 98.5% by weight of the following three compounds, each present in the following relative percentages: 33.0% to 45% by weight of difluoromethane (HFC-32), 48.5% to 67.0% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), and 1.0% to 6.0% by weight of fluoroethane (HFC-161), and the use of such compositions in heat exchange systems, including air conditioning, cooling, and heat pump applications, and as a replacement for refrigerants R-410A or R-32 or R-454B for heating and cooling applications.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Patent Application No. 17 / 872,434, filed July 25, 2022, and U.S. Provisional Patent Application No. 63 / 235,184, filed August 20, 2021, each of which is incorporated by reference in its entirety herein.

[0002] The present invention relates to compositions, methods, and systems having utility in heat transfer applications, and in particular are useful in stationary air conditioning and heat pump systems, and in certain embodiments, to refrigerant compositions as replacements for the refrigerant R-410A for various heating and cooling applications, such as (1) as a replacement for R-410A in stationary air conditioning and heat pump systems, medium temperature cooling systems, and low temperature cooling systems, and (2) as a replacement or retrofit for R-32 and R454B in stationary air conditioning and heat pump systems, medium temperature cooling systems, and low temperature cooling systems. [Background technology]

[0003] Mechanical cooling systems for industrial, commercial and domestic use, and related heat transfer devices such as heat pumps, chillers and air conditioners are well known in the art.Some fluorocarbon-based fluids have found wide use in many residential, commercial and industrial applications, including as working fluids in systems such as air conditioning, heat pumps and cooling systems.Due to certain environmental concerns, including the relatively high global warming potential associated with the use of some hydrofluorocarbon ("hydrofluorocarbon, HFC")-based compositions that have been used in these applications, it has become increasingly desirable to use fluids with a global warming potential ("GWP") of less than 300.

[0004] A refrigerant that has been commonly used in many applications is R-410A, a 50:50 blend by weight of pentafluoroethane (HFC-125) and difluoromethane (HFC-32). R-410A has an estimated GWP of 2088.

[0005] In general, it is believed to be important that any potential <300 GWP replacement for R-410A should also possess, among other properties, excellent heat transfer properties, chemical stability, acceptable mild or non-flammability, and lubricant compatibility, which are present in many of the most widely used HFC-based fluids.

[0006] With regard to efficiency of use, it is important to note that the loss of thermodynamic performance or energy efficiency of a refrigerant may have a secondary environmental impact by resulting in increased fossil fuel use as a result of increased demand for electrical energy. In other words, a proposed new refrigerant with a GWP of less than 300 may nevertheless not be as environmentally friendly as the fluid it replaces if another property of the proposed new fluid, such as efficiency of use, results in an indirect increase in environmental emissions, such as by requiring higher fuel combustion to achieve the same level of cooling. Thus, the selection of a replacement proves to be a complex and difficult endeavor that may not yield predictable results.

[0007] Furthermore, it is generally believed that it would be desirable for HFC refrigerant replacements to be effective without major engineering changes to conventional vapor compression technology currently in use with HFC refrigerants, or with changes limited to the compressor and possibly a few other components.

[0008] It is important for maintaining system efficiency and for the compressor to function properly and reliably that the lubricant circulating through a vapor compression heat transfer system be returned to the compressor to perform its intended lubricating function. Otherwise, the lubricant may accumulate and remain in the coils and pipes of the system, including in the heat transfer components. Furthermore, if the lubricant accumulates on the interior surfaces of the evaporator, the heat exchange efficiency of the evaporator decreases, thereby reducing the efficiency of the system. For these reasons, for many systems, it is desirable for the refrigerant to be miscible with the lubricant used in the system, at least over the operating temperature range of the system.

[0009] The difficulty of achieving a refrigerant capable of achieving many or all of the above-mentioned properties at once is illustrated, for example, by the refrigerants disclosed in Chinese Patent No. 102746525 ("CN525"). Specifically, "CN525" discloses a number of refrigerant blends, including blends containing combinations of R32, R161, and HFO1234yf, with the amount of each compound being within a specified range. The minimum amount of R161 in such blends is disclosed to be 20% by weight, and the maximum amount of R32 is disclosed to be 20% by weight. As a result of tests performed by the applicants, as will be explained in detail below, this refrigerant blend is lacking in at least one of the important properties identified above, and the novel refrigerant according to the present invention is unexpectedly able to achieve a difficult-to-achieve combination of important properties not possible by following the teachings of CN525, including, in particular, non-flammability. Summary of the Invention

[0010] Applicants have discovered that the compositions of the present invention meet in an exceptional and unexpected manner the need for sub-300 GWP alternatives and / or replacements for R-410A that are only slightly flammable (i.e., have a 2L classification according to ANSI / ASHRAE 34-2019, Designation and Safety Classification of Refrigerants), have acceptable toxicity (are Class A under ASHRAE 34), closely match R-410A in cooling efficiency and capacity, and preferably also have a glide that is not excessively high. As used herein, the term "sub-300 GWP" is used for convenience to refer to refrigerants having a GWP of 300 or less (measured as described below).

[0011] The present invention relates to a refrigerant comprising at least 98.5% by weight of the following three compounds, each of which is present in the following relative percentages: 33.0% to 45% by weight of difluoromethane (HFC-32); 48.5% to 67.0% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), and Includes refrigerants with 1.0% to less than 7.0% by weight of fluoroethane (HFC-161), provided that the refrigerant is a Class A2L refrigerant and has a GWP of less than 300. The refrigerants described in this paragraph may be referred to as Refrigerant 1 for convenience.

[0012] The present invention relates to a refrigerant comprising at least 98.5% by weight of the following three compounds, each of which is present in the following relative percentages: 40% to 45% by weight of HFC-32, 50% to 55% by weight of HFO-1234yf, and Refrigerants present at 1.0% to 6.0% by weight of HFC-161, provided that the refrigerant is a Class A2L refrigerant and has a GWP of less than 300. The refrigerants described in this paragraph may be referred to as "Refrigerant 2" for convenience.

[0013] The present invention relates to a refrigerant consisting essentially of the following three compounds, each of which is present in the following relative percentages: 33.0% to 45% by weight of HFC-32, 48.5% to 67.0% by weight of HFO-1234yf, and Refrigerants present at 1.0% to 6.0% by weight of HFC-161, provided that the refrigerant is a Class A2L refrigerant and has a GWP of less than 300. The refrigerants described in this paragraph may be referred to as "Refrigerant 3" for convenience.

[0014] The present invention relates to a refrigerant consisting essentially of the following three compounds, each of which is present in the following relative percentages: 40% to 45% by weight of HFC-32, 50% to 55% by weight of HFO-1234yf, and Refrigerants present at 1.0% to 6.0% by weight of HFC-161, provided that the refrigerant is a Class A2L refrigerant and has a GWP of less than 300. The refrigerants described in this paragraph may be referred to as "Refrigerant 4" for convenience.

[0015] The present invention relates to a refrigerant consisting essentially of the following three compounds, each of which is present in the following relative percentages: 41.5% to 44.5% by weight of HFC-32, 49.5% to 53.5% by weight of HFO-1234yf, and % to 6.0% by weight of HFC-161. The refrigerant described in this paragraph may be referred to as "Refrigerant 5" for convenience.

[0016] The present invention relates to a refrigerant consisting essentially of the following three compounds, each of which is present in the following relative percentages: 43.5% by weight +0.5 / -2% by weight HFC-32, 52.5% by weight +2 / -0.5% by weight HFO-1234yf, and 4% +0.5 / -2% by weight of HFC-161. The refrigerant described in this paragraph may be conveniently referred to as "Refrigerant 6".

[0017] The present invention relates to a refrigerant consisting of the following three compounds, each of which is present in the following relative percentages: 43.5% by weight +0.5 / -2% by weight HFC-32, 52.5% by weight +2 / -0.5% by weight HFO-1234yf, and 4% +0.5 / -2% by weight of HFC-161. The refrigerant described in this paragraph may be referred to as "Refrigerant 7" for convenience.

