Heat transfer compositions, methods, and systems

Abstract

To provide refrigerant compositions which can be used as a replacement for R-410A and which exhibit, in preferred embodiments, a desired mosaic of properties of excellent heat transfer properties, chemical stability, low or no toxicity, non-flammability, lubricant miscibility and lubricant compatibility in combination with low Global Warming Potential (GWP) and near-zero ODP.SOLUTION: A refrigerant comprises at least about 97 wt.% of the following three compounds, with each compound being present in the following relative percentages: 39-45 wt.% of difluoromethane (HFC-32); 1-4 wt.% of pentafluoroethane (HFC-125); and 51-57 wt.% of trifluoroiodomethane (CF3I).SELECTED DRAWING: None

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of priority of U.S. Provisional Patent Application No. 62 / 623,887, filed on January 30, 2018, which is hereby incorporated by reference in its entirety.

[0002] This application claims the benefit of priority of U.S. Provisional Patent Application No. 62 / 631,093, filed on February 15, 2018, which is hereby incorporated by reference in its entirety.

[0003] (Field of the Invention) The present invention relates to compositions, methods, and systems useful in heat transfer applications, including air - conditioning and refrigeration applications. In certain aspects, the present invention relates to compositions useful in heat transfer systems of the type in which refrigerant R - 410A would be used. The compositions of the present invention are particularly useful for introducing additional heat exchange systems, including systems designed for use as alternatives to refrigerant R - 410A for heating and cooling applications and for use with R - 410A.

Background Art

[0004] For industrial, commercial, and household use, mechanical refrigeration systems, as well as related heat transfer devices such as heat pumps and air conditioners, are well - known in the art. Chlorofluorocarbons (CFCs) were developed in the 1930s as refrigerants for such systems. However, since the 1980s, the impact of CFCs on the stratospheric ozone layer has received much attention. In 1987, many governments signed the Montreal Protocol for the protection of the global environment, which established a timetable for the phase - out of CFC products. More environmentally acceptable materials containing hydrogen, namely hydrochlorofluorocarbons (HCFCs), replaced CFCs.

[0005] One of the most commonly used hydrochlorofluorocarbons was chlorodifluoromethane (HCFC-22). However, subsequent amendments to the Montreal Protocol accelerated the phased reduction of CFCs and scheduled the phased reduction of HCFCs, including HCFC-22.

[0006] In response to the need for non-flammable, non-toxic alternatives to CFCs and HCFCs, several hydrofluorocarbons (HFCs) with a zero ozone depletion potential have been developed in the industry. Since it does not contribute to ozone depletion, R-410A (a 50:50 w / w blend of difluoromethane (HFC-32) and pentafluoroethane (HFC-125)) has been adopted as an industrial substitute for HCFC-22 in air conditioning and chiller applications. However, R-410A is not a drop-in replacement for R-22. Therefore, the replacement of R-22 with R-410A required a redesign of the major components within the heat exchange system, including the replacement and redesign of the compressor to accommodate the substantially higher operating pressures and volumes of R-410A compared to R-22.

[0007] While R-410A has an acceptable ozone depletion potential (ODP) compared to R-22, its high global warming potential of 2088 poses problems for the continued use of R-410A. Therefore, there is a need in the art for a replacement of R-410A with a more environmentally acceptable alternative.

[0008] As shown in Table 1, the EU has implemented F-gas regulations to limit the HFCs that can be marketed within the EU since 2015. By 2030, only 21% of the amount of HFCs sold in 2015 will be available. Therefore, as a long-term solution, it is desirable to limit the GWP to less than 427.

[0009]

Table 1

[0010] It is understood in the art that alternative heat transfer fluids desirably possess a mosaic of properties that are difficult to achieve, including, among other things, excellent heat transfer properties (especially those well-suited to the needs of a particular application), chemical stability, low or non-toxicity, non-flammability, lubricant miscibility, and / or lubricant compatibility. Further, any substitute for R-410A is ideally one that provides a good match to the operating conditions of R-410A in order to avoid modification or redesign of the system. Developing a heat transfer fluid that meets all of these requirements, many of which are unpredictable, is a significant challenge.

[0011] Regarding usage efficiency, it is important to note that a loss of thermodynamic performance or energy efficiency can result in an increase in the use of fossil fuels as a result of increased demand for electrical energy. Thus, the use of such refrigerants will have secondary adverse environmental impacts.

[0012] Flammability is considered an important property for many heat transfer applications. As used herein, the term “non-flammable” refers to a compound or composition that is determined to be non-flammable under the conditions described in ASTM standard E-681-2009 Standard Test Method for Concentration Limits of Flammability of Chemicals (Vapors and Gases), ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants, and Appendix B1 of ASHRAE Standard 34-2016, which is incorporated herein by reference and is referred to herein for convenience as the “non-flammability test”.

[0013] It is very important for the lubricant circulating in a vapor compression heat transfer system to be returned to the compressor in order to perform its intended lubricating function, for maintaining system efficiency and for proper and reliable operation of the compressor. Otherwise, the lubricant can accumulate and potentially remain in the system's coils and pipes, including within the heat transfer components. Further, if the lubricant deposits on the inner surface of the evaporator, the heat exchange efficiency of the evaporator is reduced, thereby reducing the efficiency of the system.

[0014] Since R-410A is miscible with polyol ester (POE) at the temperatures that occur during use of such systems, R-410A is currently commonly used with POE lubricating oil in air conditioning applications. However, R-410A is immiscible with POE at the temperatures that typically occur during operation of low temperature refrigeration systems and heat pump systems. Therefore, POE and R-410A cannot be used in low temperature refrigeration or heat pump systems unless measures are taken to mitigate this immiscibility.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0015] The present applicants have, therefore, come to understand that it would be desirable to provide a composition that can be used as a substitute for R-410A in air conditioning applications, particularly in residential and commercial air conditioning applications including rooftop air conditioning, variable refrigerant flow (VRF) air conditioning, and chiller air conditioning applications. The present applicants have also come to understand that the compositions, methods, and systems of the present invention have the advantage of eliminating the drawback of being immiscible with POE at the temperatures that occur during operation of these systems, for example, in heat pump and low temperature refrigeration systems.

[0016] The present invention includes refrigerant compositions that can be used as a substitute for R-410A and that, in preferred embodiments, exhibit a desired mosaic of properties including excellent heat transfer characteristics, chemical stability, low or no toxicity, nonflammability, lubricant miscibility, and lubricant compatibility, in combination with a low global warming potential (GWP) and near zero ozone depletion potential (ODP).

[0017] The present invention includes a refrigerant comprising at least about 97% by weight of the following three compounds, with each compound present in the following relative percentages: 39 - 45% by weight of difluoromethane (HFC - 32), 1 - 4% by weight of pentafluoroethane (HFC - 125), and 51 - 57% by weight of trifluoroiodomethane (CF3I). For convenience, the refrigerant according to this paragraph is referred to herein as Refrigerant 1.

[0018] As used herein with respect to percentages based on a list of specific compounds, the term "relative percentage" means the percentage of a specific compound based on the total weight of the listed compounds.

[0019] As used herein with respect to weight percent, the term "about" with respect to the amount of a specific component means that the amount of the specific component can vary by an amount of ±1% by weight.

[0020] The present invention also includes a refrigerant comprising at least about 98.5% by weight of the following three compounds, with each compound present in the following relative percentages: 39 - 45% by weight of difluoromethane (HFC - 32), 1 - 4% by weight of pentafluoroethane (HFC - 125), and 51 - 57% by weight of trifluoroiodomethane (CF3I). For convenience, the refrigerant according to this paragraph is referred to herein as Refrigerant 2.

[0021] The present invention includes a refrigerant comprising at least about 99.5% by weight of the following three compounds, with each compound present in the following relative percentages: 39 - 45% by weight of difluoromethane (HFC - 32), 1 - 4% by weight of pentafluoroethane (HFC - 125), and 51 - 57% by weight of trifluoroiodomethane (CF3I). For convenience, the refrigerant according to this paragraph is referred to herein as Refrigerant 3.

[0022] The present invention relates to a refrigerant consisting essentially of the following three compounds, with each compound present in the following relative percentages: 39 to 45% by weight of difluoromethane (HFC-32), 1 to 4% by weight of pentafluoroethane (HFC-125), and 51 to 57% by weight of trifluoroiodomethane (CF3I). For convenience in this specification, the refrigerant according to this paragraph is referred to as Refrigerant 4.

[0023] The present invention relates to a refrigerant comprising the following three compounds, with each compound present in the following relative percentages: 39 to 45% by weight of difluoromethane (HFC-32), 1 to 4% by weight of pentafluoroethane (HFC-125), and 51% to 57% by weight of trifluoroiodomethane (CF3I). The refrigerant is non-flammable according to the non-flammability test. For convenience in this specification, the refrigerant according to this paragraph is referred to as Refrigerant 5.

[0024] The present invention relates to a refrigerant comprising at least about 97% by weight of the following three compounds, with each compound present in the following relative percentages: About 41 to about 43% by weight of difluoromethane (HFC-32), 1 to 4% by weight of pentafluoroethane (HFC-125), and About 53 to about 56% by weight of trifluoroiodomethane (CF3I). For convenience in this specification, the refrigerant according to this paragraph is referred to as Refrigerant 6.

[0025] The present invention relates to a refrigerant comprising at least about 98.5% by weight of the following three compounds, with each compound present in the following relative percentages: About 41 to about 43% by weight of difluoromethane (HFC-32), 1 to 4% by weight of pentafluoroethane (HFC-125), and ​From about 53 to about 56% by weight of trifluoroiodomethane (CF3I). The refrigerant according to this paragraph is, for convenience in this specification, referred to as Refrigerant 7.

[0026] The present invention includes a refrigerant comprising at least about 99.5% by weight of the following three compounds, wherein each compound is present in the following relative percentages: From about 41 to about 43% by weight of difluoromethane (HFC-32), From 1 to 4% by weight of pentafluoroethane (HFC-125), and From about 53 to about 56% by weight of trifluoroiodomethane (CF3I). The refrigerant according to this paragraph is, for convenience in this specification, referred to as Refrigerant 8.

[0027] The present invention includes a refrigerant consisting essentially of the following three compounds, wherein each compound is present in the following relative percentages: From about 41 to about 43% by weight of difluoromethane (HFC-32), From 1 to 4% by weight of pentafluoroethane (HFC-125), and From about 53 to about 56% by weight of trifluoroiodomethane (CF3I). The refrigerant according to this paragraph is, for convenience in this specification, referred to as Refrigerant 9.

[0028] The present invention includes a refrigerant consisting of the following three compounds, wherein each compound is present in the following relative percentages: From about 41 to about 43% by weight of difluoromethane (HFC-32), From 1 to 4% by weight of pentafluoroethane (HFC-125), and From about 53 to about 56% by weight of trifluoroiodomethane (CF3I). The refrigerant is nonflammable according to the nonflammability test defined below. The refrigerant according to this paragraph is, for convenience in this specification, referred to as Refrigerant 10.

[0029] The present invention includes a refrigerant comprising at least about 97% by weight of the following three compounds, wherein each compound is present in the following relative percentages: 41% by weight ± 1% of difluoromethane (HFC-32), 3.5 wt% ± 0.5 wt% of pentafluoroethane (HFC-125), and 55.5 wt% ± 0.5 wt% of trifluoroiodomethane (CF3I). The refrigerant according to this paragraph is, for convenience in this specification, referred to as Refrigerant 11.

[0030] The present invention includes a refrigerant comprising at least about 98.5 wt% of the following three compounds, each compound being present in the following relative percentages: 41 wt% ± 1 wt% of difluoromethane (HFC-32), 3.5 wt% ± 0.5 wt% of pentafluoroethane (HFC-125), and 55.5 wt% ± 0.5 wt% of trifluoroiodomethane (CF3I). The refrigerant according to this paragraph is, for convenience in this specification, referred to as Refrigerant 12.

[0031] The present invention includes a refrigerant comprising at least about 99.5 wt% of the following three compounds, each compound being present in the following relative percentages: 41 wt% ± 1 wt% of difluoromethane (HFC-32), 3.5 wt% ± 0.5 wt% of pentafluoroethane (HFC-125), and 55.5 wt% ± 0.5 wt% of trifluoroiodomethane (CF3I). The refrigerant according to this paragraph is, for convenience in this specification, referred to as Refrigerant 13.

[0032] The present invention includes a refrigerant consisting essentially of the following three compounds, each compound being present in the following relative percentages: 41 wt% ± 1 wt% of difluoromethane (HFC-32), 3.5 wt% ± 0.5 wt% of pentafluoroethane (HFC-125), and 55.5 wt% ± 0.5 wt% of trifluoroiodomethane (CF3I). The refrigerant according to this paragraph is, for convenience in this specification, referred to as Refrigerant 14.

[0033] The present invention includes a refrigerant composed of the following three compounds, wherein each compound is present in the following relative percentages: 41% by weight ± 1% by weight of difluoromethane (HFC-32), 3.5% by weight ± 0.5% by weight of pentafluoroethane (HFC-125), and 55.5% by weight ± 0.5% by weight of trifluoroiodomethane (CF3I). The refrigerant is non-flammable according to the non-flammability test. The refrigerant according to this paragraph is referred to as Refrigerant 15 for convenience in this specification.

[0034] A refrigerant containing approximately the minimum weight percentages of three compounds shown in the following table. Each compound is present in the following relative percentages in any one of Refrigerants 16 - 18.

[0035]

Table 2

[0036] The present invention includes a refrigerant consisting essentially of the following three compounds, wherein each compound is present in the following relative percentages: 41% by weight ± 0.3% by weight of difluoromethane (HFC-32), 3.5% by weight ± 0.3% by weight of pentafluoroethane (HFC-125), and 55.5% by weight ± 0.3% by weight of trifluoroiodomethane (CF3I). The refrigerant according to this paragraph is referred to as Refrigerant 19 for convenience in this specification.

[0037] The present invention includes a refrigerant composed of the following three compounds, wherein each compound is present in the following relative percentages: 41% by weight ± 0.3% by weight of difluoromethane (HFC-32), 3.5% by weight ± 0.3% by weight of pentafluoroethane (HFC-125), and 55.5% by weight ± 0.3% by weight of trifluoroiodomethane (CF3I). The refrigerant is non-flammable according to the non-flammability test. The refrigerant according to this paragraph is referred to as Refrigerant 20 for convenience in this specification.

[0038] A refrigerant containing approximately minimum weight percentages of three compounds shown in the following table. Each compound is present in the following relative percentages in any one of Refrigerants 21 - 23.

[0039] [Table 3]

[0040] The present invention includes a refrigerant consisting essentially of the following three compounds, with each compound present in the following relative percentages: 41% by weight of difluoromethane (HFC - 32), 3.5% by weight of pentafluoroethane (HFC - 125), and 55.5% by weight of trifluoroiodomethane (CF3I). For convenience in this specification, the refrigerant according to this paragraph is referred to as Refrigerant 24.

[0041] The present invention includes a refrigerant consisting of the following three compounds, with each compound present in the following relative percentages: 41% by weight of difluoromethane (HFC - 32), 3.5% by weight of pentafluoroethane (HFC - 125), and 55.5% by weight of trifluoroiodomethane (CF3I). The refrigerant is non - flammable according to the non - flammability test. For convenience in this specification, the refrigerant according to this paragraph is referred to as Refrigerant 25. [Brief Description of the Drawings]

[0042]

Figure 1

[0043] The applicants have found that the refrigerant of the present invention containing refrigerants 1 to 25 as described in this specification can provide very advantageous properties, particularly non-flammability, by using any one of refrigerants 1 to 25 of the present invention, especially as a substitute for R-410A.

[0044] A specific advantage of the refrigerants 1 to 25 of the present invention in a preferred composition is that they are non-flammable, as defined below. Therefore, it is desired in the art to provide a refrigerant composition that has excellent heat transfer properties, low environmental impact (including particularly low GWP and almost zero ODP), chemical stability, low toxicity or non-toxicity, and / or lubricant compatibility, and maintains non-flammability during use, and can be used as a substitute for R-410A. This desired advantage can be achieved by the refrigerants 1 to 25 of the present invention.

[0045] The present invention particularly includes a heat transfer composition containing the refrigerant of the present invention containing any one of refrigerants 1 to 25. Preferably, the heat transfer composition of the present invention contains the refrigerant of the present invention in an amount of more than 40% by weight of the heat transfer composition, or more than about 50% by weight of the heat transfer composition, or more than 70% by weight of the heat transfer composition, or more than 80% by weight of the heat transfer composition, or more than 90% by weight of the heat transfer composition. The heat transfer composition can consist essentially of or consist of the refrigerant according to the present invention containing any one of refrigerants 1 to 25.

[0046] The heat transfer composition of the present invention may contain other components for the purpose of enhancing or providing a certain functionality to the composition. Such other components or additives may include one or more of stabilizers, lubricants, dyes, solubilizers, compatibilizers, antioxidants, corrosion inhibitors, extreme pressure additives, and anti-wear agents.

[0047] Definition: For the purposes of the present invention, the term "about" with respect to a temperature in degrees Celsius (°C) means that the specified temperature can vary by an amount of + / - 5°C. In a preferred embodiment, the temperature specified as being about is preferably + / - 2°C of the specific temperature, more preferably + / - 1°C, and even more preferably + / - 0.5°C.

[0048] The term "capacity" is the amount of cooling (BTU / hr) provided by the refrigerant in a refrigeration system. This is determined experimentally by multiplying the change in the enthalpy (BTU / lb) of the refrigerant as it passes through the evaporator by the mass flow rate of the refrigerant. Enthalpy can be determined from measurements of the pressure and temperature of the refrigerant. The capacity of an air conditioning system is related to the ability to maintain a specified temperature in the area being cooled. The capacity of the refrigerant represents the amount of cooling or heating provided by the refrigerant and provides a measure of the performance of the compressor in delivering heat for a given volume flow rate of the refrigerant. In other words, considering a particular compressor, a refrigerant with a higher capacity will supply more cooling or heating power.

[0049] The term "coefficient of performance" (hereinafter "COP") is a widely accepted measure of refrigerant performance that is particularly useful for representing the relative thermodynamic efficiency of a refrigerant in a particular heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration engineering, this term represents the ratio of the effective refrigeration or cooling capacity to the energy applied by the compressor during vapor compression, and thus represents the capacity of a given compressor to deliver heat for a given volume flow rate of a heat transfer fluid such as a refrigerant. In other words, considering a particular compressor, a refrigerant with a higher COP will supply more cooling or heating power. One method for estimating the COP of a refrigerant under specific operating conditions is derived from the thermodynamic properties of the refrigerant using standard refrigerant cycle analysis techniques (see, for example, Downing, FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988, which is hereby incorporated by reference in its entirety). The term "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 preferably allows the use of existing equipment without operating the thermal protection aspect of a system designed to protect compressor components and avoids the use of expensive control devices such as liquid injection to lower the discharge temperature.

[0050] The "Global Warming Potential" (hereinafter "GWP") was developed to enable comparison of the impacts of various gases on global warming. Specifically, it is a measure of how much energy a one-ton emission of a gas absorbs relative to a one-ton emission of carbon dioxide over a given period. The higher the GWP, the more a given gas warms the planet over that period compared to CO2. The given period used for GWP is 100 years. GWP provides a common scale that enables analysts to sum the emission estimates of different gases. See www.epa.gov. GWP as used herein includes a given period of 100 years.

[0051] The term "Life Cycle Climate Performance" (hereinafter, "LCCP") is a method by which air conditioning and refrigeration systems can be evaluated for their impact on global warming over the life of the product. LCCP includes the direct impact of refrigerant emissions and the indirect impacts of energy consumption used to operate the system, energy used to manufacture the system, and the transportation and safe disposal of the system. The direct impact of refrigerant emissions is derived from the GWP value of the refrigerant. For indirect emissions, measured refrigerant properties are used to obtain system performance and energy consumption. LCCP is determined using equations 1 and 2 as follows. Equation 1 is Direct emissions = Refrigerant charge (kg) × (Annual leak rate × Product life + Loss at end of product life) × GWP. Equation 2 is Indirect emissions = Annual electricity consumption × Product life × CO2 per kW-hr of electricity production. The direct emissions as determined by Equation 1 and the indirect emissions as determined by Equation 2 are added together to result in LCCP. TMY2 and TMY3 data generated by the National Renewable Laboratory and available in BinMaker® Pro version 4 software are used in the analysis. The GWP values reported in the Fourth Assessment Report (AR4) (2007) of the Intergovernmental Panel on Climate Change (IPCC) are used in the calculations. LCCP is the mass of carbon dioxide (kg-CO over the product life of an air conditioning or refrigeration system. 2eq) is represented as.

[0052] The term "mass flow rate" is the mass of refrigerant passing through a conduit per unit time.

[0053] The term "nonflammable" is described in Appendix B1 of ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants, which is hereby incorporated by reference in its entirety, and means a compound or composition that is determined to be nonflammable when judged in accordance with ASTM standard E-681-2009 Standard Test Method for Concentration Limits of Flammability of Chemicals (Vapors and Gases) in the conditions (the "nonflammability test") described therein. Flammability is defined as the ability of a composition to ignite and / or spread a flame. Under this test, flammability is judged by measuring the flame angle.

[0054] The term "occupational exposure limit (OEL)" is determined in accordance with ASHRAE Standard 34-2016 Designation and Safety Classification of Refrigerants.

[0055] As used herein, the term "substitute for" a particular prior refrigerant, with respect to a particular heat transfer composition or refrigerant of the present invention, means the use of the designated composition of the present invention in a heat transfer system that has heretofore been commonly used with that prior refrigerant. By way of example, in heat transfer systems that have heretofore been designed for and / or commonly used with R410A, such as residential and commercial air conditioning (including rooftop systems, variable refrigerant flow (VRF) systems, and chiller systems), when using the refrigerant or heat transfer composition of the present invention, the refrigerant of the present invention becomes a substitute for R410A in such systems.

[0056] The term "thermodynamic glide" is applied to non-azeotropic refrigerant mixtures having various temperatures during the phase change process in an evaporator or condenser at a constant pressure.

[0057] Refrigerants and heat transfer compositions The applicants have found that the refrigerants of the present invention containing each of Refrigerants 1 to 25 described herein, particularly when the refrigerants of the present invention are used as alternatives to R-410A, particularly in conventional R-410A residential air conditioning systems and conventional R-410A commercial air conditioning systems (conventional R-410A rooftop systems , conventional R-410A variable refrigerant flow (VRF) systems, and conventional R-410A chiller systems), can provide very advantageous properties, particularly non-flammability.

[0058] A particular advantage of the refrigerants of the present invention is that they are non-flammable when tested according to the non-flammability test, and as described above, they can be used in various systems as alternatives to R-410A, and have excellent heat transfer properties, low environmental impact (including particularly low GWP and substantially zero ODP), chemical stability, low toxicity or non-toxicity, and / or lubricant compatibility, and maintain non-flammability during use. It is desired in the art to provide refrigerants and heat transfer compositions. This desired advantage can be achieved by the refrigerants and heat transfer compositions of the present invention.

[0059] Preferably, the heat transfer composition contains any refrigerant of the present invention containing each of Refrigerants 1 to 25, and contains the refrigerant in an amount exceeding 40% by weight of the heat transfer composition.

[0060] Preferably, the heat transfer composition contains any refrigerant of the present invention containing each of Refrigerants 1 to 25, and contains the refrigerant in an amount exceeding 50% by weight of the heat transfer composition.

[0061] Preferably, the heat transfer composition contains any refrigerant of the present invention containing each of Refrigerants 1 to 25, and contains the refrigerant in an amount exceeding 70% by weight of the heat transfer composition.

[0062] Preferably, the heat transfer composition includes any refrigerant of the present invention that includes each of Refrigerants 1 to 25, and includes the refrigerant in an amount exceeding 80% by weight of the heat transfer composition.

[0063] Preferably, the heat transfer composition includes any refrigerant of the present invention that includes each of Refrigerants 1 to 25, and includes the refrigerant in an amount exceeding 90% by weight of the heat transfer composition.

[0064] The present applicants have found that the refrigerant according to the present invention including each of Refrigerants 1 to 25 and the heat transfer composition containing any one of such refrigerants of the present invention can overcome the difficulties for realizing a combination of characteristics including a particularly low GWP. Therefore, the GWP of the refrigerant according to the present invention and the heat transfer composition of the present invention is about 427 or less, and preferably, the GWP is from about 250 to less than 427.

[0065] Furthermore, the ozone depletion potential (ODP) of the refrigerant according to the present invention including each of Refrigerants 1 to 25 and the heat transfer composition containing any one of such refrigerants of the present invention is small. Therefore, the refrigerant according to the present invention and the heat transfer composition of the present invention have an ozone depletion potential (ODP) of 0.05 or less, preferably 0.02 or less, and more preferably about zero.

[0066] Furthermore, the heat transfer composition containing any one of the refrigerant according to the present invention including each of Refrigerants 1 to 25 and such refrigerants of the present invention exhibits acceptable toxicity, and preferably has an occupational exposure limit (OEL) of more than about 400.

[0067] The heat transfer composition of the present invention may preferably contain other components for the purpose of enhancing a specific functionality or providing a specific functionality to the composition without impairing the enhanced characteristics provided according to the present invention. Such other components or additives may include stabilizers and lubricants.

[0068] Stabilizer: The heat transfer composition of the present invention particularly includes a refrigerant as described herein including each of Refrigerants 1 to 25 and a stabilizer.

[0069] The stabilizer component is preferably provided in the heat transfer composition in an amount of more than 0 wt% to about 15 wt%, or about 0.5 to about 10 wt% of the heat transfer composition, these percentages being based on the total weight of all stabilizers in the heat transfer composition divided by the total of all components in the heat transfer composition.

[0070] The stabilizer for use in the heat transfer composition of the present invention comprises a combination of (i) at least one alkylated naphthalene compound and (ii) at least one phenolic compound. The stabilizer according to this paragraph may be referred to herein, for convenience, as stabilizer 1.

[0071] The stabilizer for use in the heat transfer composition of the present invention comprises at least one of (i) an alkylated naphthalene compound(s), (ii) a phenolic compound(s), and (iii) a diene compound(s). The stabilizer according to this paragraph may be referred to herein, for convenience, as stabilizer 2.

[0072] The stabilizer for use in the heat transfer composition of the present invention comprises a combination of (i) at least one alkylated naphthalene compound and (ii) at least a diene compound. The stabilizer according to this paragraph may be referred to herein, for convenience, as stabilizer 3.

[0073] The stabilizer for use in the heat transfer composition of the present invention comprises a combination of (i) at least one alkylated naphthalene compound and (ii) an isobutylene compound. The stabilizer according to this paragraph may be referred to herein, for convenience, as stabilizer 4.

[0074] The stabilizer for use in the heat transfer composition of the present invention comprises a combination of (i) at least one alkylated naphthalene compound, (ii) at least one phenolic compound, and (iii) at least one diene compound. The stabilizer according to this paragraph may be referred to herein, for convenience, as stabilizer 5.

[0075] The stabilizer may also contain a phosphorus compound(s) and / or a nitrogen compound(s) and / or an epoxide(s). When present, the epoxide is preferably selected from the group consisting of aromatic epoxides, alkyl epoxides, and alkenyl epoxides.

[0076] The stabilizer for use in the heat transfer composition of the present invention comprises a combination of (i) at least one alkylated naphthalene compound, (ii) at least one phenolic compound, and (iii) at least one epoxide. The stabilizer according to this paragraph may be referred to herein as stabilizer 6 for convenience.

[0077] The stabilizer for use in the heat transfer composition of the present invention comprises a combination of (i) at least one alkylated naphthalene compound, (ii) at least one phenolic compound, and (iii) at least one epoxide selected from the group consisting of aromatic epoxides, alkyl epoxides, and alkenyl epoxides. The stabilizer according to this paragraph may be referred to herein as stabilizer 7 for convenience.

[0078] The stabilizer may consist essentially of one or more alkylated naphthalenes, one or more epoxides, and one or more phenolic compounds. The stabilizer according to this paragraph may be referred to herein as stabilizer 8 for convenience.

[0079] Alkylated naphthalene The Applicants have surprisingly and unexpectedly found that alkylated naphthalene is very effective as a stabilizer for the heat transfer composition of the present invention. As used herein the term "alkylated naphthalene" refers to a compound having the following structure:

[0080]

Chemical formula

[0081] The present applicants have found that unexpected, surprising, and advantageous results are associated with the use of alkylated naphthalene as a stabilizer according to the present invention having the following properties. The alkylated naphthalene compounds having the indicated properties are herein for convenience referred to as alkylated naphthalene 1 to alkylated naphthalene 4 (AN1 to AN4), as shown in columns 1 to 5 of Table AN1 below, respectively.

[0082] [Table 4]

[0083] When used herein in relation to the viscosity at 40 °C measured in accordance with ASTM D445, the term "about" means + / - 4 cSt.

[0084] When used herein in relation to the viscosity at 100 °C measured in accordance with ASTM D445, the term "about" means + / - 0.4 cSt.

[0085] When used herein in relation to the pour point measured in accordance with ASTM D97, the term "about" means + / - 5 °C.

[0086] The present applicants have also found that unexpected, surprising and advantageous results are associated with the use of alkylated naphthalenes as stabilizers according to the present invention having the following properties, and alkylated naphthalene compounds having the indicated properties are herein for convenience referred to as alkylated naphthalene 6 to alkylated naph naphthalene 10 (AN6 to AN10), as shown respectively in columns 6 to 10 of Table AN2 below.

[0087]

Table 5

[0088] Examples of alkylated naphthalenes within the meaning of alkylated naphthalene 1 and alkylated naphthalene 6 include those sold by King Industries under the trade names NA-LUBE KR-007A, KR-008, KR-009, KR-015, KR-019, KR-005FG, KR-015FG, and KR-029FG.

[0089] Examples of alkylated naphthalenes within the meaning of alkylated naphthalene 2 and alkylated naphthalene 7 include those sold by King Industries under the trade names NA-LUBE KR-007A, KR-008, and KR-009, and KR-005FG.

[0090] Examples of alkylated naphthalenes within the scope of the meaning of alkylated naphthalene 5 and alkylated naphthalene 10 include products sold by King Industries under the product name NA-LUBE KR-008.

[0091] The alkylated naphthalene is preferably present in the heat transfer composition of the present invention comprising the refrigerant of the present invention containing each of refrigerants 1 to 25, and the alkylated naphthalene is present in an amount of 0.01% to about 10%, or about 1.5% to about 4.5%, or about 2.5% to about 3.5%, and these amounts are weight percentages based on the amounts of alkylated naphthalene and refrigerant in the system.

[0092] The alkylated naphthalene is preferably present in the heat transfer composition of the present invention comprising a lubricant and the refrigerant of the present invention containing each of refrigerants 1 to 25, and the alkylated naphthalene is present in an amount of 0.1% to about 20%, or about 5% to about 15%, or about 8% to about 12%, and these amounts are weight percentages based on the amounts of alkylated naphthalene and lubricant in the system.

[0093] The alkylated naphthalene is preferably present in the heat transfer composition of the present invention comprising a POE lubricant and the refrigerant of the present invention containing each of refrigerants 1 to 25, and the alkylated naphthalene is present in an amount of 0.1% to about 20%, or about 5% to about 15%, or about 8% to about 12%, and these amounts are weight percentages based on the amounts of alkylated naphthalene and lubricant in the system.

[0094] The alkylated naphthalene is preferably present in the heat transfer composition of the present invention comprising a POE lubricant having a viscosity at 40 °C of about 30 cSt to about 70 cSt measured in accordance with ASTM D445C and the refrigerant of the present invention containing each of refrigerants 1 to 25, and the alkylated naphthalene is present in an amount of 0.1% to about 20%, or about 5% to about 15%, or about 8% to about 12%, and these amounts are weight percentages based on the amounts of alkylated naphthalene and lubricant in the system.

[0095] Diene compound The diene compound includes a C3 - C15 diene and a compound formed by the reaction of any two or more C3 - C4 dienes. Preferably, the diene compound is selected from the group consisting of allyl ether, propadiene, butadiene, isoprene, and terpene. The diene compound is preferably a terpene, which includes, but is not limited to, terpinene, delta-3 carene, terpinolene, farnesene, pinene, nerol, citral, camphor, menthol, limonene, nerolidol, phytol, carnosic acid, and vitamin A1. Preferably, the stabilizer is farnesene. A preferred terpene stabilizer is disclosed in U.S. Provisional Patent Application No. 60 / 638,003, filed on December 12, 2004, and published as U.S. Patent Application Publication No. 2006 / 0167044(A1), which is incorporated herein by reference.

[0096] Furthermore, the diene compound can be provided in the heat transfer composition in an amount greater than 0, preferably in an amount of 0.0001 wt% to about 5 wt%, preferably 0.001 wt% to about 2.5 wt%, more preferably 0.01 wt% to about 1 wt%. In each case, the weight percentage refers to the weight of the heat transfer composition.

[0097] Phenolic compound The phenolic compound is selected from phenolic compounds including 4,4'-methylenebis(2,6-di-tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); 4,4'-bis(2-methyl-6-tert-butylphenol), 2,2- or 4,4-biphenyldiol; derivatives of 2,2- or 4,4-biphenyldiol; 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 4,4-butylidenebis(3-methyl-6-tert-butylphenol); 4,4-isopropylidenebis(2,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,6-di-tert-butyl-4-methylphenol (BHT); 2,6-di-tert-butyl-4-ethylphenol: 2,4-dimethyl-6-tert-butylphenol; 2,6-di-tert-alpha-dimethylamino-p-cresol; 2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol); 4,4'-thiobis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-methyl-6-tert-butylphenol); 2,2'-thiobis(4-methyl-6-tert-butylphenol); bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide; bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, tocopherol, hydroquinone, 2,2'6,6'-tetra-tert-butyl-4,4'-methylenediphenol, and t-butylhydroquinone, preferably one or more compounds selected from among BHT. The phenolic compound can be provided in the heat transfer composition in an amount greater than 0, preferably in an amount of from 0.0001 wt% to about 5 wt%, preferably from 0.001 wt% to about 2.5 wt%, more preferably from 0.01 wt% to about 1 wt%. In each case, the weight percentage refers to the weight of the heat transfer composition.