[0018] The present invention relates to a refrigerant consisting essentially of the following three compounds, each of which is present in the following relative percentages: 43.5% by weight +0.5 / -2% by weight HFC-32, 51.5% by weight +2 / -0.5% by weight HFO-1234yf, and 4% +0.5 / -2% by weight of HFC-161, provided that such refrigerants are Class A2L refrigerants and have a GWP of less than 300. The refrigerants described in this paragraph may be referred to as "Refrigerant 8" for convenience.

[0019] The present invention relates to a refrigerant consisting of the following three compounds, each of which is present in the following relative percentages: 43.5% by weight of HFC-32, 52.5% by weight of HFO-1234yf, and % by weight of HFC-161. The refrigerant described in this paragraph may be conveniently referred to as "Refrigerant 9."

[0020] The present invention relates to a refrigerant consisting of the following three compounds, each of which is present in the following relative percentages: 43.5% by weight of HFC-32, 52.5% by weight of HFO-1234yf, and % by weight of HFC-161, which refrigerant is a Class A2L refrigerant and has a GWP of less than 300. The refrigerant described in this paragraph may be referred to as "Refrigerant 10" for convenience. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in air conditioning, low temperature cooling, and medium temperature cooling. [Diagram 2] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low and medium temperature cooling and including a steam injector. [Diagram 3] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low and medium temperature cooling and including a liquid injector. [Figure 4] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low and medium temperature cooling and including a suction line / liquid line heat exchanger. [Diagram 5] FIG. 1 is a schematic diagram of an exemplary heat transfer system useful in low and medium temperature cooling and including a steam injector and an oil separator. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Definition: For purposes of the present invention, the term "about" in relation to amounts expressed as weight percent for amounts greater than 2% means that the amount of the component can vary by an amount of ±2% by weight.

[0023] For purposes of the present invention, the term "about" in reference to temperatures in degrees Celsius (°C) means that the stated temperature can vary by an amount of ±5°C.

[0024] The term "capacity" is the amount of cooling provided by a refrigerant in BTU / hr in a cooling system. It is determined experimentally by multiplying the change in enthalpy in BTU / lb of the refrigerant as it passes through the evaporator by the mass flow rate of the refrigerant. The enthalpy can be determined from measurements of the pressure and temperature of the refrigerant. The capacity of a cooling system is related to its ability to maintain a particular temperature in an area to be cooled. The capacity of a refrigerant represents the amount of cooling or heating it provides and provides some measure of the compressor's ability to deliver a quantity of heat for a given volumetric flow rate of refrigerant. In other words, given a particular compressor, a refrigerant with a higher capacity will provide more cooling or heating power.

[0025] The phrase "coefficient of performance" (hereinafter "COP") is a widely accepted measure of refrigerant performance that is particularly useful for expressing the relative thermodynamic efficiency of a refrigerant in a particular heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration engineering, the term represents the ratio of available refrigeration or cooling capacity to the energy added by the compressor during compression of the vapor, and thus the ability of a given compressor to deliver a quantity of heat for a given volumetric flow rate of a heat transfer fluid such as a refrigerant. In other words, given a particular compressor, a refrigerant with a higher COP will deliver more cooling or heating power. One means for estimating the COP of a refrigerant at a particular operating condition is from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see, for example, R.C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, which is incorporated herein by reference in its entirety).

[0026] The phrase "discharge temperature" refers to the temperature of the refrigerant at the outlet of the compressor. The advantage of a low discharge temperature is that it allows the use of existing equipment, preferably without activating the thermal protection aspects of the system designed to protect the compressor components, and avoids the use of expensive control devices such as liquid injection to reduce the discharge temperature.

[0027] The term "global warming potential" (hereafter "GWP") was developed to allow comparison of the global warming impact of different gases. Specifically, it is a measure of how much energy the emission of one ton of a gas absorbs over a given period of time, relative to the emission of one ton of carbon dioxide. The higher the GWP, the more a given gas will warm the earth over that period, relative to CO2. The period usually used for GWP is 100 years. GWP provides a common measure that allows analysts to add up emission estimates of different gases. See http: / / www.protocolodemontreal.org.br / site / images / publicacoes / setor_manufatura_equipamentos_refrigeracao_arcondicionado / Como_calcular_el_Potencial_de_Calentamiento_Atmosferico_en_las_mezclas_de_refrigerantes.pdf.

[0028] The term "Occupational Exposure Limit (OEL)" is determined in accordance with ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants.

[0029] As used herein, the phrase "acceptable toxicity" means that the composition is classified as Class "A" by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and is set forth in Appendix B1 of ASHRAE Standard 34-2016, as such standards exist as of the filing date of this application. A material that is non-flammable and has low toxicity is classified as "A1" by ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants and is set forth in Appendix B1 of ASHRAE Standard 34-2016, as such standards exist as of the filing date of this application.

[0030] The term "mass flow" is the mass of refrigerant passing through a conduit per unit time.

[0031] As used herein, the term "replacement" refers to the use of the compositions of the present invention in a heat transfer system designed for or suitable for use with another refrigerant. For example, when the refrigerant or heat transfer composition of the present invention is used in a heat transfer system designed for use with R-410A, the refrigerant or heat transfer composition of the present invention is a replacement for R-410A in that system. Thus, the term "replacement" will be understood to include the use of the refrigerant and heat transfer composition of the present invention in both new and existing systems designed, commonly used, or suitable for use with R-410A.

[0032] The phrase "thermodynamic glide" applies to non-azeotropic refrigerant mixtures that have different temperatures during the phase change process in an evaporator or condenser at constant pressure.

[0033] As used herein, the term "evaporator glide" refers to the difference between the saturation temperature of the refrigerant at the inlet of the evaporator and the dew point of the refrigerant at the outlet of the evaporator, assuming that the pressure at the evaporator outlet is the same as the pressure at the inlet. As used herein, the phrase "saturation temperature" refers to the temperature at which liquid refrigerant boils to a vapor at a given pressure.

[0034] The term "low temperature cooling system / refrigeration system" refers to a heat transfer system operating at a condensing temperature of about 20°C to about 60°C and an evaporating temperature of about -45°C up to and including -12°C.

[0035] The term "medium temperature cooling system / refrigeration system" refers to a heat transfer system that operates at a condensing temperature of about 20°C to about 60°C and an evaporating temperature of about -12°C to about 0°C.

[0036] As used herein, the term "residential air conditioning" refers to a heat transfer system that conditions (cools or heats) air, operating at a condensing temperature of about 20°C to about 70°C and an evaporating temperature of about 0°C to about 20°C.

[0037] As used herein, the term "residential air-to-water heat pump" refers to a heat transfer system that transfers heat from outdoor air to water within a residence, which is then used to condition the air within the residence, and operates at a condensing temperature of about 20°C to about 70°C and an evaporating temperature of about -20°C to about 3°C.

[0038] As used herein, the term "air-cooled chiller" refers to a heat transfer system that transfers heat to or from process water (typically used to cool or heat the interior of a building) and rejects or absorbs heat from the surrounding air, and operates at a condensing temperature of about 20°C to about 70°C and an evaporating temperature of about 0°C to about 10°C.

[0039] As used herein, the term "supermarket refrigeration" refers to commercial refrigeration systems used to keep foods cool or frozen, both in product display cases and in storage refrigerators.

[0040] The terms "variable refrigerant flow system" and "VRF system" each refer to an air conditioning system configuration that uses two or more indoor evaporators and has the ability to control the amount of refrigerant flowing to the multiple evaporators.

[0041] As used herein, the terms "HFO-1234yf" and "R-1234yf" each mean 2,3,3,3-tetrafluoropropene.

[0042] As used herein, the terms "HFC-32" and "R-32" each mean difluoromethane.

[0043] As used herein, the terms "HFC-161" and "R-161" each mean fluoroethane.

[0044] As used herein, the term "R-454B" refers to a refrigerant comprising a blend of 68.9% by weight R-32 and 31.1% by weight R-1234yf.