[0098] Phosphorus-based compound The phosphorus compound can be a phosphorous acid compound or a phosphoric acid compound. For the purposes of the present invention, the phosphorous acid compound can be a diaryl, dialkyl, triaryl, and / or trialkyl phosphite, and / or a mixed aryl / alkyl di- or tri-substituted phosphite, particularly a hindered phosphite, tris-(di-tert-butylphenyl) phosphite, di-n-octyl phosphite, isooctyl diphenyl phosphite, isodecyl diphenyl phosphite, tri-iso-decyl phosphate, triphenyl phosphite, and diphenyl phosphite, and one or more compounds selected therefrom, particularly diphenyl phosphite. The phosphoric acid compound can be a triaryl phosphate, trialkyl phosphate, alkyl monoacid phosphate, aryl diacid phosphate, amine phosphate, preferably a triaryl phosphate and / or a trialkyl phosphate, particularly tri-n-butyl phosphate.

[0099] The phosphorus compound can be provided in the heat transfer composition in an amount greater than 0, preferably in an amount of 0.0001 wt% to about 5 wt%, preferably 0.001 wt% to about 2.5 wt%, more preferably 0.01 wt% to about 1 wt%. In each case, by weight refers to the weight of the heat transfer composition.

[0100] Nitrogen compound When the stabilizer is a nitrogen compound, the stabilizer may include amine compounds such as one or more secondary or tertiary amines selected from diphenylamine, p-phenylenediamine, triethylamine, tributylamine, diisopropylamine, triisopropylamine, and triisobutylamine. The amine compound may be an amine antioxidant, for example, a substituted piperidine compound, that is, a derivative of an alkyl-substituted piperidyl, piperidinyl, piperazinone, or alkoxypiperidinyl, particularly 2,2,6,6-tetramethyl-4-piperidone, 2,2,6,6-tetramethyl-4-piperidinol; bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate; di(2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate; alkylated paraphenylenediamine, for example, N-phenyl-N'-(1,3-dimethyl-butyl)-p-phenylenediamine or N,N'-di-sec-butyl-p-phenylenediamine, and hydroxylamine, for example, tallow amine, methyl bis tallow amine, and bis tallow amine, or phenol-alpha-naphthylamine, or one or more amine antioxidants selected from Tinuvin® 765 (Ciba), BLS® 1944 (Mayzo Inc), and BLS® 1770 (Mayzo Inc). For the purposes of the present invention, the amine compound may also be one or more of alkyl diphenylamines such as bis(nonylphenylamine), dialkylamines such as (N-(1-methylethyl)-2-propylamine, or phenyl-alpha-naphthylamine (PANA), alkyl-phenyl-alpha-naphthyl-amine (APANA), and bis(nonylphenyl)amine. Preferably, the amine compound is one or more of phenyl-alpha-naphthylamine (PANA), alkyl-phenyl-alpha-naphthyl-amine (APANA), and bis(nonylphenyl)amine, more preferably phenyl-alpha-naphthylamine (PANA).

[0101] Alternatively, or in addition to the nitrogen compounds identified above, one or more compounds selected from dinitrobenzene, nitrobenzene, nitromethane, nitroso benzene, and TEMPO [(2,2,6,6 - tetramethylpiperidin - 1 - yl)oxyl] may be used as a stabilizer.

[0102] The nitrogen compound can be provided in the heat transfer composition in an amount greater than 0 and from 0.0001 wt% to about 5 wt%, preferably from 0.001 wt% to about 2.5 wt%, more preferably from 0.01 wt% to about 1 wt%. In each case, the weight percentage refers to the weight of the heat transfer composition.

[0103] Epoxides and others Useful epoxides include aromatic epoxides, alkyl epoxides, and alkenyl epoxides.

[0104] Isobutylene can also be used as a stabilizer according to the present invention.

[0105] Preferably, the heat transfer composition includes a refrigerant of the present invention containing each of Refrigerants 1 - 25, and a stabilizer composition containing an alkylated naphthalene selected from alkylated naphthalenes 1 - 5. For the purposes of the uses, methods, and systems described herein, the stabilizer composition can include alkylated naphthalene 5 and BHT. Preferably, the stabilizer composition consists essentially of alkylated naphthalene 5 and BHT. Preferably, the stabilizer composition consists of alkylated naphthalene 5 and BHT.

[0106] Preferably, the heat transfer composition includes a refrigerant of the present invention containing each of Refrigerants 1 - 25, and a stabilizer composition containing an alkylated naphthalene selected from alkylated naphthalenes 1 - 5. For the purposes of the uses, methods, and systems described herein, the stabilizer composition can include alkylated naphthalene 5, BHT, and an epoxide. Preferably, the stabilizer composition consists essentially of alkylated naphthalene 5, BHT, and an epoxide. Preferably, the stabilizer composition consists of alkylated naphthalene 5, BHT, and an epoxide.

[0107] Preferably, the heat transfer composition includes a refrigerant of the present invention containing each of Refrigerants 1 to 25 and a stabilizer composition containing an alkylated naphthalene selected from isobutylene and alkylated naphthalenes 1 to 5. For the purposes of the uses, methods, and systems described herein, the stabilizer composition may include isobutylene, alkylated naphthalene 5, and BHT. Preferably, the stabilizer composition consists essentially of isobutylene, alkylated naphthalene 5, and BHT. Preferably, the stabilizer composition consists of isobutylene, alkylated naphthalene 5, and BHT.

[0108] The heat transfer composition includes a refrigerant of the present invention containing each of Refrigerants 1 to 25 and a stabilizer composition containing alkylated naphthalene 4.

[0109] The heat transfer composition includes a refrigerant of the present invention containing each of Refrigerants 1 to 25 and a stabilizer composition containing alkylated naphthalene 5.

[0110] The stabilizer can include, consist essentially of, or consist of farnesene and alkylated naphthalene 5.

[0111] The stabilizer can include, consist essentially of, or consist of isobutylene and alkylated naphthalene 5.

[0112] The heat transfer composition of the present invention preferably can include any one of Refrigerants 1 to 25 and each of Refrigerants 1 to 25, and any one of Stabilizers 1 to 8 and each of Stabilizers 1 to 8.

[0113] The heat transfer composition can include the following combinations of any one of Refrigerants 1 to 25 and Stabilizer 1, and is conveniently specified herein as the indicated heat transfer composition.

[0114] [Table 6]

[0115] The heat transfer composition can include the following combinations of any one of refrigerants 1 to 25 and stabilizer 6, and is conveniently specified herein as the indicated heat transfer composition.

[0116] [Table 7]

[0117] Lubricant: Each of the heat transfer compositions containing each of refrigerants 1 to 25 and each of the heat transfer compositions of the present invention as described herein containing heat transfer compositions 1 to 50 may further contain a lubricant. Generally, the heat transfer composition contains the lubricant in an amount of about 5 to 60% by weight of the heat transfer composition, preferably about 10 to about 60% by weight of the heat transfer composition, preferably about 20 to about 50% by weight of the heat transfer composition, alternatively about 20 to about 40% by weight of the heat transfer composition, alternatively about 20 to about 30% by weight of the heat transfer composition, alternatively about 30 to about 50% by weight of the heat transfer composition, alternatively about 30 to about 40% by weight of the heat transfer composition. The heat transfer composition may contain the lubricant in an amount of about 5 to about 10% by weight of the heat transfer composition, preferably about 8% by weight of the heat transfer composition.

[0118] For example, commonly used refrigerant lubricants such as polyol ester (POE), polyalkylene glycol (PAG), silicone oil, mineral oil, alkylbenzene (AB), polyvinyl ether (PVE), and poly(α-olefin) (PAO) used in refrigeration machines can be used together with the refrigerant composition of the present invention.

[0119] Preferably, the lubricant is selected from polyol esters (POE), polyalkylene glycols (PAG), mineral oils, alkylbenzenes (AB), and polyvinyl ethers (PVE), more preferably from polyol esters (POE), mineral oils, alkylbenzenes (AB), and polyvinyl ethers (PVE), particularly from polyol esters (POE), mineral oils, and alkylbenzenes (AB), and most preferably from polyol esters (POE).

[0120] The heat transfer composition of the present invention containing each of Heat Transfer Compositions 1 to 50 preferably contains a POE lubricant and / or a PVE lubricant, and the lubricant is preferably present in an amount of about 0.1 wt% to about 5%, or 0.1 wt% to about 1%, or 0.1 wt% to about 0.5% based on the weight of the heat transfer composition.

[0121] Generally, the heat transfer composition of the present invention containing each of Heat Transfer Compositions 1 to 50 preferably contains an AB lubricant and / or a mineral oil lubricant, and the lubricant is preferably present in an amount of about 0.1 wt% to about 5%, or 0.1 wt% to about 1%, or 0.1 wt% to about 0.5% based on the weight of the heat transfer composition.

[0122] The heat transfer composition preferably contains any one of Refrigerants 1 to 25 and a polyol ester (POE) lubricant.

[0123] The heat transfer composition of the present invention containing each of the heat transfer compositions preferably contains any one of Refrigerants 1 to 25 and a polyol ester (POE) lubricant.

[0124] The heat transfer composition of the present invention containing each of the heat transfer compositions preferably contains any one of Refrigerants 1 to 25 and a PVE lubricant.

[0125] The heat transfer composition of the present invention containing each of Heat Transfer Compositions 1 to 50 preferably contains a POE lubricant.

[0126] The heat transfer composition of the present invention containing each of Heat Transfer Compositions 1 to 50 preferably contains a PVE lubricant.

[0127] Commercially available mineral oils include Witco's Witco LP 250 (registered trademark), Witco's Suniso 3GS, and Calumet's Calumet R015. Commercially available alkylbenzene lubricants include Shrieve Chemical's Zerol 150 (registered trademark) and Zerol 300 (registered trademark). Commercially available esters include neopentyl glycol diperlargonate available as Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark). Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters.

[0128] The heat transfer composition of the present invention containing each of Heat Transfer Compositions 1 to 50 may consist essentially of the refrigerant of the present invention and the lubricant described herein.

[0129] The composition of the present invention may consist essentially of or consist of a refrigerant, a stabilizer composition, and a lubricant as described herein.

[0130] The polyol ester (POE) lubricant present at 0.5 to 50% by weight based on the weight of the heat transfer composition is, for convenience, referred to as Lubricant 1.

[0131] The polyvinyl ether (PVE) lubricant present at 0.5 to 50% by weight based on the weight of the heat transfer composition is, for convenience, referred to as Lubricant 2.

[0132] The heat transfer composition can include the following combinations of any one of Refrigerants 1 to 25 and Lubricant 1 or Lubricant 2:

[0133]

Table 8

[0134] The heat transfer composition may include any one of refrigerants 1 to 25, stabilizer 1, and the following combinations of lubricant 1 or lubricant 2.

[0135]

Table 9

[0136] The heat transfer composition may include any one of refrigerants 1 to 25, stabilizer 6, and the following combinations of lubricant 1 or lubricant 2.

[0137]

Table 10

[0138] Without departing from the novel and basic characteristics of the present invention, other additives not mentioned herein may also be included in consideration of the teachings contained herein.

[0139] Also, as disclosed in U.S. Patent No. 6,516,837, the entire disclosure of which is incorporated herein by reference, a combination of a surfactant and a solubilizer may be added to the composition of the present invention to assist with oil solubility.

[0140] Any reference to any of the heat transfer compositions of the present invention refers to any one of the heat transfer compositions described herein. Thus, for the following discussion of the use or application of the compositions of the present invention, the heat transfer composition may include or may consist essentially of any refrigerant of the present invention, including any one of refrigerants 1 to 25 described herein.

[0141] Methods, Uses, and Systems The refrigerants according to the present invention and the heat transfer compositions disclosed herein are provided for use in heat transfer applications including air conditioning (including in particular residential air conditioning), refrigeration, heat pumps, and coolers (including portable water coolers and central water coolers).

[0142] The heat transfer compositions disclosed herein are provided for use in heat transfer applications including air conditioning applications. Very preferred air conditioning applications include residential air conditioning applications, commercial air conditioning applications (such as rooftop applications, VRF applications, and chillers).

[0143] The present invention also includes a method of providing heat transfer including an air conditioning method. Very preferred air conditioning methods include providing residential air conditioning, providing commercial air conditioning (such as a method of providing rooftop air conditioning, a method of providing VRF air conditioning, and a method of providing air conditioning using a chiller).

[0144] The present invention also includes a heat transfer system including an air conditioning system. Very preferred air conditioning systems include residential air conditioning systems, commercial air conditioning systems (such as rooftop air conditioning systems, VRF air conditioning systems, and air conditioning chiller systems).

[0145] The present invention also provides for the use of a heat transfer composition, a method of using a heat transfer composition, and a system including a heat transfer composition, in relation to refrigeration, heat pumps, and chillers (including portable water chillers and central water chillers).

[0146] Any reference to any of the heat transfer compositions of the present invention refers to any one of each of the heat transfer compositions described herein. Thus, for the following discussion of the use, methods, systems, or applications of the compositions of the present invention, the heat transfer composition can include, or can consist essentially of, any one of Refrigerants 1 - 25 and any one of Heat Transfer Compositions 1 - 50.

[0147] For the purposes of the present invention, each of the heat transfer compositions as described herein and any one of the heat transfer compositions can be used in a heat transfer system such as an air conditioning system (including, in particular, a residential air conditioning system), a refrigeration system, a heat pump, and a chiller system (including portable water chillers and central water chillers). The heat transfer system according to the present invention can include a compressor, an evaporator, a condenser, and an expansion device connected to each other.

[0148] Examples of commonly used compressors for the purposes of the present invention include reciprocating, rotary (including rolling piston and rotary valve), scroll, screw, and centrifugal compressors. Accordingly, the present invention provides each and any of refrigerants 1 to 25 and / or heat transfer compositions as described herein for use in a heat transfer system including a reciprocating, rotary (including rolling piston and rotary valve), scroll, screw, or centrifugal compressor.

[0149] Examples of commonly used expansion devices for the purposes of the present invention include capillary tubes, fixed orifices, thermostatic expansion valves, and electronic expansion valves. Accordingly, the present invention provides each and any of refrigerants 1 to 25 and / or heat transfer compositions as described herein for use in a heat transfer system including a capillary tube, fixed orifice, thermostatic expansion valve, or electronic expansion valve.

[0150] For the purposes of the present invention, the evaporator and the condenser preferably together form a heat exchanger selected from finned tube heat exchangers, microchannel heat exchangers, shell and tube heat exchangers, plate heat exchangers, and tube-in-tube heat exchangers. Accordingly, the present invention provides each and any of refrigerants 1 to 25 and / or heat transfer compositions as described herein for use in a heat transfer system in which the evaporator and the condenser together form a finned tube heat exchanger, a microchannel heat exchanger, a shell and tube heat exchanger, a plate heat exchanger, or a tube-in-tube heat exchanger.

[0151] Regarding the heat transfer system of the present invention including a compressor and the lubricant for the compressor in the system, the system has a lubricant filling amount in the system of about 5 wt% to 60 wt%, or about 10 wt% to about 60 wt%, or about 20 wt% to about 50 wt%, or about 20 wt% to about 40 wt%, or about 20 wt% to about 30 wt%, or about 30 wt% It can include the filling amounts of the refrigerant and the lubricant so as to be about 40% by weight or less. As used herein, the term "lubricant filling amount" refers to the total weight of the lubricant contained in the system as the total ratio of the lubricant and the refrigerant contained in the system. Such a system can also include a lubricant filling amount of about 5% to about 10% by weight, or about 8% by weight of the heat transfer composition.

[0152] The heat transfer system according to the present invention can include a compressor, an evaporator, a condenser, and an expansion device that are in fluid communication with each other, a heat transfer composition 1-50, and a sealing material in the system, and the sealing material is preferably i. copper or a copper alloy, or ii. activated alumina, or iii. a zeolite molecular sieve containing copper, silver, lead, or a combination thereof, or iv. an anion exchange resin, or v. a moisture removal material, preferably a moisture removal molecular sieve, or vi. a combination of two or more of the above.

[0153] The present invention also includes a method of transferring heat of a type including evaporating a refrigerant liquid to generate a refrigerant vapor, compressing at least a portion of the refrigerant vapor with a compressor, and condensing the refrigerant vapor in a plurality of repeating cycles, and the method includes (a) providing a heat transfer composition according to the present invention each including the heat transfer composition 1-50, (b) optionally but preferably providing a lubricant to the compressor, (b) exposing at least a portion of the refrigerant and / or at least a portion of the lubricant to the sealing material.

[0154] Use, Equipment, and Systems In a preferred embodiment, the residential air conditioning system and method have a refrigerant evaporation temperature in the range of about 0°C to about 10°C, and the condensation temperature is in the range of about 40°C to about 70°C.

[0155] In a preferred embodiment, a residential air conditioning system and method used in a heating mode have a refrigerant evaporation temperature in the range of about -20°C to about 3°C, and a condensation temperature in the range of about 35°C to about 50°C.

[0156] In a preferred embodiment, a commercial air conditioning system and method have a refrigerant evaporation temperature in the range of about 0°C to about 10°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0157] In a preferred embodiment, a hot water system and method have a refrigerant evaporation temperature in the range of about -20°C to about 3°C, and a condensation temperature in the range of about 50°C to about 90°C.

[0158] In a preferred embodiment, a medium temperature system and method have a refrigerant evaporation temperature in the range of about -12°C to about 0°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0159] In a preferred embodiment, a low temperature system and method have a refrigerant evaporation temperature in the range of about -40°C to about -12°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0160] In a preferred embodiment, a rooftop air conditioning system and method have a refrigerant evaporation temperature in the range of about 0°C to about 10°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0161] In a preferred embodiment, a VRF system and method have a refrigerant evaporation temperature in the range of about 0°C to about 10°C, and a condensation temperature in the range of about 40°C to about 70°C.

[0162] The present invention includes, as shown in the following table, any of the heat transfer compositions of the present invention containing 1 to 50 heat transfer compositions in a condenser or in a residential air conditioner.

[0163]

Table 11

[0164] Accordingly, the system of the present invention preferably includes a sealing material that contacts at least a portion of the refrigerant and / or at least a portion of the lubricant according to the present invention, and the temperature of the sealing material and / or the temperature of the refrigerant and / or the temperature of the lubricant at the time of such contact is preferably at least about 10 °C, and the sealing material is preferably an anion exchange resin, activated alumina, a zeolite molecular sieve containing silver, and a moisture removal material, preferably a moisture removal molecular sieve.

[0165] As used in this application, the term "in contact with at least a portion" is intended, in its broadest sense, to include each of the sealing materials and any combination of sealing materials that are in contact with the same or separate portions of the refrigerant and / or lubricant within the system, and, without necessarily being limiting, various types or specific sealing materials are (i) types or specific materials that are physically located together with each other when present, (ii) types or specific materials that are physically located separately from each other when present, and (iii) a combination of two or more materials being physically together and at least one sealing material being physically separate from at least one other sealing material, and is intended to include embodiments that are.

[0166] The heat transfer composition of the present invention can be used for heating and cooling applications.

[0167] In a particular feature of the present invention, the heat transfer composition can be used in a cooling method that includes condensing the refrigerant of the present invention and then evaporating the refrigerant in the vicinity of the article or body to be cooled.

[0168] Accordingly, the present invention relates to a method of cooling in a heat transfer system comprising an evaporator, a condenser, and a compressor, the process comprising: i) condensing a refrigerant as described herein, particularly comprising any one of refrigerants 1 to 25; and ii) evaporating the refrigerant near a body or article to be cooled at a temperature of about -40°C to about +10°C.

[0169] Alternatively, or additionally, the heat transfer composition can be used in a heating method comprising condensing the heat transfer composition near an article or body to be heated and then evaporating the composition.

[0170] Accordingly, the present invention relates to a method of heating within a heat transfer system comprising an evaporator, a condenser, and a compressor, the process comprising: i) condensing a refrigerant as described herein, particularly comprising any one of refrigerants 1 to 25, near a body or article to be heated; and ii) evaporating the refrigerant at a temperature of about -30°C to about 5°C.

[0171] In particular, the refrigerants and heat transfer compositions according to the present invention comprising any one of refrigerants 1 to 25 of the present invention are provided for use in air conditioning applications including both mobile air conditioning applications and stationary air conditioning applications. As used herein, the term mobile air conditioning system means a mobile non-passenger vehicle air conditioning system such as those for trucks, buses, and trains. Accordingly, in particular, any of the refrigerants and any of the heat transfer compositions according to the present invention comprising any one of refrigerants 1 to 25 described herein are Air conditioning applications including mobile air conditioning systems, particularly air conditioning systems in buses and trains, Mobile heat pumps, particularly heat pumps for electric vehicles, Coolers, particularly positive displacement coolers, especially air-cooled or water-cooled direct expansion coolers (either modular or conventionally individually packaged), Residential air conditioning systems, particularly ducted split or ductless split air conditioning systems, Residential heat pumps, Residential air-water heat pump / water heating system, Industrial air conditioning system, Commercial air conditioning system which is a packaged rooftop unit or a variable refrigerant flow (VRF) system, It can be used in any one of commercial air heat source, water heat source, or ground source heat pump systems.

[0172] In particular, the refrigerant according to the present invention containing any one of Refrigerants 1 to 25 of the present invention and the heat transfer composition of the present invention are provided for use in a refrigeration system. The term "refrigeration system" refers to any system or apparatus that uses a refrigerant to provide cooling, or any component or part of such a system or apparatus. Thus, in particular, any refrigerant according to the present invention containing any one of Refrigerants 1 to 25 described herein and any of the heat transfer compositions described herein can be used in any one of the following refrigeration systems. Low-temperature refrigeration system, Medium-temperature refrigeration system, Commercial refrigerator, Commercial freezer, Ice maker, Vending machine, Transport refrigeration system, Household refrigerator, Household chiller, Industrial freezer, Industrial chiller, and Cooler.

[0173] Each of the heat transfer compositions described herein that includes any one of Refrigerants 1-25 is particularly provided for use in a residential air conditioning system (having an evaporator temperature in the range of about 0 to about 10°C, particularly about 7°C, and / or in the range of about -20 to about 3°C, particularly about 0.5°C for heating). Alternatively, or additionally, each of the heat transfer compositions described herein that includes any one of Refrigerants 1-25 and each of Heat Transfer Compositions 1-50 is particularly provided for use in a residential air conditioning system having a reciprocating, rotary (rolling piston or rotary valve), or scroll compressor.

[0174] Each of the described heat transfer compositions that includes any one of Refrigerants 1-25 and each of Heat Transfer Compositions 1-50 is particularly provided for use in an air-cooled condenser (having an evaporator temperature in the range of about 0 to about 10°C, particularly about 4.5°C), particularly an air-cooled condenser having a positive displacement compressor, especially an air-cooled condenser having a reciprocating scroll compressor.

[0175] Each of the heat transfer compositions described herein that includes any one of Refrigerants 1-25 and each of Heat Transfer Compositions 1-50 is particularly provided for use in a residential air-to-water heat pump water heating system (having an evaporator temperature in the range of about -20 to about 3°C, particularly about 0.5°C, or in the range of about -30 to about 5°C, particularly about 0.5°C).

[0176] Each of the heat transfer compositions that includes any one of Refrigerants 1-25 and each of Heat Transfer Compositions 1-50 is particularly provided for use in a medium temperature refrigeration system (having an evaporator temperature in the range of about -12 to about 0°C, particularly about -8°C).

[0177] Each heat transfer composition containing any one of Refrigerants 1 to 25 and each heat transfer composition containing each of Heat Transfer Compositions 1 to 50 are particularly provided for use in a low-temperature refrigeration system (having an evaporator temperature in the range of about -40 to about -12°C, particularly about -40°C to about -23°C, or preferably about -32°C).

[0178] Each heat transfer composition containing any one of Refrigerants 1 to 25 and each heat transfer composition containing each of Heat Transfer Compositions 1 to 50 are provided for use in a residential air conditioning system, which is used, for example, to supply cool air (the air having a temperature of, for example, about 10°C to about 17°C, particularly about 12°C) to a building in summer. Typical system types are split type, mini-split type, and window type, duct split type, ductless split type, window type, and portable type air conditioning systems. The system usually has an air-refrigerant evaporator (indoor coil), a compressor, an air-refrigerant condenser (outdoor coil), and an expansion valve. The evaporator and condenser are usually round tube plate fins, finned tubes, or microchannel heat exchangers. The compressor is usually a reciprocating, or rotary (rolling piston or rotary valve), or scroll compressor. The expansion valve is usually a capillary tube, a thermostatic expansion valve, or an electronic expansion valve. The refrigerant evaporation temperature is preferably within the range of 0 to 10°C. The condensation temperature is preferably within the range of 40 to 70°C.

[0179] The heat transfer composition of the present invention, which contains a heat transfer composition containing any one of Refrigerants 1 to 25, is provided for use in a residential heat pump system, which is used to supply warm air (the air has a temperature of, for example, about 18°C to about 24°C, particularly about 21°C) to a building in winter. This can be the same system as a residential air conditioning system, but in the heat pump mode, the refrigerant flow is reversed, the indoor coil becomes the condenser, and the outdoor coil becomes the evaporator. Typical system types are split and mini-split heat pump systems. The evaporator and condenser are usually round tube plate fins, fin type, or microchannel heat exchangers. The compressor is usually a reciprocating, rotary (rolling piston or rotary valve), or scroll compressor. The expansion valve is usually a thermostatic expansion valve or an electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of about -20 to about 3°C or about -30 to about 5°C. The condensation temperature is preferably in the range of about 35 to about 50°C.

[0180] The heat transfer composition of the present invention, which contains a heat transfer composition containing any one of Refrigerants 1 to 25, is provided for use in a commercial air conditioning system, which can be a chiller used to supply chilled water (the water has a temperature of, for example, about 7°C) to large buildings such as offices and hospitals. Depending on the application, the chiller system may operate throughout the year. The chiller system can be air-cooled or water-cooled. An air-cooled chiller usually has a plate, tube-in-tube, or shell-in-tube evaporator for supplying chilled water, a reciprocating or scroll compressor, round tube plate fins, fin-tube, or microchannel condenser for exchanging heat with the ambient air, and a thermostatic expansion valve or an electronic expansion valve. A water-cooled system usually has a shell-and-tube evaporator for supplying chilled water, a reciprocating, scroll, screw, or centrifugal compressor, a shell-and-tube condenser for exchanging heat with water from a cooling tower or a lake, sea, and other natural sources, and a thermostatic expansion valve or an electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of about 0 to about 10°C. The condensation temperature is preferably in the range of about 40 to about 70°C.

[0181] The heat transfer composition of the present invention, which comprises a heat transfer composition containing any one of Refrigerants 1 to 25, is provided for use in a domestic air-to-water heat pump water heating system, which is used to supply hot water (the water having a temperature of, for example, about 50°C or about 55°C) to a building for floor heating or similar applications in winter. The water heating system typically has a round tube plate fin, fin-tube type, or microchannel evaporator for exchanging heat with ambient air, a reciprocating, scroll, or rotary compressor, a plate, tube-in-tube type, or shell-and-tube type condenser for heating the water, and a temperature expansion valve or an electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of about -20 to about 3°C or -30 to about 5°C. The condensation temperature is preferably in the range of about 50°C to about 90°C.

[0182] The heat transfer composition of the present invention, which comprises a heat transfer composition containing any one of Refrigerants 1 to 25, is provided for use in a medium-temperature refrigeration system, which is preferably used to cool food or beverages in a refrigerator or a bottle cooler, etc. The system typically has an air-refrigerant evaporator for cooling food or beverages, a reciprocating, scroll, screw, or rotary compressor, an air-refrigerant condenser for exchanging heat with ambient air, and a temperature expansion valve or an electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of about -12°C to about 0°C. The condensation temperature is preferably in the range of about 40 to about 70°C or about 20 to about 70°C.

[0183] The heat transfer composition of the present invention, such as a heat transfer composition containing any one of refrigerants 1 to 25, is provided for use in a low-temperature refrigeration system, which is preferably used in a refrigerator or an ice cream maker. The system usually has an air-refrigerant evaporator for cooling food or drinks, a reciprocating, scroll, or rotary compressor, an air-refrigerant condenser for exchanging heat with the ambient air, and a temperature expansion valve or an electronic expansion valve. The refrigerant evaporation temperature is preferably in the range of about -40°C to about -12°C. The condensation temperature is preferably in the range of about 4 to about 70°C or about 20 to about 70°C.

[0184] The heat transfer composition contains any one of refrigerants 1 to 25 in a cooler or a commercial air conditioning system as follows.

[0185] [Table 12]

[0186] The heat transfer composition contains any one of refrigerants 1 to 25, stabilizer 1, and a POE lubricant in a cooler or a commercial air conditioning system as follows.

[0187] [Table 13]

[0188] For the purpose of the present invention, the above heat transfer composition is provided for use in a cooler having an evaporation temperature in the range of about 0°C to about 10°C and a condensation temperature in the range of about 40°C to about 70°C. The cooler is provided for use in air conditioning or refrigeration, preferably for refrigeration. The cooler is preferably a positive displacement cooler, especially an air-cooled or water-cooled direct expansion cooler (either modular or conventionally single-packaged).

[0189] The heat transfer composition contains any one of refrigerants 1 to 25 in an air conditioning system, and residential air conditioning is hereinafter abbreviated as residential AC.

[0190] The heat transfer composition contains any one of refrigerants 1 to 25 in a residential air conditioning system or a heat pump as shown in the following table.

[0191] [Table 14]

[0192] The heat transfer composition contains any one of refrigerants 1 to 25 and stabilizer 1 in a residential AC or a heat pump as follows.

[0193]

Table 15

[0194] The heat transfer composition contains any one of refrigerants 1 to 25, stabilizer 1 and POE lubricant in a residential AC or a heat pump as follows.

[0195]

Table 16

[0196] The heat transfer composition contains any one of refrigerants 1 to 25 in a low-temperature refrigeration system or a medium-temperature system as follows.

[0197]

Table 17

[0198] The heat transfer composition contains any one of refrigerants 1 to 25 and stabilizer 1 in a low-temperature refrigeration system or a medium-temperature refrigeration system as follows.

[0199]

Table 18

[0200] The heat transfer composition includes any one of Refrigerants 1 to 25, a stabilizer 1, and a POE lubricant in a low-temperature refrigeration or medium-temperature refrigeration system as follows.

[0201]

Table 19

[0202] Accordingly, the present invention includes a method of additionally introducing an existing heat transfer system designed for and containing R-410A refrigerant without requiring substantial engineering changes to the existing system, particularly without changing the condenser, evaporator, and / or expansion valve.

[0203] In particular, the refrigerant according to the present invention containing any one of Refrigerants 1 to 25 disclosed herein and the heat transfer composition disclosed herein are provided as low-GWP alternatives to refrigerant R-410A. Accordingly, the heat transfer compositions and refrigerants of the present invention (including each of Refrigerants 1 to 25 and all heat transfer compositions containing Refrigerants 1 to 25) can be used as substitute refrigerants / heat transfer compositions.

[0204] Accordingly, the present invention also includes a method of using the refrigerant or heat transfer composition of the present invention as an alternative to R-410A, particularly as an alternative to R-410A in residential air conditioners, without requiring substantial engineering changes to the existing system, particularly without changing the condenser, evaporator, and / or expansion valve.

[0205] Accordingly, the present invention also includes a method of using the refrigerant or heat transfer composition of the present invention as an alternative to R-410A, particularly as an alternative to R-410A in a chiller system.

[0206] Accordingly, the present invention also includes a method of using the refrigerant or heat transfer composition of the present invention as an alternative to R-410A, particularly as an alternative to R-410A in a residential air conditioning system including.

[0207] Accordingly, a method for retrofitting an existing heat transfer system containing R-410A refrigerant is provided, the method including replacing at least a portion of the existing R-410A refrigerant with the heat transfer composition of the present invention, each of which comprises Heat Transfer Compositions 1-50. The replacement step preferably involves no substantial alteration of the system containing the refrigerant of the present invention and removing at least a substantial portion, preferably substantially all, of the existing refrigerant (which may be, but is not limited to, R-410A) and introducing a heat transfer composition comprising each of Heat Transfer Compositions 1-50. Preferably, the method includes removing at least about 5 wt%, about 10 wt%, about 25 wt%, about 50 wt%, or about 75 wt% of the R-410A from the system and replacing it with the heat transfer composition of the present invention.

[0208] Alternatively, the heat transfer composition can be used in a method of retrofitting an existing heat transfer system that is designed to contain or contains R410A refrigerant, and the system is modified for use with the heat transfer composition of the present invention.

[0209] Alternatively, the heat transfer composition can be used as a replacement in a heat transfer system that is designed to contain or is suitable for use with R-410A refrigerant.

[0210] Alternatively, it will be understood that the present invention encompasses the use of the heat transfer composition of the present invention as a low global warming alternative to R-410A, or for use in a method of retrofitting an existing heat transfer system, or for use in a heat transfer system suitable for use with R-410A refrigerant as described herein.

[0211] Accordingly, a method is provided for replacing the R-410A refrigerant believed to be used in a particular heat transfer system with the refrigerant or heat transfer composition of the present invention, particularly including any of Refrigerants 1-25.

[0212] It will be understood that when the heat transfer composition is used as a low GWP alternative to R-410A, the heat transfer composition can consist essentially of the refrigerant of the present invention. Alternatively, the present invention encompasses the use of the refrigerant of the present invention as a low GWP alternative to R-410A.