[0045] Reference herein to a group of defined terms includes all such defined terms, including all such terms with the suffix designation.

[0046] Refrigerants and heat transfer compositions Applicants have discovered that the refrigerants of the present invention, including each of Refrigerants 1-10 described herein, can provide exceptionally advantageous properties such as heat transfer characteristics, acceptable toxicity, mild flammability (i.e., being Class 2L), zero or near zero ozone depletion potential ("ODP"), and lubricant compatibility, including miscibility with POE and / or PVE lubricants, over the operating temperature and concentration ranges used in stationary air conditioning systems (including residential air conditioning, commercial air conditioning, and VRF air conditioning), chillers (including air-to-water chillers), heat pump systems (including residential air-to-water heat pump systems), medium temperature cooling, and low temperature cooling.

[0047] A particular advantage of the refrigerants of the present invention, particularly including each of Refrigerants 1-10, is that they are mildly flammable and have acceptable toxicity, i.e., each is a Class A2L refrigerant. It will be appreciated by those skilled in the art that flammability of a refrigerant may be a considered characteristic in certain critical heat transfer applications, and that refrigerants classified as 2L may often be more advantageous than refrigerants that are considered flammable. It is therefore desirable in the art to provide a refrigerant composition that can be used as a replacement for 410A (or as a replacement or retrofit for R-32 and R454B) and that has excellent heat transfer properties, acceptable toxicity, zero or near zero ODP, and lubricant compatibility, including miscibility with POE and / or PVE lubricants, over the operating temperature and concentration ranges used in stationary air conditioning systems (including residential air conditioning, commercial air conditioning, VRF air conditioning), chillers (including air-to-water chillers), heat pump systems (including residential air-to-water heat pump systems), and commercial cooling (including medium and low temperature cooling), and that maintains non-flammability during use. This desirable advantage can be achieved and met by the refrigerants of the present invention, which is a surprising and unexpected result.

[0048] Applicants have discovered that the refrigerant compositions of the present invention, including each of Refrigerants 1-10, can achieve a difficult to achieve combination of properties, including a particularly low GWP. Thus, the compositions of the present invention have a GWP of 300 or less, preferably 295 or less.

[0049] Additionally, the refrigerant compositions of the present invention, including each of Refrigerants 1-10, have an ODP of zero or near zero. Thus, the compositions of the present invention have an ODP of 0.02 or less, and more preferably zero.

[0050] Additionally, the refrigerant compositions of the present invention, including each of Refrigerants 1-10, exhibit acceptable toxicity and preferably have an OEL greater than about 400. As those skilled in the art will recognize, non-flammable refrigerants having an OEL greater than about 400 are advantageous because they provide refrigerants that are classified as desirable "Class A" under ASHRAE Standard 34.

[0051] Preferred refrigerant compositions of the present invention exhibit both acceptable toxicity and mild flammability under ASHRAE Standard 34, and are therefore Class A2L refrigerants. Applicants have found that the heat transfer compositions of the present invention, including those comprising each of the refrigerants 1-10 described herein, can provide an exceptionally advantageous and unexpected combination of properties, such as good heat transfer properties, chemical stability under use conditions, acceptable toxicity, mild flammability, zero or near-zero ozone depletion potential ("ODP"), and lubricant compatibility, including miscibility with POE and / or PVE lubricants over the operating temperature and concentration ranges used in stationary air conditioning systems (including residential air conditioning, commercial air conditioning, VRF air conditioning), chillers (including air-to-water chillers), heat pump systems (including residential air-to-water heat pump systems), and commercial cooling (including medium and low temperature cooling), and a GWP of less than 300 in such systems, particularly as a replacement for R-410A, or as a replacement or retrofit for R-32 or R454B.

[0052] The heat transfer composition can consist essentially of any refrigerant of the present invention, including each of Refrigerants 1-10.

[0053] The heat transfer composition of the present invention can comprise any refrigerant of the present invention, including each of Refrigerants 1-10.

[0054] The heat transfer compositions of the present invention may contain other components for the purpose of enhancing or providing certain functional properties to the composition, which may include, in addition to the refrigerants of the present invention, including each of Refrigerants 1-10, one or more of lubricants, passivators, flammability inhibitors, dyes, solubilizers, compatibilizers, stabilizers, antioxidants, corrosion inhibitors, extreme pressure additives, and antiwear additives, as well as other compounds and / or components that adjust certain properties of the heat transfer composition, and the presence of all such compounds and components is within the broad scope of the present invention.

[0055] Lubricants The heat transfer compositions of the present invention may include the refrigerants described herein, including each of Refrigerants 1-10, and lubricants. The heat transfer compositions described in this paragraph may be referred to as Heat Transfer Composition 1 for convenience.

[0056] The heat transfer composition of the present invention may also include a refrigerant as described herein, including each of Refrigerants 1-10, and a polyol ester (POE) lubricant. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 2 for convenience.

[0057] The heat transfer composition of the present invention specifically comprises a refrigerant 7 and a POE lubricant. The heat transfer composition described in this paragraph may be conveniently referred to as heat transfer composition 3.

[0058] The heat transfer composition of the present invention specifically comprises a refrigerant 8 and a POE lubricant. The heat transfer composition described in this paragraph may be conveniently referred to as heat transfer composition 4.

[0059] The heat transfer composition of the present invention specifically comprises a refrigerant 9 and a POE lubricant. The heat transfer composition described in this paragraph may be conveniently referred to as heat transfer composition 5.

[0060] The heat transfer composition of the present invention includes, inter alia, a refrigerant 10 and a POE lubricant. The heat transfer composition described in this paragraph may be conveniently referred to as heat transfer composition 6.

[0061] The heat transfer composition of the present invention specifically comprises a refrigerant 7 and a polyvinyl ether (PVE) lubricant. The heat transfer composition described in this paragraph may be conveniently referred to as heat transfer composition 7.

[0062] The heat transfer composition of the present invention specifically comprises a refrigerant 8 and a PVE lubricant. The heat transfer composition described in this paragraph may be conveniently referred to as heat transfer composition 8.

[0063] The heat transfer composition of the present invention includes, inter alia, Refrigerant 9 and PVE lubricant. The heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 9 for convenience.

[0064] The heat transfer composition of the present invention includes, inter alia, a refrigerant 10 and a PVE lubricant. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 10 for convenience.

[0065] Applicants have discovered that the heat transfer compositions of the present invention, including each of Heat Transfer Compositions 1-10, can provide an exceptionally advantageous and unexpected combination of properties, including excellent refrigerant / lubricant compatibility, including miscibility with POE and / or PVE lubricants, in addition to the advantageous properties identified herein with respect to refrigerants, over the range of operating temperatures and concentrations used in stationary air conditioning systems (including residential air conditioning, commercial air conditioning, VRF air conditioning), chillers (including air-to-water chillers), heat pump systems (including residential air-to-water heat pump systems), and commercial cooling (including medium and low temperature cooling).

[0066] A lubricant consisting essentially of POE having a viscosity of about 30 to about 70 at 40° C. as measured according to ASTM D445 is referred to herein as Lubricant 1.

[0067] Commercially available POEs preferred for use in the heat transfer compositions of the present invention include neopentyl glycol dipelargonate available as Emery 2917® and Hatcol 2370®, and pentaerythritol derivatives such as those sold under the trade names Emkarate RL32-3MAF and Emkarate RL68H by CPI Fluid Engineering. Emkarate RL32-3MAF and Emkarate RL68H are preferred POE lubricants having the properties specified below.

[0068] [Table 1]

[0069] Preferred heat transfer compositions include the refrigerants of the present invention, including each of Refrigerants 1-10, and Lubricant 1. The heat transfer composition described in this paragraph may be referred to as Heat Transfer Composition 11 for convenience.

[0070] A preferred heat transfer composition comprises a refrigerant 7 and a lubricant 1. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 12 for convenience.

[0071] A preferred heat transfer composition comprises a refrigerant 8 and a lubricant 1. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 13 for convenience.