[0213] When the heat transfer composition is provided for use in the manner of adding an existing heat transfer system as described above, it will be understood by those skilled in the art that this method preferably includes removing at least a portion of the existing R-410A refrigerant from the system. Preferably, this method includes removing at least about 5 wt%, about 10 wt%, about 25 wt%, about 50 wt%, or about 75 wt% of the R-410A from the system and replacing it with the heat transfer composition of the present invention.

[0214] The heat transfer compositions of the present invention, each comprising Refrigerants 1-25 and each comprising Heat Transfer Compositions 1-50, can be used as an alternative in systems that are used with or are suitable for use with an R-410A refrigerant, such as an existing heat transfer system or a new heat transfer system.

[0215] The compositions of the present invention exhibit many of the desired properties of R-410A, but have a substantially lower GWP than R-410A and at the same time are substantially the same as or substantially coincide with R-410A, and more preferably have operating characteristics, i.e., capacity and / or efficiency (COP), that are as high as or higher than that of R-410A. Thereby, in an existing heat transfer system, without the need for any major system changes, such as to condensers, evaporators, and / or expansion valves. the claimed compositions can be substituted for R-410A. Thus, the compositions can be used as a direct replacement for R-410A in heat transfer systems.

[0216] Therefore, the heat transfer compositions of the present invention, each containing each of the compositions containing refrigerants 1 to 25 and each of the heat transfer compositions 1 to 50, preferably exhibit operating characteristics such that the efficiency (COP) of the composition is more than 90% of the efficiency of R-410A in a heat transfer system.

[0217] Therefore, the heat transfer compositions of the present invention, each containing each of the compositions containing refrigerants 1 to 25 and each of the heat transfer compositions 1 to 50, preferably exhibit operating characteristics such that the capacity is 95 to 105% of the capacity of R-410A in a heat transfer system as compared to R-410A.

[0218] It will be appreciated that R-410A is an azeotrope-like composition. Therefore, in order for the compositions recited in the claims to match the operating characteristics of R-410A, it is desirable that any of the refrigerants included in the heat transfer compositions of the present invention, each containing each of the heat transfer compositions 1 to 50, exhibit a low level of gradient. Therefore, the refrigerants included in the heat transfer compositions of the present invention, each containing each of the heat transfer compositions 1 to 50 according to the present invention described herein, can provide an evaporator gradient of less than 2°C, preferably less than 1.5°C.

[0219] Therefore, the heat transfer compositions of the present invention, each containing each of the compositions containing refrigerants 1 to 25 and each of the heat transfer compositions 1 to 50, preferably exhibit operating characteristics such that the efficiency (COP) of the composition is 100 to 102% of the efficiency of R-410A in a heat transfer system and the capacity is 92 to 102% of the capacity of R-410A in a heat transfer system as compared to R-410A.

[0220] Preferably, the heat transfer compositions of the present invention, each containing each of the compositions containing refrigerants 1 to 25 and each of the heat transfer compositions 1 to 50, preferably, in a heat transfer system, as compared to R-410A, - the efficiency (COP) of the composition is 100 to 105% of the efficiency of R-410A and / or - the capacity is 92 to 102% of the capacity of R-410A, The compositions of the present invention replace R-410A refrigerant.

[0221] To improve the reliability of the heat transfer system, the heat transfer compositions of the present invention, each containing one of refrigerants 1 to 25 and each of heat transfer compositions 1 to 50, in the heat transfer system, compared to R-410A, - the discharge temperature is not more than 10 °C higher than the discharge temperature of R-410A, and / or - the compressor pressure ratio preferably further exhibits the characteristic that it is 98 to 102% of the compressor pressure ratio of R-410A, The compositions of the present invention are used to replace the R-410A refrigerant.

[0222] The existing heat transfer compositions used to replace R-410A are preferably heat transfer systems for air conditioners including both mobile air conditioning systems and stationary air conditioning systems. As used herein, the term mobile air conditioning system means a mobile non-passenger vehicle air conditioning system such as those for trucks, buses, and train air conditioning systems. Thus, each of the heat transfer compositions as described herein, each containing one of heat transfer compositions 1 to 50, - an air conditioning system including a mobile air conditioning system, particularly those for trucks, buses, and train air conditioning systems, - a mobile heat pump, particularly a heat pump for electric vehicles, - a cooler, particularly a positive displacement cooler, especially an air-cooled or water-cooled direct expansion cooler (either modular or individually packaged by conventional methods), - a residential air conditioning system, particularly a duct split type or ductless split type air conditioning system, - a residential heat pump, - a residential air-water heat pump / water heating system, - an industrial air conditioning system, and - a packaged rooftop unit or a variable refrigerant flow (VRF) system, - can be used to replace R-410A in any one of commercial air source, water source, or ground source heat pump systems.

[0223] The heat transfer composition of the present invention is alternatively provided to replace R410A in a refrigeration system. Thus, each of the heat transfer compositions as described herein, including each of the compositions containing refrigerants 1 to 25 and each of the heat transfer compositions 1 to 50, - a low-temperature refrigeration system, - a medium-temperature refrigeration system, - a commercial refrigerator, - a commercial freezer, - an ice maker, - a vending machine, - a transport refrigeration system, - a household freezer, - a household refrigerator, - an industrial freezer, - an industrial refrigerator, and - a chiller, can be used to replace R10A in any one of them.

[0224] To maintain the reliability of the heat transfer system, in the heat transfer system where the composition of the present invention is used in place of the R-410A refrigerant, it is preferable that the composition of the present invention further exhibits the following characteristics in which the compressor pressure ratio is 95 to 105% of the compressor pressure ratio of R-410A as compared with R-410A.

[0225] Each of the compositions containing refrigerants 1 to 25 and each of the heat transfer compositions as described herein, including each of the heat transfer compositions 1 to 50, are particularly provided to replace R-410A in an air-cooled chiller (having an evaporator temperature in the range of about 0 to about 10°C, particularly about 4.5°C), particularly an air-cooled chiller having a positive displacement compressor, especially an air-cooled chiller having a reciprocating scroll compressor.

[0226] Each of the compositions containing refrigerants 1 to 25 and each of the heat transfer compositions as described herein, including each of the heat transfer compositions 1 to 50, are particularly provided to replace R-410A in a residential air-water heat pump water heating system (having an evaporator temperature in the range of about -20 to about 3°C or about -30 to about 5°C, particularly about 0.5°C).

[0227] Each of the heat transfer compositions described herein that includes any one of Refrigerants 1 - 25 is provided specifically for replacing R - 410A in a medium - temperature refrigeration system (having an evaporator temperature in the range of about - 12 to about 0 °C, particularly about - 8 °C).

[0228] Each of the heat transfer compositions described herein that includes any one of Refrigerants 1 - 25 is provided specifically for replacing R - 410A in a low - temperature refrigeration system (having an evaporator temperature in the range of about - 40 to about - 12 °C, particularly about - 40 °C to about - 23 °C, or preferably about - 32 °C).

[0229] Accordingly, a method is provided for retrofitting an existing heat transfer system that is designed to contain or contains an R - 410A refrigerant or is suitable for use with an R - 410A refrigerant, the method including replacing at least a portion of the existing R - 410A refrigerant with a heat transfer composition of the present invention that includes any one of Heat Transfer Compositions 1 - 50.

[0230] Accordingly, a method is provided for retrofitting an existing heat transfer system that is designed to contain or contains an R - 410A refrigerant or is suitable for use with an R - 410A refrigerant, the method including replacing at least a portion of the existing R - 410A refrigerant with a heat transfer composition according to the present invention that includes any one of Heat Transfer Compositions 1 - 50.

[0231] The present invention further provides a heat transfer system including a compressor, a condenser, and an evaporator in fluid communication and containing a heat transfer composition therein, the heat transfer composition including any one of Refrigerants 1 - 25.

[0232] In particular, the heat transfer system is a residential air - conditioning system (having an evaporator temperature in the range of about 0 to about 10 °C for cooling, particularly about 7 °C, and / or in the range of about - 20 to about 3 °C or about - 30 to about 5 °C for heating, particularly about 0.5 °C) and includes any one of Refrigerants 1 - 25.

[0233] In particular, the heat transfer system is an air-cooled cooler (having an evaporator temperature in the range of about 0 to about 10 °C, particularly about 4.5 °C), in particular an air-cooled cooler having a positive displacement compressor, especially an air-cooled cooler having a reciprocating or scroll compressor, and contains any one of refrigerants 1 to 25.

[0234] In particular, the heat transfer system is a residential air-water heating system (having an evaporator temperature in the range of about -20 to about 3 °C or about -30 to about 5 °C, particularly about 0.5 °C), and contains any one of refrigerants 1 to 25.

[0235] The heat transfer system can be a refrigeration system, such as a low-temperature refrigeration system, a medium-temperature refrigeration system, a commercial refrigerator, a commercial freezer, an ice maker, a vending machine, a transport refrigeration system, a household refrigerator, a household freezer, an industrial freezer, and a cooler, and contains any one of refrigerants 1 to 25.

Example

[0236] The refrigerant compositions specified in Table 2 below as Refrigerants A1, A2, and A3 are refrigerants within the scope of the present invention as described herein. Each of the refrigerants was subjected to a thermodynamic analysis to determine its ability to match the operating characteristics of R-4104A in various refrigeration systems. The analysis was carried out using experimental data collected on the properties of various binary pairs of the components used in the compositions. The vapor / liquid equilibrium behavior of CF3I was measured and investigated in a series of binary pairs each containing HFC-32 and R125. In the experimental evaluation, the composition of each binary pair was varied over a series of relative percentages, and the mixing parameters of each binary pair were regressed to the experimentally obtained data. In the examples, vapor / liquid equilibrium behavior data for the binary pair of HFC-32 and HFC-125, which are 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), were used. The parameters selected for the analysis were the same compressor volume for all refrigerants, the same operating conditions for all refrigerants, and the same compressor adiabatic efficiency and volumetric efficiency for all refrigerants. In each example, simulations were performed using the measured vapor-liquid equilibrium data. The simulation results are reported for each example. Simulations were performed using the measured vapor-liquid equilibrium data.

[0237]

Table 20

[0238] Refrigerant A1 contains 100% by weight of the three compounds listed in Table 2 in relative percentages and is non-flammable. Refrigerant A2 contains 100% by weight of the three compounds listed in Table 2 in relative percentages and is non-flammable. Refrigerant A3 contains 100% by weight of the three compounds listed in Table 2 in relative percentages and is non-flammable.

[0239] Example 1 - Environment / GWP The LCCP was determined for R410, other known refrigerants, and the refrigerant of the present invention and reported in Table 3. In Table 3, the refrigerant with a GWP of 399 is the refrigerant of the present invention. As known refrigerants, refrigerants with GWPs of 1, 150, 250, 750, and 2088 were used. The known refrigerant with a GWP of 2088 is R410A.

[0240] Table 3 shows the LCCP results in four regions: the United States, the EU, China, and Brazil. As the GWP decreases, the direct emissions decrease. However, due to the lower system efficiency, more energy is consumed and the indirect emissions increase. Therefore, the total emissions (kg-CO 2eq ) first decrease and then increase as the GWP decreases. The various energy structures within these regions show the optimal GWP value with the lowest total emissions. The number of AC units also varies between these regions. That is, the USA and the EU have more AC units than China and Brazil. The last columns of Figure 1 and Table 3 show the total emissions considering all four regions and the total number of AC units. As the GWP decreases, the total emissions decrease until they reach the lowest value for the refrigerant of the present invention with a GWP of 400. In the range of GWP from 250 to 750, the total emissions are very similar. However, when the GWP is less than 150, the total emissions increase significantly because the indirect emissions increase significantly. Therefore, the present invention demonstrates surprising and unexpected results.

[0241]

Table 21

[0242] Example 2 - Residential air conditioning system (cooling) The residential air conditioning system is used to supply cold air (12°C) to a building in summer. Refrigerants A1, A2, and A3 are used in the simulation of the residential air conditioning system as described above, and the performance results are shown in Table 4 below. Examples of residential air conditioning systems include split air conditioning systems, mini-split air conditioning systems, and window air conditioning systems, and the tests described in this specification are representative of the results obtained from such systems. The experimental system includes an air-refrigerant evaporator (indoor coil), a compressor, an air-refrigerant condenser (outdoor coil), and an expansion valve. The operating conditions of the test are as follows. Condensing temperature = 46°C, condenser subcooling = 5.5°C, evaporating temperature = 7°C, evaporator superheat = 5.5°C, isentropic efficiency = 70%, volumetric efficiency: 100%, temperature rise in the suction line = 5.5°C.

[0243]

Table 22

[0244] Table 4 shows the thermodynamic performance of the residential air conditioning system compared to the R410A system. Refrigerants A1 - A3 show 92% or more capacity and efficiency compared to R410A. This indicates that the system performance is similar to that of R410A. Refrigerants A1 - A3 show a pressure ratio of 100% compared to R410A. This indicates that the compressor efficiency is similar to that of R410A, and no change to the R410A compressor is necessary.

[0245] Example 3 - Residential Heat Pump System (Heating) Residential heat pump systems are used to supply warm air (21.1 °C) to buildings in winter. Refrigerants A1, A2, and A3 are used in the simulation of the residential air conditioning system as described above, and the performance results are shown in Table 5 below. The experimental system includes a residential air conditioning system, but when the system is in the heat pump mode, the refrigerant flow is reversed, the indoor coil becomes the condenser, and the outdoor coil becomes the evaporator. Examples of residential heat pump systems include split air conditioning systems, mini-split air conditioning systems, and window air conditioning systems, and the tests described in this specification are representative of the results obtained from such systems. The operating conditions are as follows. 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%, temperature rise in the suction line = 5.5 °C.

[0246]

Table 23

[0247] Table 5 shows the thermodynamic performance of the residential heat pump system compared to the R410A system. The capacity of Refrigerant A1 can be recovered with a larger compressor. Refrigerants A2 - A3 show more than 90% capacity and efficiency compared to R410A. This indicates that the system performance is similar to that of R410A. Refrigerants A1 - A3 show a pressure ratio of 100% compared to R410A. This indicates that the compressor efficiency is similar to that of R410A, and no change to the R410A compressor is necessary.

[0248] Example 4 - Commercial Air Conditioning System - Cooler Commercial air conditioning systems (coolers) are used to supply chilled water (7°C) to large buildings such as offices and hospitals. Depending on the specific application, the cooler system may operate throughout the year. The tests described in this document are representative of the results obtained from such systems. Refrigerants A1, A2, and A3 are used in the simulation of commercial air conditioning systems as described above, and the performance results are shown in Table 6 below. The operating conditions are as follows: 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%, temperature rise in the suction line = 2°C.

[0249]

Table 24

[0250] Table 6 shows the thermodynamic performance of the commercial air conditioning system compared to the R410A system. Refrigerants A1 - A3 show a capacity and efficiency of 92% or more compared to R410A. This indicates that the system performance is similar to that of R410A. Refrigerants A1 - A3 show a pressure ratio of 100% compared to R410A. This indicates that the compressor efficiency is similar to that of R410A, and no change to the R410A compressor is necessary.

[0251] Example 5 - Residential air - water heat pump water heating system Test a residential air - water heat pump water heating system used to supply hot water (50°C) to a building for floor heating or similar applications in winter. Refrigerants A1, A2, and A3 are used in the simulation of the residential heat pump system as described above, and the performance results described in this document represent the results from such a system and are shown in Table 7 below. The operating conditions are: Condensing temperature = 60°C (corresponding indoor outlet water temperature of approximately 50°C), condenser subcooling = 5.5°C, evaporating temperature = approximately 0.5°C (corresponding outdoor ambient temperature = approximately 8.3°C), evaporator superheat = 5.5°C, isentropic efficiency = 70%, volumetric efficiency: 100%, temperature rise in the suction line = 2°C.

[0252]

Table 25

[0253] Table 7 shows the thermodynamic performance of a residential heat pump system compared with the R410A system. Refrigerants A1 - A3 exhibit over 93% capacity and efficiency compared with R410A, indicating that the system performance is similar to that of R410A. Refrigerants A1 - A2 show a pressure ratio of 100% compared with R410A, indicating that the compressor efficiency is similar to that of R410A and no modification to the R410A compressor is necessary. Furthermore, Refrigerant A2 shows a pressure ratio of 100% compared with R - 410A, indicating that the compressor efficiency is sufficiently equivalent to that of R - 410A and no modification to the compressor used with R - 410A is required.

[0254] Example 6 - Medium - temperature refrigeration system Test a medium - temperature refrigeration system used for cooling food or drinks in refrigerators and bottle coolers, etc. The experimental system includes an air - refrigerant evaporator for cooling food or drinks, a compressor, an air - refrigerant condenser for exchanging heat with the ambient air, and an expansion valve. Refrigerants A1, A2, and A3 are used in the simulation of the medium - temperature refrigeration system as described above, and the performance results are shown in Table 8 below. Operating conditions: Condensing temperature = 40.6 °C, condenser sub - cooling = 0 °C (system with receiver), Evaporating temperature = - 6.7 °C, Evaporator superheat = 5.5 °C, Isentropic efficiency = 70%, Volumetric efficiency: 100%, and Superheat in the suction line = 19.5 °C.

[0255]

Table 26

[0256] Table 8 shows the thermodynamic performance of the medium-temperature refrigeration system compared with the R410A system. Refrigerants A1 - A3 show over 94% capacity and efficiency compared with R410A, indicating that the system performance is similar to that of R410A. Refrigerants A1 - A2 show a pressure ratio of 100% compared with R410A, indicating that the compressor efficiency is similar to that of R410A and no change to the R410A compressor is necessary. Furthermore, Refrigerant A2 shows a pressure ratio of 100% compared with R - 410A, indicating that the compressor efficiency is fully equivalent to that of R - 410A and no change to the compressor used with R - 410A is necessary.

[0257] Example 7 - Low - temperature Refrigeration System The low - temperature refrigeration system is used in ice cream makers, refrigerators, etc. for freezing food. The experimental system includes an air - refrigerant evaporator for cooling or freezing food or drinks, a compressor, an air - refrigerant condenser for exchanging heat with the ambient air, and an expansion valve. The tests described herein are representative of the results obtained from such systems. Refrigerants A1, A2, and A3 are used in the simulation of the low - temperature refrigeration system as described above, and the performance results are shown in Table 9 below. Operating conditions: Condensing temperature = 40.6 °C, condenser sub - cooling = 0 °C (system with receiver), evaporating temperature = - 28.9 °C, superheat at the evaporator outlet = 5.5 °C, isentropic efficiency = 65%, volumetric efficiency: 100%, and superheat in the suction line = 44.4 °C.

[0258]

Table 27

[0259] Table 9 shows the thermodynamic performance of the low - temperature refrigeration system compared with the R410A system. Refrigerants A1 - A3 show over 96% capacity and efficiency compared with R410A, indicating that the system performance is similar to that of R410A. Refrigerants A1 - A3 show a pressure ratio of 99% or 100% compared with R410A, indicating that the compressor efficiency is similar to that of R410A and no change to the R410A compressor is necessary.

[0260] Example 8. Commercial Air Conditioning System - Packaged Rooftop Test a packaged rooftop commercial air conditioning system configured to supply cooled or heated air to a building. The experimental system includes a packaged rooftop air conditioning / heat pump system having an air-refrigerant evaporator (indoor coil), a compressor, an air-refrigerant condenser (outdoor coil), and an expansion valve. The tests described herein are representative of the results obtained from such systems. The operating conditions of the tests are as follows. 1. Condensing temperature = about 46 °C (corresponding outdoor ambient temperature = about 35 °C) 2. Condenser subcooling = about 5.5 °C 3. Evaporating temperature = about 7 °C (corresponding indoor ambient temperature = 26.7 °C) 4. Evaporator superheat = about 5.5 °C 5. Insulation efficiency = 70% 6. Volumetric efficiency = 100% 7. Temperature rise in the suction line = 5.5 °C

[0261] Report the performance results of the tests in Table 8 below.

[0262] [Table 28]

[0263] Table 8 shows the thermodynamic performance of a rooftop commercial air conditioning system operating with Refrigerants A1, A2, and A3 of the present invention compared to R-410A, and Refrigerants A2 and A3 exhibit more than 90% of the capacity and efficiency of R410A. This indicates that the system performance is similar to that of R410A. The capacity of Refrigerants A2 and A3 can be recovered with a larger compressor. Refrigerants A1 - A3 exhibit a pressure ratio of 100% compared to R410A. This indicates that the compressor efficiency is similar to that of R410A and shows that no significant design changes to the compressor of R410A are required.

[0264] Example 9 - Commercial Air Conditioning System - Variable Refrigerant Flow System Test a commercial air conditioning system that uses a variable refrigerant flow configured to supply cooled or heated air to a building. The system includes a plurality (four or more) of air-refrigerant evaporators (indoor coils), a compressor, an air-refrigerant condenser (outdoor coil), and an expansion valve. The conditions described herein represent the operating conditions obtained from such a system. The operating conditions are listed below. 1. Condensing temperature = about 46 °C, corresponding outdoor ambient temperature = 35 °C 2. Condenser subcooling = about 5.5 °C 3. Evaporating temperature = about 7 °C (corresponding indoor ambient temperature = 26.7 °C) 4. Evaporator superheat = about 5.5 °C 5. Insulation efficiency = 70% 6. Volumetric efficiency = 100% 7. Temperature rise in the suction line = 5.5 °C

[0265]

Table 29

[0266] Table 9 shows the thermodynamic performance of a rooftop commercial air conditioning system operating with refrigerants A1, A2, and A3 of the present invention compared to R-410A. Refrigerants A2 and A3 exhibit more than 90% of the capacity and efficiency of R410A. This indicates that the system performance is similar to that of R410A. The capacity of refrigerants A2 and A3 can be recovered with a larger compressor. Refrigerants A1 - A3 exhibit a pressure ratio of 100% compared to R410A. This indicates that the compressor efficiency is similar to that of R410A, showing that no significant design changes to the R410A compressor are required.

[0267] Example 10 - Stabilizers for Heat Transfer Compositions Containing Refrigerants and Lubricants The heat transfer composition of the present invention was tested in accordance with ASHRAE Standard 97 - “Sealed Test according to the "Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems" to simulate the long-term stability of the heat transfer composition by accelerated aging. After the test, the concentration of the halide is considered to reflect the stability of the refrigerant under the use conditions in the heat transfer composition, and the total acid number (TAN) is considered to reflect the stability of the lubricant under the use conditions in the heat transfer composition.

[0268] To show the effect of adding the stabilizer according to the present invention to the refrigerant / lubricant composition, the following experiments were conducted. After degassing each, a sealed tube containing 50% by weight of the indicated refrigerant and 50% by weight of the indicated lubricant is prepared. Each tube contains coupons of steel, copper, aluminum, and bronze. The stability is tested by placing the sealed tube in a furnace maintained at about 175 °C for 14 days. In each case, the lubricants tested are ISO 32 POE (Lubricant A) having a viscosity of about 32 cSt at 40 °C and ISO 68 POE (Lubricant B) having a viscosity of about 68 cSt at 40 °C, and each lubricant has a water content of less than 300 ppm. The following refrigerants shown in Table 10A are tested.

[0269]

Table 30

[0270] Tests were conducted on each pair of lubricant and refrigerant without any stabilizer, and the results were as follows. Lubricant - Visual - Opaque or black Metal - Visual - Without luster Presence of solid - Yes Halide > 100 ppm TAN > 10 mg KOH / g

[0271] The following stabilizers shown in Table 10B have the weight percentages in the table as weight percentages in the stabilizer package of the indicated stabilizers and are tested in amounts of about 1.5% to about 10% based on the total weight of the stabilizer and the refrigerant.

[0272]

Table 31

[0273] The results of tests using these stabilizers and lubricants A1, A2, and A3 are reported below in Table 10C.

[0274]

Table 32

[0275] This test shows that the lubricants in each of these tests were colorless and transparent, the metals had a luster (no change), there were no solids present, and the concentrations of halides and TAN were within the allowable limits, all indicating that the stabilizers were effective.

[0276] Example 11 - Miscibility with POE Oil The miscibility of ISO POE - 32 oil (having a viscosity of about 32 cSt at a temperature of 40 °C) is tested for different weight ratios of lubricant to refrigerant and different temperatures with respect to R - 410A refrigerant and with respect to refrigerant A2 shown in Table 1 of Example 1 above. The results of this test are reported in Table 11 below.

[0277]

Table 33

[0278] As can be seen from the above table, R-410A is immiscible with POE oil at temperatures below about -22°C. Therefore, without taking measures to overcome the accumulation of POE oil in the evaporator, R-410A cannot be used in low-temperature refrigeration applications. Further, R-410A is immiscible with POE oil at temperatures above 50°C, which causes problems in the condenser and the liquid line when using R-410A under high ambient conditions (e.g., the separated POE oil is trapped and deposited). Conversely, the applicants have surprisingly and unexpectedly found that the refrigerant of the present invention is completely miscible with POE oil over a temperature range of -40°C to 80°C, and thus provides substantial and unexpected advantages when used in such a system.

[0279] Example 12 - Residential air conditioning system (cooling) with a seal and heat transfer composition with a stabilizer Repeat Example 2, except that an oil separator is included in the system and some of the sealing materials consisting independently of sealing materials 1 - 4 are included in the liquid portion of the oil separator. The heat transfer composition includes the lubricant 1 and stabilizer 1 in the amounts described herein. The system operates in each case as shown in Example 2 and exhibits a high level of stability such that an operation with an acceptable level of stability persists for at least one year in accordance with the tests shown in Examples 10 and 20 - 30 herein.

[0280] Example 13 - Residential heat pump system (heating) with a seal and heat transfer composition with a stabilizer Repeat Example 3, except that an oil separator is included in the system and some of the sealing materials consisting independently of sealing materials 1 - 4 are included in the liquid portion of the oil separator. The heat transfer composition includes the lubricant 1 and stabilizer 1 in the amounts described herein. The system operates in each case as shown in Example 2 and exhibits a high level of stability such that an operation with an acceptable level of stability persists for at least one year in accordance with the tests shown in Examples 10 and 20 - 30 herein.

[0281] Example 14 - Commercial Air Conditioning System (Cooler) with Blocking and Heat Transfer Composition with Stabilizer Repeat Example 4, except that an oil separator is included in the system and several blocking materials, independently consisting of blocking materials 1 to 4, are included in the liquid portion of the oil separator. The heat transfer composition includes lubricant 1 and stabilizer 1 in the amounts described herein. The system operates as shown in Example 2 in each case and operates to exhibit a high level of stability such that operation with an acceptable level of stability persists for at least one year, in accordance with the tests shown in Examples 10 and 20 - 30 of this specification.

[0282] Example 15 - Residential Air - Water Heat Pump Water Heating System with Blocking and Heat Transfer Composition with Stabilizer Repeat Example 5, except that an oil separator is included in the system and several blocking materials, independently consisting of blocking materials 1 to 4, are included in the liquid portion of the oil separator. The heat transfer composition includes lubricant 1 and stabilizer 1 in the amounts described herein. The system operates as shown in Example 2 in each case and operates to exhibit a high level of stability such that operation with an acceptable level of stability persists for at least one year, in accordance with the tests shown in Examples 10 and 20 - 30 of this specification.

[0283] Example 16 - Medium - Temperature Refrigeration System with Blocking and Heat Transfer Composition with Stabilizer Repeat Example 6, except that an oil separator is included in the system and several blocking materials, independently consisting of blocking materials 1 to 4, are included in the liquid portion of the oil separator. The heat transfer composition includes lubricant 1 and stabilizer 1 in the amounts described herein. The system operates as shown in Example 2 in each case and operates to exhibit a high level of stability such that operation with an acceptable level of stability persists for at least one year, in accordance with the tests shown in Examples 10 and 20 - 30 of this specification.

[0284] Example 17 - Low - Temperature Refrigeration System with Blocking and Heat Transfer Composition with Stabilizer Repeat Example 7, except that an oil separator is included in the system and several sealing materials, independently consisting of Sealing Materials 1-4, are included in the liquid portion of the oil separator. The heat transfer composition contains the amounts of Lubricant 1 and Stabilizer 1 described herein. The system operates as shown in Example 2 in each case and operates to exhibit a high level of stability such that operation with an acceptable level of stability persists for at least one year according to the tests shown in Examples 10 and 20-30 herein.

[0285] Example 18 - Commercial Air Conditioning System with Sealing - Packaged Rooftop and Heat Transfer Composition with Stabilizer Repeat Example 8, except that an oil separator is included in the system and several sealing materials, independently consisting of Sealing Materials 1-4, are included in the liquid portion of the oil separator. The heat transfer composition contains the amounts of Lubricant 1 and Stabilizer 1 described herein. The system operates as shown in Example 2 in each case and operates to exhibit a high level of stability such that operation with an acceptable level of stability persists for at least one year according to the tests shown in Examples 10 and 20-30 herein.

[0286] Example 19 - Commercial Air Conditioning System with Sealing - Variable Refrigerant Flow System and Heat Transfer Composition with Stabilizer Repeat Example 9, except that an oil separator is included in the system and several sealing materials, independently consisting of Sealing Materials 1-4, are included in the liquid portion of the oil separator. The heat transfer composition contains the amounts of Lubricant 1 and Stabilizer 1 described herein. The system operates as shown in Example 2 in each case and operates to exhibit a high level of stability such that operation with an acceptable level of stability persists for at least one year according to the tests shown in Examples 10 and 20-30 herein.

[0287] Example 20 - Sealing Material Containing Silver Zeolite The ability of silver containing zeolite acting as a blocking material was tested. The zeolite tested was UPO IONSIV D7310-C available from Honeywell UOP. The openings have sizes over their maximum dimensions of about 15 to about 35 Å .

[0288] A formulation of 80 wt% POE oil (POE ISO32, Emkarate RL 32-3MAF) containing 1000 ppm of the primary antioxidant stabilizer BHT and 20 wt% CF3I was placed in a sealed tube and heated at 190 °C for 2 days. Under these conditions, destruction of the refrigerant and lubricant occurred. The sealed tube was then opened and a sample of the oil was removed.

[0289] The oil sample was then placed in a Fischer-Porter tube together with the zeolite. The amount of dry zeolite relative to the sample (lubricant) was measured. The tube was then maintained at either 15 °C or 50 °C for 114 hours (4.75 days). The tube was shaken every 2 hours to ensure proper mixing of the zeolite and the sample.

[0290] The total acid number (TAN), iodide ppm, and fluoride ppm of the sample were measured at the start (i.e., after decomposition of CF3I and POE oil and before combination with zeolite), and at the end (i.e., after combination with zeolite and at the end of 114 hours at 15 °C or 50 °C). The concentrations of TAN, fluoride, and iodide were measured according to the same method described in Example 10.

[0291] The results of the test are described in Table 20.

[0292]

Table 34

[0293] The above tests demonstrate the ability of zeolite to effectively "restore" the composition of POE oil and CF3I refrigerant after it has decomposed.

[0294] This result demonstrates that when using either about 5 pphl zeolite or about 21 pphl zeolite, the zeolite was able to reduce the iodide and fluoride levels in the decomposed samples at both 15°C and 50°C. However, the zeolite functioned better at 50°C than at 15°C, and also better with about 21 pphl zeolite than with about 5 pphl zeolite. Surprisingly, at 50°C with about 21 pphl zeolite, only trace amounts of iodide were detected.

[0295] This result also shows that at a concentration of about 21 pphl zeolite, the TAN was reduced at both 15°C and 50°C.

[0296] Example 21 The ability of an anion exchange resin acting as a blocking material was tested.

[0297] Two different anion exchange resins were tested.

[0298] The first resin The first resin was a strongly basic (type 1) anion exchange resin (Dowex® 1X8 chloride form) with chloride-exchangeable ions.

[0299] [Table 35]

[0300] The first resin was used without modification.

[0301] The second resin The second resin was a strongly basic (type 1) anion exchange resin (Dowex® 1X8 chloride form) with chloride-exchangeable ions.

[0302]

Table 36

[0303] The second resin was gently washed with 4% NaOH of 5 - 10 bed volumes for at least 1 hour before use in the following examples, and then washed with deionized water until the pH of the effluent became 7 ± 0.5, thereby converting it from the chloride form to the hydroxy form. The pH was measured using litmus test paper.

[0304] Method and Results A formulation of 80 wt% POE oil (POE ISO32, Emkarate RL 32 - 3MAF) containing about 1000 ppm of the primary antioxidant BHT and 20 wt% of CF3I was placed in a sealed tube and heated at 190 °C for 2 days. Under these conditions, the refrigerant and lubricant were destroyed. Then, the sealed tube was opened and a sample of the oil was taken out.

[0305] The sample was then placed in a Fischer - Porter tube together with an anion - exchange resin. The amount of dry resin relative to the sample was measured. Then, the tube was maintained at either 15 °C or 50 °C for 114 hours (4.75 days). The tube was shaken every 2 hours to ensure proper mixing of the resin and the sample.

[0306] The total acid number (TAN), iodide ppm, and fluoride ppm of the sample were measured at the start (i.e., after the decomposition of CF3I and POE oil and before combination with the resin), and at the end (i.e., after combination with the resin and at the end of 114 hours at 15 °C or 50 °C). The concentrations of TAN, fluoride, and iodide were measured according to the same method as in Example 10. The results are presented in Table 21 below.

[0307] The results are described in Table 21 below.

[0308]

Table 37

[0309] The above test demonstrates the ability of an anion exchange resin to effectively "restore" the composition of POE oil and CF3I refrigerant after it has decomposed.

[0310] This result demonstrates that when using either about 4 pphl zeolite or about 16 pphl resin, both resins were able to reduce the iodide and fluoride levels of the decomposed sample at both 15°C and 50°C. Both resins functioned better at 50°C than at 15°C, and about 16 pphl zeolite functioned better than about 4 pphl.