[0072] A preferred heat transfer composition comprises a refrigerant 9 and a lubricant 1. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 14 for convenience.

[0073] A preferred heat transfer composition comprises a refrigerant 10 and a lubricant 1. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 15 for convenience.

[0074] A lubricant having a viscosity of about 30 to about 70 at 40° C., measured in accordance with ASTM D445, and consisting essentially of POE, based on the weight of the heat transfer composition, is referred to herein as Lubricant 2.

[0075] Commercially available polyvinyl ethers having a viscosity of about 30 to about 70 at 40° C., as measured in accordance with ASTM D445, suitable for use in the heat transfer compositions of the present invention include those sold by Idemitsu under the trade names FVC32D and FVC68D.

[0076] Preferred heat transfer compositions include a refrigerant of the present invention, including each of Refrigerants 1-10, and Lubricant 2. The heat transfer composition described in this paragraph may be conveniently referred to as Heat Transfer Composition 16.

[0077] A preferred heat transfer composition comprises a refrigerant 7 and a lubricant 2. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 17 for convenience.

[0078] A preferred heat transfer composition includes a refrigerant 8 and a lubricant 2. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 18 for convenience.

[0079] A preferred heat transfer composition comprises a refrigerant 9 and a lubricant 2. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 19 for convenience.

[0080] A preferred heat transfer composition comprises a refrigerant 10 and a lubricant 2. The heat transfer composition described in this paragraph may be referred to as heat transfer composition 20 for convenience.

[0081] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-20, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.1% to about 5% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as heat transfer composition 21.

[0082] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-20, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.1% to about 2% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as heat transfer composition 22.

[0083] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-20, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.1% to about 1% by weight of the heat transfer composition. The heat transfer composition described in this paragraph may be conveniently referred to as heat transfer composition 23.

[0084] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-20, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.1% to about 0.5% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as heat transfer composition 24.

[0085] The present invention includes heat transfer compositions of the present invention, including each of heat transfer compositions 1-20, wherein the lubricant is present in the heat transfer composition in an amount of from about 0.2% to about 0.5% by weight of the heat transfer composition. For convenience, the heat transfer composition described in this paragraph may be referred to as heat transfer composition 25.

[0086] Other additives not mentioned herein may also be included by one skilled in the art in view of the teachings contained herein without departing from the novel and essential features of the present invention.

[0087] Combinations of surfactants and solubilizers may also be added to the compositions of the present invention to aid oil solubility, as disclosed in U.S. Pat. No. 6,516,837, the disclosure of which is incorporated by reference in its entirety.

[0088] Methods, Uses, and Systems system The present invention includes all types of heat transfer systems comprising a refrigerant of the present invention, including each of Refrigerants 1-10, and / or a heat transfer composition of the present invention, including each of Heat Transfer Compositions 1-25. The heat transfer system described in this paragraph may be referred to as Heat Transfer System 1 for convenience.

[0089] The present invention also includes, and provides certain advantages in connection with, stationary air conditioning systems comprising a refrigerant of the present invention, including each of Refrigerants 1-10, and / or a heat transfer composition of the present invention, including each of Heat Transfer Compositions 1-25. The heat transfer system described in this paragraph may be referred to as Heat Transfer System 2 for convenience.

[0090] The present invention also includes, and provides certain advantages in connection with, stationary residential air conditioning systems comprising a refrigerant of the present invention, including each of Refrigerants 1-10, and / or a heat transfer composition of the present invention, including each of Heat Transfer Compositions 1-25. The heat transfer system described in this paragraph may be referred to as Heat Transfer System 3 for convenience.

[0091] The present invention also includes, and provides certain advantages in connection with, stationary commercial air conditioning systems comprising a refrigerant of the present invention, including each of Refrigerants 1-10, and / or a heat transfer composition of the present invention, including each of Heat Transfer Compositions 1-25. The heat transfer system described in this paragraph may be referred to as Heat Transfer System 4 for convenience.

[0092] The present invention also includes, and provides certain advantages in connection with, stationary VRF air conditioning systems comprising a refrigerant of the present invention, including each of Refrigerants 1-10, and / or a heat transfer composition of the present invention, including each of Heat Transfer Compositions 1-25. The heat transfer system described in this paragraph may be referred to as Heat Transfer System 5 for convenience.

[0093] The present invention also includes, and provides certain advantages in connection with, coolers (including air-cooled coolers) that comprise a refrigerant of the present invention, including each of Refrigerants 1-10, and / or a heat transfer composition of the present invention, including each of Heat Transfer Compositions 1-25. The heat transfer system described in this paragraph may be referred to as Heat Transfer System 6 for convenience.

[0094] The present invention also includes, and provides certain advantages in connection with, heat pump systems (including residential air-to-water heat pump systems) comprising a refrigerant of the invention, including each of Refrigerants 1-10, and / or a heat transfer composition of the invention, including each of Heat Transfer Compositions 1-25. The heat transfer system described in this paragraph may be referred to as Heat Transfer System 7 for convenience.

[0095] The present invention also includes, and provides certain advantages in connection with, commercial cooling (including low temperature commercial cooling and medium temperature commercial cooling) comprising a refrigerant of the present invention, including each of Refrigerants 1-10, and / or comprising a heat transfer composition of the present invention, including each of Heat Transfer Compositions 1-25. The heat transfer system described in this paragraph may be referred to as heat transfer system 8 for convenience.

[0096] Heat transfer systems include those identified by the heat transfer system numbers shown in the table below, where the numbers in the refrigerant column refer to the refrigerant numbers defined herein.

[0097] [Table 2-1]

[0098] [Table 2-2]

[0099] Examples of residential air conditioning systems that may be advantageously used with a refrigerant of the invention, including each of Refrigerants 1-10, and / or a heat transfer composition of the invention, including each of Heat Transfer Compositions 1-25, include ducted or non-ducted split, window, or portable air conditioning systems.

[0100] Examples of commercial air conditioning systems that may be advantageously used with the refrigerants of the invention, including each of Refrigerants 1-10, and / or with the heat transfer compositions of the invention, including each of Heat Transfer Compositions 1-25, include chiller systems, supermarket refrigeration, packaged rooftop units, and commercially available variable refrigerant flow (VRF) systems.

[0101] Examples of heat pumps that can be advantageously used with the refrigerants of the invention, including each of Refrigerants 1-10, and / or the heat transfer compositions of the invention, including each of Heat Transfer Compositions 1-25, include residential air-to-water heat pump / hot water systems, and commercial air-source, water-source, or geothermal source heat pump systems.

[0102] Examples of coolers that may be advantageously used with the refrigerants of the present invention, including each of Refrigerants 1-10, and / or the heat transfer compositions of the present invention, including each of Heat Transfer Compositions 1-25, include positive displacement coolers, and air- or water-cooled direct expansion coolers, either modular or conventionally packaged.

[0103] In the case of a heat transfer system of the present invention including a compressor and a compressor lubricant in the system, the system can include a lubricant loading of the refrigerants of the present invention including each of refrigerants 1-10 and lubricants including POE and PVE such that the lubricant loading in the system is about 5% to 60% by weight, or about 10% to about 60% by weight, or about 20% to about 50% by weight, or about 20% to about 40% by weight, or about 20% to about 30% by weight, or about 30% to about 50% by weight, or about 30% to about 40% by weight. As used herein, the term "lubricant loading" refers to the total weight of the lubricant contained in the system as a percentage of the sum of the lubricant and refrigerant contained in the system. Such a system can also include a lubricant loading of about 5% to about 10% by weight, or about 8% by weight of the heat transfer composition.

[0104] Exemplary Heat Transfer Systems As described in detail below, the preferred system of the present invention includes a compressor, a condenser, an expansion device, and an evaporator, all in fluid communication using piping, valves, and control systems so that the refrigerant and associated components of the heat transfer composition can flow through the system in a known manner to complete a cooling cycle. An exemplary schematic diagram of such a basic system is shown in FIG. 1. Specifically, the system shown generally in FIG. 1 shows a compressor 10, which provides compressed refrigerant vapor to a condenser 20. The compressed refrigerant vapor condenses to produce liquid refrigerant, which is then directed to an expansion device 40, which produces refrigerant at a low pressure, and then provided to an evaporator 50. Within the evaporator 50, the liquid refrigerant absorbs heat from the body or cooled fluid to produce a refrigerant vapor, which is then provided to the suction line of the compressor.

[0105] The cooling system shown in Figure 2 is the same as that described above in connection with Figure 1, except that it includes a vapor injection system including a heat exchanger 30 and a bypass expansion valve 25. The bypass expansion device 25 provides liquid refrigerant to the heat exchanger 30 at a reduced pressure, and therefore at a low temperature, by diverting a portion of the refrigerant flow at the condenser outlet through the device. This relatively cool liquid refrigerant then exchanges heat with the relatively hotter remaining liquid from the condenser. This action produces subcooled liquid in the main expansion device 40 and the evaporator 50, and relatively cool refrigerant vapor is returned to the compressor 10. Injecting cooled refrigerant vapor into the suction side of the compressor in this manner serves to maintain the compressor discharge temperature within acceptable limits, which may be particularly advantageous in low temperature systems utilizing high compression ratios.

[0106] The cooling system shown in Figure 3 is similar to that described above in connection with Figure 1, except that it includes a liquid injection system that includes a bypass valve 26. Bypass valve 26 diverts a portion of the liquid refrigerant exiting the condenser to a liquid injection port in the compressor, preferably compressor 10. Injecting liquid refrigerant into the suction side of the compressor in this manner serves to maintain the compressor discharge temperature within acceptable limits, which can be particularly advantageous in low temperature systems that utilize high compression ratios.

[0107] The cooling system shown in Figure 4 is the same as that described above in connection with Figure 1, except that it includes a liquid line / suction line heat exchanger 35. Valve 26 diverts a portion of the refrigerant flow at the condenser outlet to the liquid line / suction line heat exchanger where heat is transferred from the liquid refrigerant to the refrigerant vapor exiting the evaporator 50.

[0108] The cooling system shown in Figure 5 is the same as that described above in connection with Figure 1, except that it includes an oil separator 60 connected to the outlet of the compressor 10. As known to those skilled in the art, a certain amount of compressor lubricant is typically carried over into the compressor discharge refrigerant vapor, and the oil separator is included to provide a means to separate the lubricant liquid from the refrigerant vapor, with the resulting refrigerant vapor having a reduced lubricant oil content proceeding to a condenser inlet, and then the liquid lubricant is returned to a lubricant reservoir, such as a lubricant receiver, for use in lubricating the compressor. In a preferred embodiment, the oil separator includes a sealing material as described herein, preferably in the form of a filter or solid core.

[0109] It will be appreciated by those skilled in the art that the different device / configuration options shown separately in each of Figures 2-5 may be combined and used together as deemed advantageous for any given application.

[0110] use General Use The present invention also includes the use of the refrigerants of the present invention, including each of Refrigerants 1-10, in stationary air conditioning systems and provides certain advantages associated therewith.

[0111] The present invention also includes the use of refrigerant 7 in stationary air conditioning systems and provides certain advantages in connection therewith.

[0112] The present invention also includes the use of refrigerant 8 in stationary air conditioning systems and provides certain advantages in connection therewith.

[0113] The present invention also includes the use of the refrigerant 9 in stationary air conditioning systems and provides certain advantages in connection therewith.

[0114] The present invention also includes the use of the refrigerant 10 in stationary air conditioning systems and provides certain advantages in connection therewith.

[0115] The present invention also includes the use of the refrigerants of the present invention, including each of Refrigerants 1-10, in a chiller and provides certain advantages associated therewith.

[0116] The present invention also includes the use of a refrigerant 7 in the chiller and provides certain advantages associated therewith.

[0117] The present invention also includes the use of a refrigerant 8 in a chiller and provides certain advantages associated therewith.

[0118] The present invention also includes the use of refrigerant 9 in a chiller system and provides certain advantages associated therewith.

[0119] The present invention also includes the use of the refrigerant 10 in a chiller system and provides certain advantages associated therewith.

[0120] The present invention also includes the use of the refrigerants of the present invention, including each of Refrigerants 1-10, in heat pump systems and provides certain advantages associated therewith.

[0121] The present invention also includes the use of refrigerant 7 in a heat pump system and provides certain advantages in connection therewith.

[0122] The present invention also includes the use of refrigerant 8 in a heat pump system and provides certain advantages in connection therewith.

[0123] The present invention also includes the use of the refrigerant 9 in a heat pump system and provides certain advantages in connection therewith.

[0124] The present invention also includes the use of the refrigerant 10 in a heat pump system and provides certain advantages in connection therewith.

[0125] The present invention also includes the use of the refrigerants of the present invention, including each of Refrigerants 1-10, in commercial refrigeration systems and provides certain advantages associated therewith.

[0126] The present invention also includes the use of refrigerant 7 in commercial refrigeration systems and provides certain advantages in connection therewith.

[0127] The present invention also includes the use of refrigerant 8 in commercial refrigeration systems and provides certain advantages in connection therewith.

[0128] The present invention also includes the use of refrigerant 9 in commercial refrigeration systems and provides certain advantages in connection therewith.

[0129] The present invention also includes the use of the refrigerant 10 in commercial refrigeration systems and provides certain advantages in connection therewith.

[0130] Use of Substitutes The present invention also includes the use of the refrigerants of the present invention, including each of Refrigerants 1-10, as replacements for R-410 and provides certain advantages associated therewith. Use of the various replacements set forth in the table below is included in the present invention, with the numbers in the Replacement Refrigerant column referring to the refrigerant number as defined herein.

[0131] [Table 3-1]

[0132] [Table 3-2]

[0133] [Table 3-3]

[0134] [Table 3-4]

[0135] [Table 3-5]

[0136] [Table 3-6]

[0137] [Table 3-7]

[0138] [Table 3-8]

[0139] Retrofit use The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as retrofits for heat transfer systems and provides certain advantages associated therewith.

[0140] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-32 in stationary air conditioning systems and provides certain advantages associated therewith.

[0141] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-32 in chiller systems and provides certain advantages associated therewith.

[0142] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-32 in heat pump systems and provides certain advantages associated therewith.

[0143] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-32 in commercial cooling systems and provides certain advantages associated therewith.

[0144] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-454B in heat transfer systems and provides certain advantages associated therewith.

[0145] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-454B in stationary air conditioning systems and provides certain advantages associated therewith.

[0146] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-454B in chiller systems and provides certain advantages associated therewith.

[0147] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-454B in heat pump systems and provides certain advantages associated therewith.

[0148] The present invention also includes the use of the refrigerants of the present invention, including Refrigerants 1-10, as a retrofit for R-454B in commercial cooling systems and provides certain advantages associated therewith.

[0149] Cooling method The present invention provides a method for providing cooling, comprising: (a) evaporating a refrigerant according to the present invention (including any refrigerant selected from each of Refrigerants 1 to 10) in the vicinity of a body, article, or fluid to be cooled at a temperature of about -40°C to about +10°C to produce a refrigerant vapor; (b) compressing the refrigerant vapor to produce a refrigerant having a discharge temperature of less than about 150° C.; (c) condensing the refrigerant from the compressor at a temperature between about 20° C. and about 70° C. to produce a refrigerant vapor. The cooling method according to this paragraph is referred to herein as Method 1.

[0150] The present invention includes a method according to Cooling Method 1, wherein the refrigerant in the evaporation step has a refrigerant glide of less than 3.5° C. The cooling method according to this paragraph is referred to herein as Cooling Method 2.

[0151] The present invention includes a process according to Cooling Method 1, wherein the refrigerant in the evaporation step has a refrigerant glide of less than 3.0° C. The cooling method according to this paragraph is referred to herein as Cooling Method 3.