[0311] The second resin was able to reduce the TAN of the sample at both temperatures (i.e., 15°C and 50°C) and at both resin concentrations (i.e., about 4 pphl and about 16 pphl resin).

[0312] Example 22 Repeat Example 22 except that the following two anion resins were used: A - An industrial grade weak base anion exchange resin sold under the trade name Amberlyst A21 (free base) with the following characteristics:

[0313] [Table 38]

[0314] B - An industrial grade weak base anion exchange resin sold under the trade name Amberlyst A22 with the following characteristics:

[0315] [Table 39]

[0316] Each of these resins was found to be effective in removing and / or reducing the above materials.

[0317] Example 23 The ability of a combination of an anion exchange resin and zeolite acting as a blocking material was tested.

[0318] Anion exchange resin The resin was a strongly basic (type 1) anion exchange resin having hydroxide-exchangeable ions (Dowex® Marathon® A, hydroxide form).

[0319] [Table 40]

[0320] The resin was used without modification.

[0321] Zeolite The zeolite tested was UPO IONSIV D7310-C available from Honeywell UOP. The openings have sizes over their maximum dimensions of about 15 to about 35 Å.

[0322] Method and results A formulation of 80 wt% POE oil (POE ISO32, Emkarate RL 32-3MAF) containing about 1000 ppm of the primary antioxidant BHT and 20 wt% CF3I was placed in a sealed tube and heated at 175 °C for 2 days. Under these conditions, destruction of the refrigerant and lubricant occurred. The sealed tube was then opened and a sample of the oil (i.e., the lubricant) was removed.

[0323] The lubricant sample was then placed in a Fischer-Porter tube together with a combination of an anion exchange resin and zeolite. The amount of dry resin and zeolite relative to the sample was measured. The tube was then maintained at about 50 °C for 192 hours (8 days). The tube was shaken every 2 hours to ensure proper mixing of the resin and the sample.

[0324] The total acid number (TAN), iodide ppm, and fluoride ppm of the oil were measured at the start (i.e., after the decomposition of CF3I and POE oil and before the combination with the resin and zeolite), and at the end (i.e., after the combination with the resin and zeolite and at the end of 192 hours at 50 °C). The concentrations of TAN, fluoride, and iodide were measured according to the same method as in Example 1.

[0325] The results are presented in Table 23 below.

[0326]

Table 41

[0327] The above test demonstrates the ability of a combination of anion exchange resin and zeolite to effectively "restore" the composition of POE oil and CF3I refrigerant after it has decomposed. This result shows that when using different ratios of anion exchange resin and zeolite, both resins were able to reduce the iodide and fluoride levels of the decomposed sample at 50 °C. A zeolite to ion exchange weight of 25:75 showed the greatest reduction in the TAN of the sample and further showed the highest decrease in the iodide and fluoride content (ppm).

[0328] Example 24 The levels of fluoride and iodide removal and TAN reduction were studied as a function of the amount of zeolite in percentage of the heat transfer composition being treated.

[0329] The zeolite tested was UPO IONSIV D7310-C available from Honeywell UOP. The apertures have sizes ranging over their maximum dimensions from about 15 to about 35 Å.

[0330] A formulation of 80 wt% POE oil (POE ISO32, Emkarate RL 32 - 3MAF) containing the primary antioxidant BHT in an amount of about 1000 ppm and 20 wt% CF3I was placed in a sealed tube and heated at 175 °C for 2 days. Under these conditions, destruction of the refrigerant and lubricant occurred. Then, the sealed tube was opened and a sample of the oil was taken out.

[0331] Next, following the preceding paragraph, a portion of the lubricant sample produced after destruction was filled into five Parr cells, each of which had different amounts (by weight) of zeolite based on the weight of the lubricant placed in the cell. Then, the Parr cells were maintained at 50 °C and the materials in each cell were tested every 24 hours for 15 days. The Parr cells were shaken daily to ensure that the zeolite and lubricant were properly mixed.

[0332] The total acid number (TAN), iodide ppm, and fluoride ppm of the oil were measured at the start (i.e., after decomposition of CF3I and POE oil and before combination with zeolite), and every 24 hours over 15 days (i.e., after combination with zeolite at 50 °C). done.

[0333] The results of the test are presented in Table 5 below:

[0334]

Table 42

[0335] The above test demonstrates the ability of zeolite to effectively “restore” a composition of lubricant, a specific POE oil, and CF3I refrigerant after it has decomposed.

[0336] This result shows that an amount of zeolite exceeding 10 pphl is more effective in reducing the iodide level to the undetectable limit, and that an amount of zeolite material exceeding 5 pphl is more effective in reducing the fluoride level to the undetectable limit. This result also shows that an amount of zeolite exceeding 15 pphl is most effective in reducing TAN.

[0337] Example 25 - Preferred Ion Exchange Materials The ability of the industrial grade weak base anion exchange adsorbent resin Amberlyst A21 (free base), which acts as a blocking material, was tested. The weak base anion resin is in the free base form and is functionalized with a tertiary amine (uncharged). The tertiary amine contains a pair of free lone electrons on the nitrogen and is easily protonated in the presence of an acid. The ion exchange resin is protonated by the acid and then attracts and binds the counter ion of the anion in order to completely remove the acid without contributing to returning any additional species into the solution.

[0338] The Applicants have found that Amberlyst A21 is an excellent material for use according to the present invention. This material has a macroporous structure which is physically very stable and resistant to breakage in the method and system, and can withstand the high flow rates of the refrigeration system over its lifetime.

[0339] Example 26 The ability of the industrial grade weakly basic anion exchange adsorbent resin Amberlyst A21 (free base), which acts as a blocking material, was tested. The weakly basic anion resin is in the free base form and is functionalized by a tertiary amine (uncharged). The tertiary amine contains a pair of free lone electrons on the nitrogen and is easily protonated in the presence of an acid. The ion exchange resin is protonated by an acid and then attracts and binds the counterions of the anions to completely remove the acid without contributing to returning any additional species into the solution. The matrix of Amberlyst A21 is macroporous. Its macroporous structure is physically very stable and resistant to breakage. Also, it can withstand the high flow rate of the refrigeration system over its lifetime. An industrial grade weakly basic anion exchange resin sold under the trade name of Amberlyst A21 (free base) with the following properties:

[0340]

Table 43

[0341] A mixture of 80 wt% POE oil (POE ISO32, Emkarate RL 32-3MAF) containing about 1000 ppm of the primary antioxidant stabilizer BHT and 20 wt% CF3I was placed in a cylinder and heated at 175 °C for 2 days. Under these conditions, destruction of the refrigerant and lubricant occurred. Then the cylinder was opened and a sample of the oil was taken out.

[0342] The sample was then placed in a Parr cell together with Amberlyst A21. The amount of dry Amberlyst A21 relative to the sample was measured. The Parr cell was then maintained at either 50 °C for 20 days. The cell was shaken daily to ensure proper mixing of Amberlyst A21 and the sample.

[0343] The total acid number (TAN), iodide ppm, and fluoride ppm of the sample were measured at the start (i.e., after decomposition of CF3I and POE oil and before combination with Amberlyst A21), and at the end (i.e., after combination with Amberlyst A21). The concentrations of TAN, fluoride, and iodide were measured according to the methods described herein.

[0344] The results of the test are set forth in Table 26.

[0345]

Table 44

[0346] The above test demonstrates the ability of Amberlyst A21 to effectively "restore" the composition of POE oil and CF3I refrigerant after it has decomposed.

[0347] This result demonstrates that when using 30 wt% or more of Amberlyst A21, Amberlyst A21 was able to reduce the levels of iodide and fluoride below the detectable level of the decomposed sample at 50°C.

[0348] Example 27 The ability of the industrial grade weak base anion exchange adsorbent resin Amberl yst A22 (free base) acting as a blocking material was tested. The weak base anion resin is in the free base form and is functionalized by a tertiary amine (uncharged). The tertiary amine contains a pair of free lone electrons on the nitrogen and is easily protonated in the presence of an acid. The ion exchange resin is protonated by an acid and then attracts and binds the counter ion of the anion in order to completely remove the acid without contributing to returning any additional species into the solution. Its macroporous structure is physically very stable and resistant to breakage. Also, it can withstand the high flow rates of the refrigeration system over its lifetime. An industrial grade weak base anion exchange resin sold under the trade name Amberlyst A22 having the following properties:

[0349]

Table 45

[0350] A mixture of 80 wt% POE oil (POE ISO32, Emkarate RL 32 - 3MAF) containing primary antioxidant BHT in an amount of about 1000 ppm and 20 wt% CF3I was placed in a cylinder and heated at 175 °C for 2 days. Under these conditions, destruction of the refrigerant and lubricant occurred. Then, the cylinder was opened and a sample of the oil was taken out.

[0351] The sample was then placed in a Parr cell with Amberlyst A22. The amount of dry Amberlyst A22 relative to the sample was measured. The Parr cell was then maintained at either 50 °C for 20 days. The cell was shaken daily to ensure proper mixing of the Amberlyst A22 and the sample.

[0352] The total acid number (TAN), iodide ppm, and fluoride ppm of the sample were measured at the start (i.e., after decomposition of the CF3I and POE oil and before combination with Amberlyst A22) and at the end (i.e., after combination with Amberlyst A22). The concentrations of TAN, fluoride, and iodide were measured according to the methods described herein.

[0353] The results of the test are described in Table 27.

[0354]

Table 46

[0355] The above test demonstrates the ability of Amberlyst A22 to effectively "restore" the composition of the POE oil and CF3I refrigerant after it has decomposed.

[0356] This result demonstrates that when using 10 wt% and 30 wt% of Amberlyst A22, Amberlyst A22 was able to reduce the iodide and fluoride levels of the decomposed sample at 50 °C.

[0357] Example 28 The ability of the industrial grade weak base anion exchange adsorbent resin Amberlite IRA96, which acts as a blocking material, was tested. The weak base anion resin is in the free base form and is functionalized by a tertiary amine (uncharged). The tertiary amine contains a pair of free lone electrons on nitrogen and is easily protonated in the presence of an acid. The ion exchange resin is protonated by an acid and then attracts and binds the counter ion of the anion to completely remove the acid without contributing to returning any additional species into the solution. Its macroporous structure is physically very stable and resistant to breakage. Also, it can withstand the high flow rate of the refrigeration system over its lifetime. The high porosity of this resin enables efficient adsorption of large organic molecules. An industrial grade weak base anion exchange resin sold under the trade name Amberlite IRA96 with the following properties:

[0358] [Table 47]

[0359] A mixture of 80 wt% POE oil (POE ISO32, Emkarate RL 32 - 3MAF) containing about 1000 ppm of the primary antioxidant stabilizer BHT and 20 wt% of CF3I was placed in a cylinder and heated at 175 °C for 2 days. Under these conditions, destruction of the refrigerant and lubricant occurred. Then, the cylinder was opened and a sample of the oil was taken out.

[0360] Next, the sample was placed in a Parr cell together with Amberlite IRA96. The amount of dry Amberlite IRA96 relative to the sample was measured. The Parr cell was then maintained at either 50 °C for 20 days. The cell was shaken daily to ensure proper mixing of the Amberlite IRA96 and the sample.

[0361] The total acid number (TAN), iodide ppm, and fluoride ppm of the sample were measured at the start (i.e., after decomposition of CF3I and POE oil and before combination with Amberlite IRA96) and at the end (i.e., after combination with Amberlite IRA96). The concentrations of TAN, fluoride, and iodide were measured according to the methods described herein.

[0362] The results of the test are presented in Table 28.

[0363]

Table 48

[0364] The above test demonstrates the ability of Amberlite IRA96 to effectively "restore" the composition of POE oil and CF3I refrigerant after it has decomposed.

[0365] This result demonstrates that when using 30 wt% or more of Amberlite IRA96, Amberlite IRA96 was able to reduce the levels of iodide and fluoride below the detectable level of the decomposed sample at 50 °C.

[0366] Example 29 The ability of industrial grade activated alumina F200, which acts as a blocking material, was tested.

[0367] A mixture of 80 wt% POE oil (POE ISO32, Emkarate RL 32 - 3MAF) containing primary antioxidant stabilizer BHT in an amount of about 1000 ppm and 20 wt% CF3I was placed in a cylinder and heated at 175 °C for 2 days. Under these conditions, destruction of the refrigerant and lubricant occurred. Then, the cylinder was opened and a sample of the oil was taken out.

[0368] The sample was then placed in a Parr cell with industrial grade activated alumina F200. The amount of activated alumina relative to the sample was measured. The Parr cell was then maintained at either 50 °C for 20 days. The cell was shaken daily to ensure proper mixing of the sample.

[0369] The total acid number (TAN), iodide ppm, and fluoride ppm of the sample were measured at the start (i.e., after decomposition of CF3I and POE oil and before exposure to F200), and at the end (i.e., after exposure to F200). The concentrations of TAN, fluoride, and iodide were measured by the methods described herein.

[0370] The results of the test are presented in Table 29A.

[0371]

Table 49

[0372] Example 30 Amberlyst A21 and zeolite IONSIV D73 as blocking materials The ability of the 10 - C combination was tested.

[0373] A mixture of 80 wt% POE oil (POE ISO32, Emkarate RL 32 - 3MAF) containing primary antioxidant stabilizer BHT in an amount of about 1000 ppm and 20 wt% CF3I was placed in a cylinder and heated at 175 °C for 2 days. Under these conditions, destruction of the refrigerant and lubricant occurred. Then, the cylinder was opened and a sample of the oil was taken out.

[0374] Next, the sample was placed in a Parr cell together with the blocking material. The amount of the blocking material with respect to the sample was 20% by weight. Next, the Parr cell was maintained at either 50 °C for 20 days. The cell was shaken daily to ensure proper mixing of the sample.

[0375] The total acid number (TAN), iodide ppm, and fluoride ppm of the sample were measured at the start (i.e., after decomposition of CF3I and POE oil and before exposure to the blocking material) and at the end (i.e., after exposure to the blocking material). The concentrations of TAN, fluoride, and iodide were measured by the methods described herein. The results of the test are described in Table 30.

[0376]

Table 50

[0377] Although the present invention has been described with reference to preferred compositions, it will be understood by those skilled in the art that various changes can be made and equivalents can be substituted for its elements without departing from the scope of the present invention. Further, many modifications can be made to adapt the teachings of the present invention to a particular situation or material without departing from the essential scope thereof. Accordingly, the present invention is not intended to be limited to the particular compositions disclosed, but rather the present invention is intended to include all compositions included within the scope of the appended claims or any later added claims.

[0378] Numbered Embodiment 1 A refrigerant comprising at least about 97% by weight of the following three compounds, each compound being present in the following relative percentages: 39 - 45% by weight of difluoromethane (HFC - 32), 1 - 4% by weight of pentafluoroethane (HFC - 125), and 51 - 57% by weight of trifluoroiodomethane (CF3I).

[0379] Numbered Embodiment 2 The refrigerant of three compounds is about 41 to about 43% by weight of difluoromethane (HFC-32), 1 to 4% by weight of pentafluoroethane (HFC-125), and about 53 to about 56% by weight of trifluoroiodomethane (CF3I), the refrigerant according to numbered Embodiment 1.

[0380] Numbered Embodiment 3 The refrigerant of three compounds is 41% by weight ± 1% by weight of difluoromethane (HFC-32), 3.5% by weight ± 0.5% by weight of pentafluoroethane (HFC-125), and 55.5% by weight ± 0.5% by weight of trifluoroiodomethane (CF3I), the refrigerant according to numbered Embodiment 1.

[0381] Numbered Embodiment 4 The refrigerant of three compounds is 41% by weight of difluoromethane (HFC-32), 3.5% by weight of pentafluoroethane (HFC-125), and 55.5% by weight of trifluoroiodomethane (CF3I), the refrigerant according to numbered Embodiment 1.

[0382] Numbered Embodiment 5 The refrigerant contains at least about 98.5% by weight of the three compounds, the refrigerant according to numbered Embodiments 1 to 4.

[0383] Numbered Embodiment 6 The refrigerant contains at least about 99.5% by weight of the three compounds, the refrigerant according to numbered Embodiments 1 to 4.

[0384] Numbered Embodiment 7 39 to 45% by weight of difluoromethane (HFC-32) and 1 to 4% by weight of pentafluoroethane (HFC-125) and A refrigerant consisting essentially of 51 to 57% by weight of trifluoroiodomethane (CF3I).

[0385] Numbered Embodiment 8 About 41 to about 43% by weight of difluoromethane (HFC-32), 1 to 4% by weight of pentafluoroethane (HFC-125), The refrigerant according to claim 7, consisting essentially of about 53 to about 56% by weight of trifluoroiodomethane (CF3I).

[0386] Numbered Embodiment 9 41% by weight ± 1% by weight of difluoromethane (HFC-32), 3.5% by weight ± 0.5% by weight of pentafluoroethane (HFC-125), The refrigerant according to numbered Embodiment 7 or numbered Embodiment 8, consisting essentially of 55.5% by weight ± 0.5% by weight of trifluoroiodomethane (CF3I).