[0152] The present invention includes a method according to Cooling Method 1, wherein the refrigerant in the evaporation step has a refrigerant glide of less than 2.5° C. Cooling methods according to this paragraph are referred to herein as Cooling Method 4.

[0153] The present invention includes carrying out cooling according to any one of cooling methods 1 to 4 in a stationary air-conditioning system.

[0154] The present invention includes performing cooling according to any one of cooling methods 1 to 4 in a stationary residential air conditioning system.

[0155] The present invention includes providing cooling according to any one of cooling methods 1 to 4 in a stationary commercial air conditioning system.

[0156] The present invention includes performing cooling according to any one of cooling methods 1 to 4 in a stationary VRF air conditioning system.

[0157] The present invention includes performing cooling in a chiller system according to any one of cooling methods 1 to 4.

[0158] The present invention includes performing cooling according to any one of cooling methods 1 to 4 in an air-cooled chiller system.

[0159] The present invention includes performing cooling according to any one of cooling methods 1 to 4 in a heat pump system.

[0160] The present invention includes performing cooling according to any one of cooling methods 1 to 4 in a residential air-water heat pump system.

[0161] The present invention includes providing cooling in a commercial cooling system according to any one of cooling methods 1-4.

[0162] The present invention includes providing cooling according to any one of cooling methods 1-4 in a commercial low-temperature cooling system.

[0163] The present invention includes providing cooling according to any of Cooling Methods 1-4 in a commercial medium temperature cooling system.

[0164] Specific cooling methods include those identified by the cooling method numbers set forth in the table below, where the numbers in the refrigerant column refer to the refrigerant numbers defined herein, and all temperature values ​​are preceded by "about."

[0165] [Table 4]

[0166] Heating method Specific heating methods include those identified by the heating method numbers set forth in the table below, where the numbers in the refrigerant column refer to the refrigerant numbers defined herein, and all temperature values ​​are preceded by "about."

[0167] [Table 5]

[0168] The present invention includes methods for providing heated air, including each of the heating methods 1, which provide heated air at a temperature of about 15°C to about 25°C.

[0169] The present invention includes methods for providing heated air, including each of heating methods 1, which provide heated air at a temperature of about 18°C ​​to about 24°C.

[0170] The present invention includes methods of providing heat, including each of heating methods 2 and 3, which provide hot water at a temperature of about 50°C to about 65°C.

[0171] The present invention includes methods of providing heat, including each of heating methods 2 and 3, which provide hot water at a temperature of about 50°C to about 60°C.

[0172] The present invention includes methods of providing heat, including each of heating methods 2 and 3, which provide hot water at a temperature of about 50°C to about 55°C.

[0173] Systems, methods and apparatus for use Examples of commonly used compressors, for purposes of this invention, include reciprocating, rotary (including rolling piston and rotary vane), scroll, screw, and centrifugal compressors. Thus, the present invention provides each and any of the heat transfer compositions described herein, including refrigerants including each of Refrigerants 1-10, and / or those containing any one of Refrigerants 1-10, for use in a heat transfer system comprising a reciprocating, rotary (including rolling piston and rotary vane), scroll, screw, or centrifugal compressor.

[0174] Examples of commonly used expansion devices, for purposes of this invention, include capillary tubes, fixed orifices, thermal expansion valves, and electronic expansion valves. Accordingly, the present invention provides each and any of the refrigerants, including each of Refrigerants 1-10, and / or heat transfer compositions, including those containing any one of Refrigerants 1-10, described herein for use in a heat transfer system comprising a capillary tube, fixed orifice, thermal expansion valve, or electronic expansion valve.

[0175] For purposes of the present invention, the evaporator and condenser may each independently be selected from a finned tube heat exchanger, a microchannel heat exchanger, a shell-and-tube, a plate heat exchanger, and a tube-in-tube heat exchanger. Accordingly, the present invention provides each and any of the refrigerants and / or heat transfer compositions described herein for use in a heat transfer system in which the evaporator and condenser together form a finned tube heat exchanger, a microchannel heat exchanger, a shell-and-tube, a plate heat exchanger, or a tube-in-tube heat exchanger.

[0176] The heat transfer compositions of the present invention can be used in heating and cooling applications. In a particular aspect of the present invention, the heat transfer compositions can be used in cooling methods that involve condensing the heat transfer composition and then evaporating it in the vicinity of the article or body to be cooled.

[0177] The refrigerants of the present invention, including Refrigerants 1-10, and heat transfer compositions of the present invention, including Heat Transfer Compositions 1-25, are each provided for use in commercial refrigeration systems, including use in each of the following: Low temperature commercial refrigerators, Supermarket refrigeration, low temperature commercial freezer, Ice maker, Vending machines, Refrigeration systems for low-temperature transport, Industrial freezers, Industrial refrigerators, and Cryogenic cooler.

[0178] The heat transfer compositions of the present invention are provided for use in medium temperature refrigeration systems, preferably used to cool food or beverages, such as in refrigerators or bottle coolers, etc. The system typically has an air-refrigerant evaporator for cooling the food or beverage, a reciprocating, scroll, or screw, or rotary compressor, an air-refrigerant condenser for exchanging heat with ambient air, and a thermal or electronic expansion valve.

[0179] The heat transfer compositions of the present invention are provided for use in low temperature refrigeration systems, preferably used in freezers or ice machines. The system typically includes an air-refrigerant evaporator for cooling food or beverages, a reciprocating, scroll, or rotary compressor, an air-refrigerant condenser for exchanging heat with ambient air, and a thermal or electronic expansion valve.

[0180] Each of the heat transfer compositions described herein, including those containing any one of refrigerants 1-10, is provided specifically for use in low temperature systems equipped with reciprocating, rotary (rolling piston or rotary vane), or scroll compressors.

[0181] Each of the heat transfer compositions described herein, including those containing any one of refrigerants 1-10, are provided specifically for use in medium temperature systems equipped with reciprocating, rotary (rolling piston or rotary vane), or scroll compressors.

[0182] The compositions of the present invention exhibit many of the desirable properties of R-410A, but have operating characteristics, i.e., capacity and efficiency (COP), that are substantially similar or substantially consistent with R-410A, while having a GWP of less than 300. This allows the claimed compositions to replace R-410A in existing heat transfer systems without requiring any major system modifications, e.g., to the condenser, evaporator, and / or expansion valve. Thus, the compositions may be used as direct replacements for R-410A that are used or suitable for use with R-410A.

[0183] Thus, the refrigerants of the present invention, including each of Refrigerants 1-10, preferably exhibit operating characteristics compared to R-410A, and the efficiency (COP) of the compositions is between 95% and 105% of the efficiency of R-410A in heat transfer systems, such that the compositions of the present invention should replace R-410A refrigerant.

[0184] Thus, the refrigerants of the present invention, including each of Refrigerants 1-10, preferably exhibit operating characteristics comparable to R-410A, and the capacity of the compositions is 97-103% of the capacity of R-410A in heat transfer systems, such that the compositions of the present invention should replace R-410A refrigerant.

[0185] Thus, the refrigerants of the present invention, including each of Refrigerants 1-10, preferably exhibit operating characteristics comparable to R-410A, the capacity of the compositions being 97-103% of the capacity of R-410A in a heat transfer system, and the efficiency (COP) being equal to or greater than the efficiency of R-410A in a heat transfer system, such that the compositions of the present invention should replace the R-410A refrigerant.

[0186] Preferably, the refrigerants of the present invention, including each of Refrigerants 1-102, preferably exhibit operating characteristics comparable to R-410A, and the efficiency (COP) of the compositions is 100-105% of the efficiency of R-410A in heat transfer systems, such that the compositions of the present invention should replace R-410A refrigerant.

[0187] In order to maintain the reliability of the heat transfer system, it is preferred that the compositions of the present invention further exhibit the following properties compared to R-410A: The discharge temperature is 10°C or less higher than that of R-410A. The compressor pressure ratio is 95 to 105% of that of R-410A. The compositions of the present invention are used to replace R-410A refrigerant.