[0387] Numbered Embodiment 10 41% by weight of difluoromethane (HFC-32), 3.5% by weight of pentafluoroethane (HFC-125), The refrigerant according to numbered Embodiment 7 or numbered Embodiment 8, consisting essentially of 55.5% by weight of trifluoroiodomethane (CF3I).

[0388] Numbered Embodiment 11 39 to 45% by weight of difluoromethane (HFC-32), 1 to 4% by weight of pentafluoroethane (HFC-125), A refrigerant consisting of 51 to 57% by weight of trifluoroiodomethane (CF3I).

[0389] Numbered Embodiment 12 About 41 to about 43% by weight of difluoromethane (HFC-32), 1 to 4% by weight of pentafluoroethane (HFC-125), The refrigerant described in numbered Embodiment 11, consisting of about 53 to about 56% by weight of trifluoroiodomethane (CF3I).

[0390] Numbered Embodiment 13 41% by weight ± 1% by weight of difluoromethane (HFC-32), 3.5% by weight ± 0.5% by weight of pentafluoroethane (HFC-125), 55.5% by weight ± 0.5% by weight of trifluoroiodomethane (CF3I), the refrigerant described in numbered Embodiment 11 or numbered Embodiment 12.

[0391] Numbered Embodiment 14 41% by weight of difluoromethane (HFC-32), 3.5% by weight of pentafluoroethane (HFC-125), 55.5% by weight of trifluoroiodomethane (CF3I), the refrigerant described in numbered Embodiment 11 or numbered Embodiment 12.

[0392] Numbered Embodiment 15 A heat transfer composition containing the refrigerant of any one of numbered Embodiments 1 to 14.

[0393] Numbered Embodiment 16 The heat transfer composition according to numbered Embodiment 15, wherein the refrigerant constitutes more than 40% by weight of the composition.

[0394] Numbered Embodiment 17 The heat transfer composition according to numbered Embodiment 15, wherein the refrigerant constitutes more than 50% by weight of the composition.

[0395] Numbered Embodiment 18 The heat transfer composition according to numbered Embodiment 15, wherein the refrigerant constitutes more than 60% by weight of the composition.

[0396] Numbered Embodiment 19 The refrigerant constitutes more than 70% by weight of the composition, and is the heat transfer composition according to numbered embodiment 15.

[0397] Numbered embodiment 20 The refrigerant constitutes more than 80% by weight of the composition, and is the heat transfer composition according to numbered embodiment 15.

[0398] Numbered embodiment 21 The refrigerant constitutes more than 90% by weight of the composition, and is the heat transfer composition according to numbered embodiment 15.

[0399] Numbered embodiment 22 The heat transfer composition according to any one of numbered embodiments 15 to 21, further comprising an alkylated naphthalene stabilizer.

[0400] Numbered embodiment 23 The heat transfer composition according to any one of numbered embodiments 15 to 22, further comprising a stabilizer containing a phenolic compound.

[0401] Numbered embodiment 24 The heat transfer composition according to numbered embodiments 22 to 23, further comprising a stabilizer containing an epoxide.

[0402] Numbered embodiment 25 The phenolic compound is provided in the heat transfer composition in an amount greater than 0, preferably from 0.0001% to about 5% by weight, more preferably from 0.001% to about 2.5% by weight, and most preferably from 0.01% to about 1% by weight, according to any one of numbered embodiments 24.

[0403] Numbered embodiment 26 The phenolic compound is BHT, and the BHT is present in an amount of about 0.0001% to about 5% by weight based on the weight of the heat transfer composition, according to numbered embodiment 25.

[0404] Numbered Embodiment 27 The heat transfer composition according to numbered Embodiment 26, further comprising a lubricant selected from polyol esters (POE), mineral oils, and alkylbenzenes (AB).

[0405] Numbered Embodiment 28 The heat transfer composition according to numbered Embodiment 27, wherein the lubricant is a polyol ester (POE).

[0406] Numbered Embodiment 29 A cooling method in a heat transfer system comprising an evaporator, a condenser, and a compressor, the process comprising: i) condensing the heat transfer composition according to any one of numbered Embodiments 21 to 29; and ii) evaporating the composition in the vicinity of the body or article to be cooled, wherein the evaporator temperature of the heat transfer system is in the range of about -40°C to about -10°C.

[0407] Numbered Embodiment 30 A heating method in a heat transfer system comprising an evaporator, a condenser, and a compressor, the process comprising: i) condensing the heat transfer composition according to any one of numbered Embodiments 21 to 29 in the vicinity of the body or article to be heated; and ii) evaporating the composition, wherein the evaporator temperature of the heat transfer system is in the range of about -20°C to about 3°C.

[0408] Numbered Embodiment 31 A heating method in a heat transfer system comprising an evaporator, a condenser, and a compressor, the process comprising: i) condensing the heat transfer composition according to any one of numbered Embodiments 21 to 29 in the vicinity of the body or article to be heated; and ii) evaporating the composition, wherein the evaporator temperature of the heat transfer system is in the range of about -30°C to about 5°C.

[0409] Numbered Embodiment 32 A cooling method in a heat transfer system comprising an evaporator, a condenser, and a compressor, the process comprising: i) condensing a heat transfer composition according to any one of numbered embodiments 21 to 29; and ii) evaporating the composition in the vicinity of a body or article to be cooled, wherein the heat transfer system is a refrigeration system.

[0410] Numbered embodiment 33 The method according to numbered embodiment 32, wherein the refrigeration system is a low-temperature refrigeration system or a medium-temperature refrigeration system.

[0411] Numbered embodiment 34 The method according to numbered embodiment 33, wherein the refrigeration system is a low-temperature refrigeration system.

[0412] Numbered embodiment 35 The method according to numbered embodiment 33, wherein the refrigeration system is a medium-temperature refrigeration system.

[0413] Numbered embodiment 36 The method according to numbered embodiment 35, wherein the refrigeration system is a medium-temperature refrigeration system (having an evaporator temperature in the range of about -12 to about 0 °C, particularly about -8 °C).

[0414] Numbered embodiment 37 The method according to numbered embodiment 34, wherein the refrigeration system is a low-temperature refrigeration system (having an evaporator temperature in the range of about -40 to about -12 °C, particularly about -23 °C, or preferably -32 °C).

[0415] Numbered embodiment 38 A method of replacing an existing refrigerant contained in a heat transfer system, the method comprising removing at least a portion of the existing refrigerant, which is R-410a, from the system and replacing at least a portion of the existing refrigerant by introducing into the system a refrigerant according to any one of numbered embodiments 1 to 14 or a heat transfer composition according to any one of numbered embodiments 21 to 29.

[0416] Numbered Embodiment 39 The method according to numbered Embodiment 38, wherein a portion of the existing R410A refrigerant is at least about 5% by weight of the R410A from the system.

[0417] Numbered Embodiment 40 The method according to numbered Embodiment 38, wherein a portion of the existing R-410A refrigerant is at least about 50% by weight of the R-410A from the system.

[0418] Numbered Embodiment 41 The method according to numbered Embodiment 38, wherein a portion of the existing R-410A refrigerant is about 100% by weight of the R-410A from the system.

[0419] Numbered Embodiment 42 Use of the refrigerant according to any one of numbered Embodiments 1 to 14 in an air conditioning system.

[0420] Numbered Embodiment 43 The use according to numbered Embodiment 42, wherein the air conditioning system is a residential air conditioning system.

[0421] Numbered Embodiment 44 The use according to numbered Embodiment 42, wherein the air conditioning system is a residential heat pump.

[0422] Numbered Embodiment 45 The use according to numbered Embodiment 58, wherein the air conditioning system is a chiller.

[0423] Numbered Embodiment 46 The refrigerant is (a) having a COP that matches or exceeds the efficiency of R410A, (b) having a capacity exceeding 90% of the capacity of R410A, the refrigerant according to any one of numbered Embodiments 1 to 14.

[0424] Numbered Embodiment 47 The refrigerant provided to replace the R410A refrigerant in the system, the refrigerant according to the numbered Embodiment 46.

[0425] Numbered Embodiment 48 In a heat transfer system in which the refrigerant is used to replace the R-410A refrigerant, the refrigerant according to the numbered Embodiment 47, having a discharge temperature not higher than 10 °C higher than that of R-410A.

[0426] Numbered Embodiment 49 In a heat transfer system in which the refrigerant is used to replace the R-410A refrigerant, the refrigerant according to the numbered Embodiment 48, having a compressor pressure ratio of 95-105% of the compressor pressure ratio of R-410A.

[0427] Numbered Embodiment 50 The refrigerant according to any one of the numbered Embodiments 1-14 or 46-49, having a GWP of 427 or less over a period of 100 years.

[0428] Numbered Embodiment 51 The refrigerant according to any one of the numbered Embodiments 1-14 or 46-49, being non-flammable when determined according to the non-flammability test.

[0429] Numbered Embodiment 52 The refrigerant described in any one of numbered embodiments 1 to 14 or 46 to 49, which is non-flammable when determined in accordance with ASTM Standard E-681-2009, Standard Test Method for Concentration Limits of Flammability of Chemicals (Vapors and Gases), under the conditions described in ASHRAE Standard 34-2016, Designation and Safety Classification of Refrigerants, and Appendix B1 of ASHRAE Standard 34-2016. The present invention includes the following aspects. [1] A refrigerant comprising at least about 97% by weight of the following three compounds, each compound being present in the following relative percentages: Refrigerant 39 - 45% by weight of difluoromethane (HFC-32), 1 - 4% by weight of pentafluoroethane (HFC-125), and 51 - 57% by weight of trifluoroiodomethane (CF 3 I)。 [2] The refrigerant according to [1], comprising at least about 99.5% by weight of the following three compounds, each compound being present in the following relative percentages: 39 - 45% by weight of difluoromethane (HFC-32), 1 - 4% by weight of pentafluoroethane (HFC-125), and 51 - 57% by weight of trifluoroiodomethane (CF 3 I)。 [3] The refrigerant according to [1], consisting of the following three compounds, each compound being present in the following relative percentages: 39 - 45% by weight of difluoromethane (HFC-32), 1 - 4% by weight of pentafluoroethane (HFC-125), and 51 - 57% by weight of trifluoroiodomethane (CF 3 I)。 [4] A refrigerant comprising at least about 97% by weight of the following three compounds, each compound being present in the following relative percentages: Refrigerant About 41 - about 43% by weight of difluoromethane (HFC-32), 1 - 4% by weight of pentafluoroethane (HFC-125), and About 53 - about 56% by weight of trifluoroiodomethane (CF 3 I)。 [5] The refrigerant according to [4], comprising at least about 99.5% by weight of the following three compounds, each compound being present in the following relative percentages: About 41 - about 43% by weight of difluoromethane (HFC-32), 1 - 4% by weight of pentafluoroethane (HFC-125), and About 53 - about 56% by weight of trifluoroiodomethane (CF 3 I)。 [6] A refrigerant consisting essentially of the following three compounds, each compound being present in the following relative percentages: Refrigerant 41% by weight ± 1% of difluoromethane (HFC-32), 3.5% by weight ± 0.5% of pentafluoroethane (HFC-125), and 55.5% by weight ± 0.5% of trifluoroiodomethane (CF 3 I)。 [7] The refrigerant according to [6], consisting of the following three compounds, each compound being present in the following relative percentages: 41% by weight ± 1% of difluoromethane (HFC-32), 3.5% by weight ± 0.5% of pentafluoroethane (HFC-125), and 55.5% by weight ± 0.5% of trifluoroiodomethane (CF 3 I)。 [8] The refrigerant described in [6], consisting essentially of the following three compounds, with each compound present in the following relative percentages: 41% by weight of difluoromethane (HFC-32), 3.5% by weight of pentafluoroethane (HFC-125), and 55.5% by weight of trifluoroiodomethane (CF 3 I)。 [9] A heat transfer composition containing the refrigerant described in [1].

[10] The heat transfer composition described in [9], further comprising alkylated naphthalene.

[11] The heat transfer composition described in

[10] , further comprising BHT in an amount of about 0.0001% to about 5% by weight of the heat transfer composition.

[12] The heat transfer composition described in

[11] , further comprising a lubricant selected from polyol ester (POE), polyvinyl ether (PVE), mineral oil, and alkylbenzene (AB).

[13] The heat transfer composition described in

[12] , wherein the lubricant is polyol ester (POE).

[14] The heat transfer composition described in

[12] , wherein the lubricant is PVE. ■

[15] A cooling method in a heat transfer system comprising an evaporator, a condenser, and a compressor, the process comprising: i) a step of condensing the refrigerant described in [1]; and ii) a step of evaporating the refrigerant in the vicinity of the body or article to be cooled, wherein the temperature of the refrigerant in the evaporator is in the range of about -40°C to about -10°C.

Claims

1. A refrigerant comprising the following three compounds, wherein each compound is present in the following relative percentages: Refrigerant: 41% by weight ± 1% by weight of difluoromethane (HFC-32), 3.5% by weight ± 0.5% by weight of pentafluoroethane (HFC-125), and 55.5 wt% ± 0.5 wt% trifluoroiodomethane (CF ３ I).

2. The refrigerant according to claim 1, comprising the following three compounds, wherein each compound is present in the following relative percentages: 41% by weight ± 0.3% by weight of difluoromethane (HFC-32), 3.5% by weight ± 0.3% by weight of pentafluoroethane (HFC-125), and 55.5 wt% ± 0.3 wt% trifluoroiodomethane (CF ３ I).

3. The refrigerant according to claim 1, comprising the following three compounds, wherein each compound is present in the following relative percentages: 41% by weight of difluoromethane (HFC-32), 3.5% by weight of pentafluoroethane (HFC-125), and 55.5 wt% trifluoroiodomethane (CF ３ I).

4. A heat transfer composition comprising the refrigerant according to any one of claims 1 to 3.

5. The heat transfer composition according to claim 4, further comprising a lubricant selected from polyol ester (POE), polyvinyl ether (PVE), mineral oil, and alkylbenzene (AB).

6. The heat transfer composition according to claim 5, wherein the lubricant is polyol ester (POE).

7. The heat transfer composition according to claim 5, wherein the lubricant is polyvinyl ether (PVE). ■

8. The heat transfer composition according to claim 4, further comprising alkylated naphthalene.

9. The heat transfer composition according to claim 8, wherein the alkylated naphthalene is present in an amount of 0.1% to 20% by weight based on the total weight of the alkylated naphthalene and the lubricant in the heat transfer composition.

10. The heat transfer composition according to claim 9, further comprising BHT in an amount of 0.0001% to 5% by weight of the heat transfer composition.

11. The heat transfer composition according to claim 4, wherein the alkylated naphthalene is present in an amount of 0.1% to 20% by weight based on the total weight of the alkylated naphthalene and the lubricant in the heat transfer composition, and further comprising a polyol ester (POE) lubricant.

12. The heat transfer composition according to claim 4, wherein the alkylated naphthalene is present in an amount of 0.1% to 20% by weight based on the total weight of the alkylated naphthalene and the lubricant in the heat transfer composition, and further comprising a polyvinyl ether (PVE) lubricant.

13. The heat transfer composition according to claim 11 or 12, wherein the refrigerant consists of the following three compounds and each compound is present in the following relative percentages: 41% by weight of difluoromethane (HFC-32), 3.5% by weight of pentafluoroethane (HFC-125), and 55.5 wt% trifluoroiodomethane (CF ３ I).

14. A cooling method in a heat transfer system comprising an evaporator, a condenser, and a compressor, the process comprising: i) condensing the refrigerant according to any one of claims 1 to 3; and ii) evaporating the refrigerant near the body or article to be cooled, wherein the temperature of the refrigerant in the evaporator is in the range of about -40°C to about +10°C.

15. A method for replacing an existing refrigerant contained in a heat transfer system, the method comprising removing at least a portion of the existing refrigerant, which is R-410a, from the system and introducing into the system the refrigerant according to any one of claims 1 to 3 or the heat transfer composition according to any one of claims 4 to 13 to replace at least a portion of the existing refrigerant.

16. A heat transfer system comprising a fluidly connected compressor, evaporator, and condenser and the heat transfer composition according to any one of claims 4 to 13.

17. Use of the heat transfer composition according to any one of claims 4 to 13 in a cooler, or a stationary air conditioner, or commercial cooling, or a heat pump.

18. Use of the heat transfer composition according to claim 17 in a commercial air conditioner.

19. Use of the heat transfer composition according to claim 17 in a residential air conditioner.

20. Use of the heat transfer composition according to claim 17 in an air-cooled cooler.

21. Use of the heat transfer composition according to claim 17 in a positive displacement cooler.

22. Use of the heat transfer composition according to claim 17 in a water-cooled direct expansion cooler.

23. Use of the heat transfer composition according to claim 17 in a commercial refrigerator.

24. Use of the heat transfer composition according to claim 17 in a commercial freezer.

25. Use of the heat transfer composition according to claim 17 in a vending machine.

26. Use of the heat transfer composition according to claim 17 in a residential heat pump.

27. Use of the heat transfer composition according to claim 17 in a mobile heat pump.

Images