[0188] The compositions of the present invention are alternatively provided to replace R-410A in cooling systems. Thus, each of the heat transfer compositions described herein, including the heat transfer compositions comprising any one of refrigerants 1-10, can be used to replace R-410A in any one of the systems disclosed herein.

[0189] The present invention relates to the use of the refrigerants of the present invention, including each of refrigerants 1 to 10, in a medium or low temperature cooling system, the refrigerant being: (a) In the system, the efficiency (COP) is about 95% to about 105% of the efficiency of R-410A; and (b) It is slightly flammable. EXAMPLES

[0190] Comparative Example 1 Two compositions, shown in Table CE1 below, were evaluated for comparison with the preferred formulation of the present invention.

[0191] [Table 6]

[0192] A composition identified as CE1 was tested to obtain the experimental data necessary to determine by simulation its burn rate under ASHRAE Standard 34 and was found to have a burn rate of 10.8 cm / sec. Accordingly, this composition did not meet the requirements for a Class 2L refrigerant (mildly flammable) by ASHRAE. A composition identified as CE1 was tested in accordance with ASHRAE Standard 34 and found to have a burn rate well above 10 and would not be classified as Class 2L and would therefore be considered flammable.

[0193] Examples 1 to 6 Two compositions according to the invention are formulated as shown in Tables E1-6 below.

[0194] [Table 7]

[0195] As can be seen from Table E1-6 above, all of the compositions tested achieve a burn rate of less than 10 and are therefore Class 2L refrigerants, while at the same time each refrigerant also has a GWP of less than 300. This is an unexpected combination of properties.

[0196] Example of system performance In the following system performance examples, the refrigerants identified as E1 and E2 in Tables E1-6 above were analyzed as described herein. Each composition was subjected to thermodynamic analysis to determine its capacity to match the operating characteristics of R-410A in various cooling systems. The analysis was performed using experimental data collected on the properties of various binary pairs of the components used in the compositions. The vapor / liquid equilibrium behavior of each component was determined and tested in a series of binary pairs including each of HFO-1234yf, HFC-32, and HFC-161. The composition of each binary pair was varied over a series of relative percentages in the experimental evaluation, and the mixing parameters of each binary pair were regressed to the experimentally obtained data. The vapor / liquid equilibrium behavior data for the binary pairs was available in the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database software (Refprop 9.1 NIST Standard Database 2013) and was used in the examples. The parameters selected to perform the analysis were the same compressor volume for all refrigerants, the same operating conditions for all refrigerants, and the same compressor isentropic efficiency and volumetric efficiency for all refrigerants. For each example, simulations were performed using measured vapor-liquid equilibrium data. Simulation results are reported for each example.

[0197] Example E7 - Residential Air Conditioning System (Cooling) Residential air conditioning systems used to provide cool air (approximately 12°C) to buildings during the summer are tested. Typical system types include ducted split, ductless split, window, and portable air conditioning systems. The systems typically have an air-refrigerant evaporator (indoor coil), a compressor, an air-refrigerant condenser (outdoor coil), and an expansion device. The evaporator and condenser are typically finned tube or microchannel heat exchangers. The compressor is typically a reciprocating, rotary (rolling piston or rotary vane), or scroll compressor. The expansion device is typically a capillary tube, thermal expansion valve, or electronic expansion valve. The refrigerant evaporation temperature is typically in the range of about 0 to about 10°C, while the condensation temperature is in the range of about 40 to about 70°C.

[0198] Refrigerants E1 and E2 were used in a simulation of the residential air conditioning system described above, and the performance results are reported below in Table 7. The operating conditions were as follows: condensing temperature = 46°C (corresponding outdoor ambient temperature = 35°C), condenser subcooling = 5.5°C, evaporating temperature = 7°C (corresponding indoor ambient temperature = 26.7°C), evaporator superheat = 5.5°C, isentropic efficiency = 70%, volumetric efficiency: 100%, and temperature rise in the suction line = 5.5°C.

[0199] [Table 8] • Table E7 shows the thermodynamic performance of residential air conditioning systems compared to R410A systems. • In newer systems, compressor volume can be increased to compensate for capacity. Compositions E1 and E2 are each unexpectedly capable of achieving an evaporator glide of less than 4°C in this system while simultaneously achieving a GWP of less than 300 and a flammability rating of 2L.

[0200] Example 8 - Variable refrigerant flow air conditioning system (cooling) Variable refrigerant flow air conditioning systems (VRF) are commonly used to supply cool air (approximately 12°C) to buildings during the summer months. VRFs are typically installed with an air conditioner inverter that adds a DC inverter to the compressor to support variable motor speeds and therefore variable refrigerant flow, rather than simply performing an on / off operation. By operating at various speeds, the VRF unit only operates at the rate required, allowing for significant energy savings at load conditions. The compressor is typically a rotary or scroll compressor. The expansion device is typically a thermal expansion valve or an electronic expansion valve. The refrigerant evaporation temperature is typically in the range of about 0 to about 10°C, while the condensation temperature is typically in the range of about 40 to about 70°C.

[0201] The VRF used to supply cool air (approximately 12°C) to a building during the summer season is tested. Refrigerants E1 and E2 were used to simulate the VRF as described above, and the performance results are reported in Table E8 below. The operating conditions were: condensing temperature = 46°C (corresponding outdoor ambient temperature = 35°C), condenser subcooling = 5.5°C, evaporating temperature = 7°C (corresponding indoor ambient temperature = 26.7°C), evaporator superheat = 5.5°C, isentropic efficiency = 70%, volumetric efficiency: 100%, and temperature rise in the suction line = 5.5°C.

[0202] [Table 9] • Table E8 shows the thermodynamic performance of the variable refrigerant flow air conditioning system compared to the R410A system. • In newer systems, compressor volume can be increased to compensate for capacity. Compositions E1 and E2 are each unexpectedly capable of achieving an evaporator glide of less than 4°C in this system while simultaneously achieving a GWP of less than 300 and a flammability rating of 2L.

[0203] Example 9 - Commercial Air Conditioning System - Chiller Commercial air conditioning systems (chillers) are typically used to provide chilled water (approximately 7°C) to large buildings such as offices, hospitals, etc. Depending on the application, chiller systems may operate year-round. Chiller systems can be air-cooled or water-cooled. Air-cooled chillers typically have a plate, tube-in-tube, or shell-in-tube evaporator to provide the chilled water, a reciprocating or scroll compressor, a round-tube plate-fin or microchannel condenser to exchange heat with the ambient air, and a thermal or electronic expansion valve. Water-cooled systems typically have a shell-and-tube evaporator to provide the chilled water, a reciprocating or scroll compressor, a shell-and-tube condenser to exchange heat with a cooling tower or water from lakes, oceans, and other natural sources, and a thermal or electronic expansion valve. Refrigerant evaporation temperatures are typically in the range of about 0 to about 10°C, while condensation temperatures are in the range of about 40 to about 70°C.

[0204] A commercial air conditioning system (chiller) used to supply chilled water (7°C) to large buildings (such as office and hospital buildings) was tested for refrigerants E1 and E2 and the performance results are reported in Table E9 below. The operating conditions were: condensing temperature = 46°C, condenser subcooling = 5.5°C, evaporating temperature = 4.5°C, evaporator superheat = 5.5°C, isentropic efficiency = 70%, volumetric efficiency: 100%, and temperature rise in the suction line = 2°C.

[0205] [Table 10] • Table E9 shows the thermodynamic performance of a commercial air-cooled chiller system compared to an R410A system.

[0206] In the new system, the compressor volume can be increased to compensate for the capacity. Compositions E1 and E2 are each unexpectedly able to achieve an evaporator glide of less than 4°C in this system while simultaneously achieving a GWP of less than 300 and a flammability rating of 2L.

[0207] Example 10 - Residential heat pump system (heating) Residential heat pump systems are used to provide warm air (21°C) to buildings during the winter and are typically configured the same as residential air conditioning systems. However, when such systems are operating in heat pump mode, the refrigerant flow is reversed and the indoor coil becomes the condenser and the outdoor coil becomes the evaporator. Typical system types are ducted split and ductless split heat pump systems. The evaporator and condenser are typically finned tube or microchannel heat exchangers and the compressor is typically a reciprocating or rotary (rolling piston or rotary vane) or scroll compressor. The expansion device is typically a capillary tube, a thermal expansion valve or an electronic expansion valve. The refrigerant evaporation temperature is typically in the range of about -30 to about 5°C, while the condensation temperature is in the range of about 35 to about 50°C.

[0208] Refrigerants E1 and E2 were used in a simulation of a residential heat pump system as described above, and the performance results are in Table E10 below. The operating conditions were: condensing temperature = 41°C, condenser subcooling = 5.5°C, evaporating temperature = 0.5°C, evaporator superheat = 5.5°C, isentropic efficiency = 70%, volumetric efficiency: 100%, and temperature rise in the suction line = 5.5°C.

[0209] [Table 11] • Table E10 shows the thermodynamic performance of residential heat pump systems compared to R410A systems. • In newer systems, compressor volume can be increased to compensate for capacity. Compositions E1 and E2 are each unexpectedly capable of achieving an evaporator glide of less than 4°C in this system while simultaneously achieving a GWP of less than 300 and a flammability rating of 2L.

[0210] Example 11 - Residential Air-to-Water Heat Pump Hot Water System Residential air-to-water heat pump hot water systems are typically used to supply hot water (about 55°C) to buildings for underfloor heating or similar applications during the winter. Hot water systems usually have a finned or microchannel evaporator to exchange heat with the ambient air, a reciprocating, rotary, or scroll compressor, a plate, tube-in-tube, or shell-and-tube condenser to heat the water, and a thermal or electronic expansion valve. Refrigerant evaporation temperatures are typically in the range of about -30 to about 5°C, while condensation temperatures are typically in the range of about 50 to about 90°C.

[0211] A residential air-to-water heat pump hot water system used to supply hot water (55°C) to a building for underfloor heating or similar applications in winter was tested with refrigerants E1 and E2, and the performance results are reported in Table E115. The operating conditions were as follows: condensing temperature = 60°C (corresponding indoor outlet water temperature = 50°C), condenser subcooling = 5.5°C, evaporating temperature = 0.5°C (corresponding outdoor ambient temperature = 8.3°C), evaporator superheat = 5.5°C, isentropic efficiency = 70%, volumetric efficiency: 100%, and temperature rise in the suction line = 2°C.

[0212] [Table 12] ●Table E11 shows the thermodynamic performance of a residential air-to-water heat pump hot water system compared to an R410A system. • In newer systems, compressor volume can be increased to compensate for capacity.

[0213] Compositions E1 and E2 are each unexpectedly capable of achieving an evaporator glide of less than 3° C. in this system while simultaneously achieving a GWP of less than 300 and a flammability rating of 2L.

[0214] Example 12 - Medium Temperature Refrigeration System Medium temperature refrigeration systems are used to cool food or beverages in refrigerators and bottle coolers, etc. The systems typically have an air-refrigerant evaporator for cooling the food or beverage, a reciprocating, scroll, or screw compressor, an air-refrigerant condenser for exchanging heat with ambient air, and a thermal or electronic expansion valve. The refrigerant evaporation temperature is in the range of about -12 to about 0°C, while the condensation temperature is in the range of about 20 to about 70°C.

[0215] A medium temperature refrigeration system used to cool food or beverages in refrigerators and bottle coolers etc. was tested using refrigerants EA1 and E2 and the performance results are reported in Table E12 below. Operating conditions were: Condensing temperature = 40.6°C, Condenser subcooling = 5.5°C, Evaporating temperature = -6.7°C, Evaporator superheat = 5.5°C, Isentropic efficiency = 70%, Volumetric efficiency: 100%, Superheat in suction line = 15°C.

[0216] [Table 13] • Table E12 shows the thermodynamic performance of the medium temperature refrigeration system compared to the R410A system. • In newer systems, compressor volume can be increased to compensate for capacity. Compositions E1 and E2 are each unexpectedly capable of achieving an evaporator glide of less than 4°C in this system while simultaneously achieving a GWP of less than 300 and a flammability rating of 2L.

[0217] Example 13 - Low temperature refrigeration system Low temperature refrigeration systems are used to freeze food, for example in ice cream makers and freezers. The systems usually have an air-refrigerant evaporator, a reciprocating, scroll, or screw compressor, an air-refrigerant condenser for exchanging heat with ambient air, and a thermal or electronic expansion valve. The refrigerant evaporation temperature is in the range of about -40 to about -12°C, while the condensation temperature is in the range of about 20 to about 70°C.

[0218] A low temperature refrigeration system used for freezing food such as ice cream in ice cream makers and freezers etc. was tested using refrigerants E1 and E2 and the performance results are given in Table E13. The operating conditions were: condensing temperature = 40.6°C, condenser subcooling = 1°C, evaporating temperature = -31.6°C, superheat at evaporator outlet = 5.5°C, isentropic efficiency = 70%, volumetric efficiency: 100%, superheat in suction line = 30.6°C.

[0219] [Table 14] • Table E13 shows the thermodynamic performance of the low temperature refrigeration system compared to the R410A system. • In newer systems, compressor volume can be increased to compensate for capacity. Compositions E1 and E2 are each unexpectedly capable of achieving an evaporator glide of less than 4°C in this system while simultaneously achieving a GWP of less than 300 and a flammability rating of 2L.

Claims

1. A refrigerant comprising at least about 98.5% by weight of the following three compounds, each compound being present in the following relative percentages: 33.0% to 43.5% by weight of difluoromethane (HFC-32), 48.5% to 67.0% by weight of 2,3,3,3-tetrafluoropropene (HFO-1234yf), and A refrigerant present in the range of 1.0 wt% to 6.0 wt% fluoroethane (HFC-161), said refrigerant being a Class 2L refrigerant and having a GWP of less than 300, preferably 295 or less.

2. A refrigerant consisting essentially of the following three compounds, each compound being present in the following relative percentages: 40% to 45% by weight of HFC-32, 49% to 55% by weight of HFO-1234yf, and A refrigerant present at 1.0% to 6.0% by weight of HFC-161.

3. consisting essentially of the following three compounds, each compound being present in the following relative percentages: 41.5% by weight to 44.5% by weight of HFC-32, 49.5% to 53.5% by weight of HFO-1234yf, and 3. The refrigerant of claim 2 present at 2.0% to 6.0% by weight of HFC-161.

4. consisting essentially of the following three compounds, each compound being present in the following relative percentages: 43.5 wt% + 0.5 / - 2 wt% HFC-32, 52.5 wt% + 1 / - 2 wt% HFO-1234yf, and 4. The refrigerant of claim 3, which is present at 4% + 1 / - 2% by weight of HFC-161.

5. It consists of the following three compounds, each compound being present in the following relative percentages: 43.5 wt% + 0.5 / - 2 wt% HFC-32, 52.5 wt% + 1 / - 2 wt% HFO-1234yf, and 5. The refrigerant of claim 4, which is present at 4% + 1 / - 2% by weight of HFC-161.

6. 6. A method of heat transfer comprising evaporating a refrigerant according to any one of claims 1 to 5, wherein the refrigerant has an evaporator glide of less than 5°C.

7. 7. The refrigerant of claim 6, wherein the refrigerant has an evaporator glide of less than 4°C.

8. A heat transfer composition comprising the refrigerant of claim 5 and at least one lubricant selected from POE and PVE.

9. A heat transfer system comprising a compressor, an evaporator, and a condenser, and comprising the heat transfer composition of claim 8, preferably the heat transfer system comprising one or more of an air conditioning system, a chiller, and a heat pump.

10. 10. The heat transfer system of claim 9, wherein the heat transfer system comprises one or more of residential air conditioning, commercial air conditioning, chillers, residential air-to-water heat pump hot water systems, medium temperature cooling, and low temperature cooling.

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